CN110643898B - Wear-resistant corrosion-resistant nonmagnetic alloy material and preparation method thereof - Google Patents

Wear-resistant corrosion-resistant nonmagnetic alloy material and preparation method thereof Download PDF

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CN110643898B
CN110643898B CN201910977189.2A CN201910977189A CN110643898B CN 110643898 B CN110643898 B CN 110643898B CN 201910977189 A CN201910977189 A CN 201910977189A CN 110643898 B CN110643898 B CN 110643898B
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许晓嫦
宁兆祥
谭騛
宁晋奎
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Central South University
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • 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
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Abstract

The invention provides a wear-resistant corrosion-resistant nonmagnetic alloy material which comprises the following chemical elements in percentage by mass: 1.1-1.5% of carbon, 0.2-1.4% of silicon, 0.4-1.2% of manganese, 26-32% of chromium, 6.0-15.0% of nickel, 0.7-2.0% of copper, 2.5-5.0% of molybdenum, 0.1-0.9% of tungsten, 0-0.1% of phosphorus, 0-0.1% of sulfur, 0.01-0.1% of titanium, 0.1-0.3% of vanadium, 0.01-0.1% of niobium, 0.01-0.1% of cerium and the balance of iron. The material is non-magnetic, has high wear resistance, high temperature resistance and scouring resistance, and has super-strong corrosion resistance in sulfuric acid, hydrochloric acid and hydrofluoric acid environments. The invention has reasonable raw material formula and simple process, and can be widely applied to industries with strong acidity, alkalinity and serious solid scour, such as chemical industry, flue gas desulfurization devices, metallurgy and the like.

Description

Wear-resistant corrosion-resistant nonmagnetic alloy material and preparation method thereof
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a wear-resistant corrosion-resistant nonmagnetic alloy material and a preparation method thereof.
Background
At present, slurry pump materials used in the fields of mines, metallurgy, petroleum, chemical industry, ocean exploration and the like all face the phenomenon of serious corrosive wear and reduction of service life. Corrosive media such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and the like generated in flue gas desulfurization devices and the like in phosphoric acid and sulfuric acid industries and thermal power generation and severe two-phase fluid transportation industries have strong corrosive effects on slurry pumps, and meanwhile, a large amount of solid particles are usually carried in service environments. In the service process of the material, the material is corroded by a corrosive medium and simultaneously faces the scouring and wearing action of solid particles, so that the service life of the material is greatly shortened.
The materials of slurry pump used for manufacturing and transporting solid-liquid two-phase fluid industry in China mainly comprise high-chromium cast iron materials and cast steel materials. However, high-chromium cast iron materials (such as Cr15Mo3 and Cr26) are increasingly unable to meet production requirements, and the materials have good wear resistance and poor corrosion resistance, especially acid corrosion resistance. The acid corrosion resistance of cast steel materials (such as 316L, ZG40Cr25Ni20Si2) is high, but the hardness is relatively low, and the wear resistance of the cast steel materials cannot meet the performance requirements of special service environments. The existing materials have the current situation that the wear resistance and the corrosion resistance can not be matched with the service environment, so that the service life of equipment is greatly reduced, and even serious accidents occur in the service process. Therefore, the research on the materials for slurry pumps plays an important role in the industries.
At present, a plurality of related documents refer to the research of wear-resistant and corrosion-resistant materials, mainly refer to materials such as A49, Cr30A, ZG40CrNi20Si2 and the like, and the materials have own defects
1) A49: the as-cast hardness is about 40HRC, the material has high brittleness, and the material is easy to crack in the casting, heat treatment and processing processes and has magnetism.
2) Cr 30A: the fluidity of the material is low and the castability is poor. Shrinkage cavity, shrinkage porosity and casting cracks are easy to occur during casting.
3) ZG40Cr25Ni20Si 2: low high-temperature strength, low as-cast hardness (about 25 HRC), poor fatigue resistance, easy deformation and poor wear resistance.
In addition, the chinese invention patent CN103952616A discloses a preparation method of corrosion-resistant and wear-resistant alloy cast iron, which comprises the following elements by weight percent: 0.6 to 1.5 parts of carbon, 0.05 to 0.3 part of boron, 30 to 40 parts of chromium, 20 to 35 parts of nickel, 0.05 to 1 part of niobium, 3 to 6 parts of molybdenum, 1 to 3 parts of copper, 2 to 4 parts of tungsten, 0.1 to 0.3 part of titanium and the balance of iron.
The method is mainly characterized in that the content of alloy elements and a heat treatment process (air cooling for 3 hours at 1000-1150 ℃) are adjusted to improve the material performance.
The invention of Chinese patent CN106756496A discloses a novel corrosion-resistant, wear-resistant and high-temperature-resistant alloy material, which comprises the following components in percentage by weight: 0.05 to 0.1 percent of boron; 1.0 to 1.5 carbon; 0.5 to 1.0% of silicon; 0.05 to 0.1 of phosphorus; 0.05 to 0.1 percent of sulfur; 30-35% of chromium; 3-6 parts of manganese; 0.05-0.1 of cobalt; 2-4 parts of nickel; 1.0-1.5% of molybdenum; 0.5 to 1.5 of copper; 1.0-1.5% of titanium; the balance being iron.
The erosion and corrosion resistance of the material can not meet the requirement due to the difference of certain single factors such as corrosion resistance, wear resistance and the like, so that the requirement can not be met in an extreme environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a wear-resistant corrosion-resistant nonmagnetic alloy material with high chromium cast iron hardness and acid corrosion resistance even higher than that of materials such as 316L, ZG40Cr25Ni20Si2 and the like and a preparation method thereof. The alloy material can improve the current working condition of some special service environments.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a wear-resistant corrosion-resistant nonmagnetic alloy material which comprises the following components in percentage by mass:
1.1-1.5% of carbon, 0.2-1.4% of silicon, 0.4-1.2% of manganese, 26-32% of chromium, 6.0-15.0% of nickel, 0.7-2.0% of copper, 2.5-5.0% of molybdenum, 0.1-0.9% of tungsten, 0-0.1% of phosphorus, 0-0.1% of sulfur, 0.01-0.1% of titanium, 0.1-0.3% of vanadium, 0.01-0.1% of niobium, 0.01-0.1% of cerium and the balance of iron.
In a preferred scheme, the wear-resistant corrosion-resistant nonmagnetic alloy material comprises the following components in percentage by mass:
1.1-1.5% of carbon, 0.2-1.4% of silicon, 0.4-0.9% of manganese, 29-31% of chromium, 9-12.0% of nickel, 1.0-2.0% of copper, 3.4-3.7% of molybdenum, 0.2-0.9% of tungsten, 0.016-0.019% of phosphorus, 0.021-0.025% of sulfur, 0.03-0.1% of titanium, 0.2-0.28% of vanadium, 0.04-0.09% of niobium, 0.05-0.1% of cerium and the balance of iron.
Preferably, the wear-resistant and corrosion-resistant nonmagnetic alloy material comprises the following components in percentage by mass:
1.3-1.5% of carbon, 0.5-1.4% of silicon, 0.4-0.9% of manganese, 29-31% of chromium, 9-10.0% of nickel, 1.0-2.0% of copper, 3.6-3.7% of molybdenum, 0.5-0.9% of tungsten, 0.016-0.018% of phosphorus, 0.021-0.025% of sulfur, 0.03-0.1% of titanium, 0.2-0.28% of vanadium, 0.04-0.0.09% of niobium, 0.05-0.07% of cerium and the balance of iron.
In a preferred scheme, the microstructure of the wear-resistant corrosion-resistant nonmagnetic alloy material is as follows: austenite + M23C6 carbide.
The inventor finds that the collocation of the microstructure can effectively reduce the corrosion potential difference and reduce the driving force of corrosion reaction.
The invention relates to a preparation method of a wear-resistant corrosion-resistant nonmagnetic alloy material, which comprises the following steps: carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium and pure niobium are smelted according to the material component ratio, and the temperature of molten iron is controlled to be 1620-1650 ℃ in the smelting process; and after the raw materials are completely melted, sequentially carrying out pre-deoxidation, desulfurization and deoxidation treatment, discharging molten iron when the temperature of the molten iron is reduced to 1600 ℃ or below, then casting and molding the molten iron to obtain a casting, and annealing the casting to obtain the wear-resistant corrosion-resistant nonmagnetic alloy material.
In the preferred scheme, ferromanganese is adopted for pre-deoxidation treatment after the raw materials are completely melted.
In the preferable scheme, the temperature of molten iron is controlled to be 1620-1640 ℃ during desulfurization.
The desulfurizing agent is prepared from lime: the calcium carbide is obtained by mixing according to the mass ratio of 1: 3.
In the actual operation process, a two-way ladle shaking process is adopted to carry out desulfurization, deoxidation and other treatments on purified iron liquid. And then discharging the molten iron when the temperature of the molten iron is reduced to 1600 ℃, and carrying out component detection control and modification treatment before discharging.
In the preferable scheme, the pouring temperature is 1530-1560 ℃.
In the actual operation process, the iron liquid is subjected to slag skimming before casting, and then the iron liquid is placed in a shaking ladle for 3 minutes and then the casting is started.
In the preferred scheme, the periphery of the material is wrapped by carbon powder in the annealing process.
As a further preference, the annealing procedure is: heating to 900-980 ℃ at a speed of 3-7 ℃/min, preserving heat for 1.5-2 h, then cooling to 820-840 ℃ along with the furnace, preserving heat for 1.5-2 h, then cooling to 630-680 ℃ along with the furnace, preserving heat for 3-5 h, and then cooling to room temperature along with the furnace.
The annealing process of the invention carries out heat treatment on the material in a slow heating way, and the periphery of the material is wrapped by carbon powder, thereby preventing the decarburization phenomenon in the heating process.
The annealing process adopts gradient cooling during cooling, and the inventor finds that the impact toughness, hardness and wear resistance of the material can be further improved by adopting the process, firstly, secondary net-shaped carbide is dissolved into an austenite matrix in the heat preservation process in the temperature rise stage, the carbide at the grain boundary is reduced as much as possible, the impact toughness is improved, and then the carbide can be precipitated from the matrix in a granular form as much as possible through multi-pass heat preservation in the temperature reduction process, so that the hardness and wear resistance of the material are improved.
In the annealing process, the annealing temperature needs to be controlled in a limited way, if the annealing temperature is too high, the carbide precipitation driving force is small, and the resistance in the precipitation process is large; the annealing temperature is too low, and the diffusion resistance of atoms such as carbon, chromium and the like is large.
Advantages and attainments of the invention
The wear-resistant corrosion-resistant nonmagnetic alloy provided by the invention has the advantages that the microstructure of the alloy is controlled to be austenite + M23C6 carbide through the combination of components and the process, and the inventor finds that the collocation of the microstructure can effectively reduce the corrosion potential difference and reduce the driving force of corrosion reaction; meanwhile, the corrosion potential of the austenite matrix is improved by adding the content of the Ni element, and the corrosion potential difference is further reduced.
Specifically, in the invention, carbon is a main element for improving the wear resistance and hardness of the material, and the content of C is properly increased, so that the content of carbide is properly increased, the mechanical property of a matrix is improved, and the wear resistance of the material is greatly improved.
Chromium is a main element for improving the corrosion resistance of the material, and can quickly form an oxide film in a corrosive environment to prevent corrosive ions from contacting with a metal matrix to be damaged. Cr element can improve the corrosion resistance of the material, mainly improves the passivation effect of a surface passivation film, when the content is more than 13%, the corrosion resistance of the material is greatly improved, and when the content reaches a certain value, the passivation effect is increased gradually. However, when the high corrosion resistance of the material reaches the peak value under the action of chromium content, the corrosion potential difference between the matrix structure and the carbide is reduced by changing the type of the collocation of the microstructure of the metal under the passivation film, and the rate of the galvanic cell reaction of the matrix structure of the material is slowed down, so that the corrosion resistance of the material is improved.
Molybdenum mainly improves the corrosion resistance of the material, promotes the passivation of chromium element, and improves the self-repairing capability of the passivation film.
The nickel is a main element for adjusting the matrix structure of the material to obtain austenite, and the material with high strength, good toughness and no magnetism is obtained by adding the nickel element, so that the point corrosion position of the matrix structure is improved, and the wear resistance and corrosion resistance of the material can be improved by matching with the chromium element.
Tungsten mainly improves the wear resistance of the material, forms carbide with carbon in the material, improves the hardness index of the material, and can promote the formation of the carbide. The wear resistance of the material is improved.
Vanadium, titanium, niobium, cerium: in the invention, the carbon forms carbide to promote secondary hardening and improve the wear resistance of the material; meanwhile, the corrosion potential difference of the surface matrix of the material and the passivation film is reduced by the combined action of the elements such as titanium, vanadium, niobium, cerium, Ni, Mo, Cu and the like, and the corrosion resistance of the material is further improved.
In summary: according to the invention, through reasonably regulating and controlling the content of alloy elements, the wear resistance is improved and the corrosion resistance in an extreme acid environment is improved; the method is mainly used for scouring corrosion abrasion in an extreme acid environment and serious abrasion, and is carried out under the action of carbon powder in the annealing process to prevent the decarburization phenomenon in the temperature rise process, and simultaneously, the refining of matrix crystal materials and the precipitation of more granular carbides are obtained by combining element components through the annealing process.
The alloy material provided by the invention has the hardness of 40-45 HRC. The erosion corrosion resistance of the material under strong corrosive wear environment such as phosphoric acid industry and sulfuric acid industry is 47.72 times, 3.43 times and 3.17 times of that of materials such as Cr26, 316L, ZG40Cr25Ni20Si2 and the like. Meanwhile, the invention has the advantages of simple process, convenient operation and low cost. The method is particularly suitable for industries with particularly strict requirements on corrosion, corrosive wear, non-magnetism and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the wear-resistant and corrosion-resistant nonmagnetic alloy material obtained in example 1 under different magnification.
FIG. 2 is an XRD spectrum of the wear-resistant and corrosion-resistant nonmagnetic alloy material obtained in example 1.
Detailed Description
Example 1
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.1% of carbon, 0.2% of silicon, 0.7% of manganese, 30% of chromium, 12% of nickel, 1.2% of copper, 3.4% of molybdenum, 0.2% of tungsten, 0.019% of phosphorus, 0.023% of sulfur, 0.08% of titanium, 0.27% of vanadium, 0.09% of niobium, 0.1% of cerium and the balance of iron.
The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, a casting is subjected to three times of annealing treatment in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 980 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, then the material is cooled to 830 ℃ along with the furnace, the temperature is kept for 2h, then the material is cooled to 650 ℃ along with the furnace, the temperature is kept for 4h, and then the material is cooled to room temperature. Obtaining the wear-resistant corrosion-resistant nonmagnetic alloy material.
1) Hardness index: 22 to 27HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.223 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.098 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the etching rate was 3.634 mm/y.
FIG. 1 is a scanning electron microscope image of the wear-resistant and corrosion-resistant nonmagnetic alloy material obtained in example 1 under different magnification. As can be seen from the figure, the microstructure of the application material consists of a matrix, a eutectic structure and a small amount of grain boundary carbides; in combination with FIG. 2(XRD pattern), it can be seen that the matrix is austenite structure, and the eutectic structure is (austenite + M)23C6) And the carbide type at the grain boundary is M23C6。
Example 2
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.016% of phosphorus, 0.022% of sulfur, 0.1% of titanium, 0.28% of vanadium, 0.09% of niobium, 0.07% of cerium and the balance of iron. Through tests, the performance indexes of the alloy material produced by the invention are as follows:
the preparation procedure was the same as in example 1:
1) hardness index: 40-45 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.271 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.219 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 2.25 mm/y;
example 3
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.5% of carbon, 1.4% of silicon, 0.4% of manganese, 31% of chromium, 9% of nickel, 1.0% of copper, 3.7% of molybdenum, 0.9% of tungsten, 0.016% of phosphorus, 0.025% of sulfur, 0.03% of titanium, 0.2% of vanadium, 0.04% of niobium, 0.05% of cerium and the balance of iron.
The preparation procedure was the same as in example 1:
1) hardness index: 42-47 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.378 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 2.274 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 3.483. mm/y;
example 4
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.018% of phosphorus, 0.021% of sulfur, 0.09% of titanium, 0.25% of vanadium, 0.08% of niobium, 0.1% of cerium and the balance of iron.
The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 980 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, then the material is cooled to 840 ℃ along with the furnace, the temperature is kept for 2h, then the material is cooled to 680 ℃ along with the furnace, the temperature is kept for 4h, and then the material is cooled to room temperature. Obtaining the wear-resistant corrosion-resistant nonmagnetic alloy material.
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 40-42 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.263 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.188 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 3.184 mm/y;
example 5
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.018% of phosphorus, 0.022% of sulfur, 0.08% of titanium, 0.28% of vanadium, 0.07% of niobium, 0.08% of cerium and the balance iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 900 ℃ at the speed of 5 ℃/min, the material is kept warm for 2h, then the material is cooled to 820 ℃ along with the furnace, the temperature is kept for 2h, the material is cooled to 630 ℃ and kept warm for 4h, and then the material is cooled to room temperature
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 41-43 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.284 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.268 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 2.878 mm/y;
comparative example 1
1.38% of carbon, 1.3% of silicon, 0.8% of manganese, 30.5% of chromium, 9.8% of nickel, 1.3% of copper, 3.62% of molybdenum, 0.7% of tungsten, 0.02% of phosphorus, 0.023% of sulfur, 0.07% of titanium, 0.1% of vanadium, 0.04% of niobium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, performing three times of annealing treatment on a casting in a heat treatment furnace, wherein in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 980 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, then the material is cooled to 830 ℃ along with the furnace, the temperature is kept for 2h, then the material is cooled to 650 ℃ along with the furnace, the temperature is kept for 4h, and then the material is cooled to room temperature to obtain the wear-resistant corrosion-resistant nonmagnetic alloy material.
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 37-42 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.407 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 2.012 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate was 5.237 mm/y.
Comparative example 2
1.31% of carbon, 0.7% of silicon, 0.5% of manganese, 29% of chromium, 9.2% of nickel, 1.1% of copper, 3.65% of molybdenum, 0.5% of tungsten, 0.017% of phosphorus, 0.024% of sulfur and the balance of iron.
The preparation procedure was the same as in comparative example 1.
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 33-36 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.343 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.625 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 5.85 mm/y;
comparative example 3
1.31% of carbon, 0.6% of silicon, 0.5% of manganese, 29.7% of chromium, 9.3% of nickel, 0.017% of phosphorus, 0.022% of sulfur, 0.09% of titanium, 0.26% of vanadium, 0.08% of niobium, 0.05% of cerium and the balance of iron. The preparation process is the same as that of comparative example 1:
through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 30 to 36HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 2.043 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 4.625 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 10.42 mm/y;
comparative example 4
1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.018% of phosphorus, 0.022% of sulfur, 0.09% of titanium, 0.26% of vanadium, 0.08% of niobium, 0.05% of cerium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 850 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, then the material is cooled to 780 ℃ along with the furnace, the temperature is kept for 2h, then the furnace is cooled to 580 ℃ and the temperature is kept for 4h, and then the furnace is cooled to room temperature
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 37 to 41HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.324 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.618 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 4.878 mm/y;
comparative example 5
1.31 percent of carbon, 0.5 percent of silicon, 0.9 percent of manganese, 29.3 percent of chromium, 10.0 percent of nickel, 2.0 percent of copper, 3.64 percent of molybdenum, 0.016 percent of phosphorus, 0.021 percent of sulfur, 0.09 percent of titanium, 0.24 percent of vanadium, 0.09 percent of niobium, 0.05 percent of cerium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 1050 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, then the material is cooled to 900 ℃ along with the furnace, the temperature is kept for 2h, the furnace is cooled to 720 ℃, the temperature is kept for 4h, and then the furnace is cooled to room temperature
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 34-38 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.284 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.335 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 4.036 mm/y;
comparative example 6
1.34 percent of carbon, 0.6 percent of silicon, 0.7 percent of manganese, 29.8 percent of chromium, 9.6 percent of nickel, 1.8 percent of copper, 3.61 percent of molybdenum, 0.019 percent of phosphorus, 0.025 percent of sulfur, 0.06 percent of titanium, 0.19 percent of vanadium, 0.07 percent of niobium, 0.06 percent of cerium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is not protected, the temperature is raised to 980 ℃ at the speed of 5 ℃/min, the temperature is preserved for 2h, then the material is cooled to 830 ℃ along with the furnace, the temperature is preserved for 2h, then the furnace is cooled to 650 ℃ and the temperature is preserved for 4h, and then the furnace is cooled to room temperature
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 29 to 35HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.294 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.443 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 4.92 mm/y;
comparative example 7
1.37% of carbon, 0.8% of silicon, 0.6% of manganese, 29.3% of chromium, 9.7% of nickel, 1.5% of copper, 3.6% of molybdenum, 0.5% of tungsten, 0.021% of phosphorus, 0.023% of sulfur, 0.07% of titanium, 0.16% of vanadium, 0.05% of niobium, 0.07% of cerium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 980 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, and then the material is cooled to room temperature along with the furnace
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 29 to 33HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.314 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.765 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 7.24 mm/y;
comparative example 8
1.38% of carbon, 0.9% of silicon, 0.8% of manganese, 29.6% of chromium, 9.67% of nickel, 1.7% of copper, 3.68% of molybdenum, 0.019% of phosphorus, 0.025% of sulfur, 0.07% of titanium, 0.23% of vanadium, 0.07% of niobium, 0.08% of cerium and the balance of iron. The preparation process comprises the following steps:
(1) smelting: adding carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium, pure niobium and other charging materials into a medium-frequency induction furnace in sequence according to the material component ratio, controlling the temperature of molten iron at 1650 ℃, and adding part of ferromanganese for pre-deoxidation treatment when the materials are completely melted.
(2) Discharging: when the temperature of molten iron is controlled to be about 1630 ℃, lime is adopted: the mixture with the calcium carbide ratio of 1:3 is used as a desulfurizer, the mixture is discharged when the temperature reaches 1600 ℃, and component detection control and modification treatment are carried out before the mixture is discharged.
(3) Pouring: the liquid iron is subjected to slagging-off treatment before casting, and casting is started after 3 minutes of sedation, wherein the casting temperature is 1560 ℃.
(4) And (3) heat treatment: after casting forming, the casting is annealed for three times in a heat treatment furnace, in the treatment process, the periphery of the material is wrapped by carbon powder, the temperature is raised to 980 ℃ at the speed of 10 ℃/min, the temperature is preserved for 2h, then the material is cooled to 830 ℃ along with the furnace, the temperature is preserved for 2h, then the furnace is cooled to 650 ℃ and the temperature is preserved for 4h, and then the furnace is cooled to room temperature
Through tests, the performance indexes of the alloy material produced by the invention are as follows:
1) hardness index: 29 to 35HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.294 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.443 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 4.92 mm/y;
comparative example 9
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.02% of phosphorus, 0.025% of sulfur and the balance of iron. Through tests, the performance indexes of the alloy material produced by the invention are as follows:
the preparation process is the same as that of example 1
1) Hardness index: 37-40 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.348 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.873 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate is 7.846 mm/y;
comparative example 10
The embodiment provides a wear-resistant corrosion-resistant nonmagnetic alloy material which is prepared by smelting the following components in parts by weight: 1.3% of carbon, 0.5% of silicon, 0.9% of manganese, 29% of chromium, 10% of nickel, 2% of copper, 3.7% of molybdenum, 0.5% of tungsten, 0.02% of phosphorus, 0.023% of sulfur, 0.5% of vanadium, more than 0.2% of titanium, niobium and cerium, and the balance iron. Through tests, the performance indexes of the alloy material produced by the invention are as follows:
the preparation process is the same as that of example 1
1) Hardness index: 41-46 HRC
2) And corrosion resistance:
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 25 ℃: the corrosion rate is 0.263 mm/y;
160g/L sulfuric acid +8g/L hydrochloric acid +13g/L hydrofluoric acid, 85 ℃: the corrosion rate is 1.138 mm/y;
160g/L sulfuric acid, 8g/L hydrochloric acid, 13g/L hydrofluoric acid and 40-70 # quartz sand, wherein the scouring speed of the slurry is 2m/s at 25 ℃: the corrosion rate was 3.898 mm/y.

Claims (6)

1. A preparation method of a wear-resistant corrosion-resistant nonmagnetic alloy material is characterized by comprising the following steps: the method comprises the following steps: carbon steel, foundry returns, ferrochrome, ferromolybdenum, electrolytic copper, electrolytic nickel, ferrosilicon, pure titanium, rare earth cerium, pure vanadium and pure niobium are smelted according to the material component ratio, and the temperature of molten iron is controlled to be 1620-1650 ℃ in the smelting process; after the raw materials are completely melted, sequentially carrying out pre-deoxidation, desulfurization and deoxidation treatment, discharging molten iron when the temperature of the molten iron is reduced to 1600 ℃ or below, then casting and molding the molten iron to obtain a casting, and annealing the casting to obtain the wear-resistant corrosion-resistant nonmagnetic alloy material;
the annealing procedure is as follows: heating to 900-980 ℃ at a speed of 3-7 ℃/min, preserving heat for 1.5-2 h, then cooling to 820-840 ℃ along with the furnace, preserving heat for 1.5-2 h, then cooling to 630-680 ℃ along with the furnace, preserving heat for 3-5 h, and then cooling to room temperature along with the furnace;
the wear-resistant corrosion-resistant nonmagnetic alloy material comprises the following components in percentage by mass:
1.1 to 1.5 percent of carbon, 0.2 to 1.4 percent of silicon, 0.4 to 0.9 percent of manganese, 29 to 31 percent of chromium, 9 to 12.0 percent of nickel, 1.0 to 2.0 percent of copper, 3.4 to 3.7 percent of molybdenum, 0.2 to 0.9 percent of tungsten, 0.016 to 0.019 percent of phosphorus, 0.021 to 0.025 percent of sulfur, 0.03 to 0.1 percent of titanium, 0.2 to 0.28 percent of vanadium, 0.04 to 0.09 percent of niobium, 0.05 to 0.1 percent of cerium, and the balance of iron,
the microstructure of the wear-resistant corrosion-resistant nonmagnetic alloy material is as follows: austenite + M23C6 carbide.
2. The method for preparing the wear-resistant corrosion-resistant nonmagnetic alloy material according to claim 1, characterized in that: and after the raw materials are completely melted, carrying out pre-deoxidation treatment by adopting ferromanganese.
3. The method for preparing the wear-resistant corrosion-resistant nonmagnetic alloy material according to claim 1, characterized in that: during desulfurization, the temperature of molten iron is controlled to be 1620-1640 ℃, and the desulfurizing agent is prepared from lime: the calcium carbide is obtained by mixing according to the mass ratio of 1: 3.
4. The method for preparing the wear-resistant corrosion-resistant nonmagnetic alloy material according to claim 1, characterized in that: the pouring temperature is 1530-1560 ℃.
5. The method for preparing the wear-resistant corrosion-resistant nonmagnetic alloy material according to claim 1, characterized in that: in the annealing process, the periphery of the material is wrapped by carbon powder.
6. The method for preparing the wear-resistant corrosion-resistant nonmagnetic alloy material according to claim 1, characterized in that: the wear-resistant corrosion-resistant nonmagnetic alloy material comprises the following components in percentage by mass:
1.3-1.5% of carbon, 0.5-1.4% of silicon, 0.4-0.9% of manganese, 29-31% of chromium, 9-10.0% of nickel, 1.0-2.0% of copper, 3.6-3.7% of molybdenum, 0.5-0.9% of tungsten, 0.016-0.018% of phosphorus, 0.021-0.025% of sulfur, 0.03-0.1% of titanium, 0.2-0.28% of vanadium, 0.04-0.0.09% of niobium, 0.05-0.07% of cerium and the balance of iron.
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