CN117660725A - Rare earth treatment method for low-alloy wear-resistant steel - Google Patents
Rare earth treatment method for low-alloy wear-resistant steel Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 238000007664 blowing Methods 0.000 claims description 21
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- 239000001301 oxygen Substances 0.000 claims description 15
- GSVIBLVMWGSPRZ-UHFFFAOYSA-N cerium iron Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Ce].[Ce] GSVIBLVMWGSPRZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 9
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- AKWFBKKYZNGQGT-UHFFFAOYSA-N [Fe].[Ce].[La] Chemical compound [Fe].[Ce].[La] AKWFBKKYZNGQGT-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to a rare earth treatment method of low-alloy wear-resistant steel, which is characterized in that refining slag is modified at the end of LF refining of the low-alloy wear-resistant steel, rare earth oxide, lime, quartz sand, alumina and the like are added to modify the refining slag into a novel slag system, the reactivity between the refining slag and rare earth in the steel is reduced by the design of the novel slag system, and meanwhile, the dissolution absorption capacity and the desulfurization capacity of the refining slag for inclusions are enhanced; finally, the rare earth content in the low alloy wear-resistant steel reaches 0.0050% -0.0300% by matching with the addition of the rare earth-iron alloy, the formation of large-size high-melting-point inclusions is inhibited, and the nozzle nodulation in the continuous casting process is avoided. The addition of the rare earth improves the thermoplasticity of the steel plate, further increases the thickness of a plastic deformation zone of the wear surface of the low-alloy wear-resistant steel under the action of impact load, increases the work hardening degree of the surface of the steel plate, enhances the microhardness of the surface of the steel plate, and remarkably improves the wear resistance and corrosion resistance of the low-alloy wear-resistant steel.
Description
Technical Field
The invention relates to the technical field of low-alloy wear-resistant steel plate smelting, in particular to a rare earth treatment method for low-alloy wear-resistant steel.
Background
China is a rare earth resource country. With the continuous development of rare earth resources, light rare earth such as lanthanum, cerium and the like is seriously excessive due to the fact that the application fields are small, and steel materials are used as basic structural materials with irreplaceable and maximum use amount, so that the method becomes a main field of light rare earth resource development and utilization. The steel industry in China is in the key stages of transformation upgrading and green development, and a great amount of light rare earth resources such as lanthanum, cerium and the like in China are fully utilized, so that the variety development and quality improvement of steel products are carried out, and the method has important strategic significance.
The mechanism of action of rare earth in steel is conventionally thought to mainly include: purifying molten steel, metamorphic inclusion and microalloying. The unique microalloying effect of the rare earth is now an important means for developing high-quality steel grades at home and abroad, but the industrial application of the rare earth steel is undeniably still facing serious challenges. The prior rare earth treatment process generally adopts the method of directly adding rare earth metal or rare earth alloy into molten steel. The rare earth metal has strong activity under the high temperature condition, and is very easy to be matched with impurity elements such as oxygen, sulfur and the like in molten steel and SiO in slag 2 The equal oxidizing components react to cause larger fluctuation of the content of dissolved rare earth, thereby affecting the microalloying effect of the rare earth, and meanwhile, if large-size high-melting-point rare earth inclusions formed by the reaction cannot be effectively removed, the performance of the product is inevitably deteriorated, and meanwhile, the nozzle is easy to nodulation.
Patent CN202011194183.7 discloses a rare earth wear-resistant steel NM400 coiled plate with excellent low-temperature toughness and a production method thereof, wherein the low-temperature toughness of the coiled plate is remarkably improved by adopting the rare earth microalloying (Ce content is 0.0005-0.0015%) component design and combining with a TMCP on-line quenching technology to produce a thin wear-resistant steel coiled plate by a two-stage cooling process. Patent CN2020103804264. X discloses a HB500 grade high wear resistance steel plate treated by rare earth and a production method thereof, and the produced steel plate contains trace rare earth (Ce content is less than or equal to 0.0015%), and has the characteristics of high strength, high hardness, high low temperature toughness and high wear resistance. Patent CN201910880333.0 discloses a rare earth NM500 wide and thick steel plate and a production method thereof, and the produced wide and thick steel plate also contains trace rare earth (Ce content is 0.0009-0.0020%), and has high strength, high toughness, high shaping and high wear resistance. The above patents all adopt a mode of directly adding rare earth into molten steel to carry out rare earth treatment. The rare earth content in the steel can be maintained below 0.0020%, and although the product performance is improved by the inclusion in the modified steel, almost all the rare earth in the steel is attributed to the inclusion, and the microalloying effect of the rare earth cannot be truly exerted.
The low alloy wear resistant steel is widely applied to various fields of thermal power plants, coal yards, cement plants, loading machines, mining machines, construction machines, engineering machines, metallurgical machines and the like. With the high-speed development of science and technology and modern industry, the operation speed of mechanical equipment is higher and higher, the worn speed of friction parts is higher and higher, the service life of the friction parts becomes an important factor affecting the production efficiency of modern equipment, especially an automatic production line running at high speed, and the failure of mechanical parts caused by wear becomes more and more prominent. With the continuous progress of the production process technology of the low-alloy high-strength wear-resistant steel in China, the grade and grade of the low-alloy wear-resistant steel are also continuously improved. In view of the severe use environment of low alloy wear-resistant steel, the corrosion resistance and wear resistance of the product need to be improved.
Disclosure of Invention
Technical scheme (one)
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a rare earth treatment method for low-alloy wear-resistant steel.
The embodiment of the invention provides a rare earth treatment method for low-alloy wear-resistant steel, which comprises the following steps: s100: molten iron pretreatment, S200: converter smelting, S300: LF refining, S400: RH vacuum refining, S500: continuous casting, S600: hot rolling, S700: heat treatment; in S300 LF refining includes:
s310: deoxidizing the first molten steel to ensure that the total oxygen mass fraction in the first molten steel is less than or equal to 0.0020 percent and the dissolved oxygen mass fraction in the first molten steel is less than or equal to 0.0003 percent, thereby generating refining slag and deoxidized second molten steel;
s320: adding rare earth oxide into the refining slag to modify the refining slag components, and simultaneously adding lime, quartz sand or alumina to enable the mass ratio of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide) in the modified refining slag to be 5-8;
s330: and adding rare earth-iron alloy into the second molten steel at the exposed position of the slag surface, wherein the addition amount of the rare earth-iron alloy is 0.5-2 kg/t of steel.
Optionally, in step S310, the step of deoxidizing the molten steel includes:
aluminum particles, aluminum powder or aluminum wires are added into the molten steel for deoxidization.
Optionally, in step S320, argon soft blowing is performed into the second molten steel after finishing modification of the refining slag, wherein the argon soft blowing time is not less than 8min.
Optionally, in step S330, the surface of the second molten steel is exposed by soft blowing of argon gas, and the exposed diameter is less than or equal to 10cm.
Optionally, in step S330, the rare earth-iron alloy includes one or more of lanthanum-iron alloy, cerium-iron alloy, and lanthanum-cerium-iron alloy, where the mass fraction of rare earth in the alloy is 10-30%.
Optionally, in step S320, the added rare earth oxide includes lanthanum oxide and/or cerium oxide, and the addition amount is 3-10% of the weight of the refining slag.
Preferably, the rare earth oxide comprises lanthanum oxide and/or cerium oxide.
(II) advantageous effects
The beneficial effects of the invention are as follows: the invention relates to a rare earth treatment method of low-alloy wear-resistant steel, which is characterized in that refining slag is modified at the end of LF refining of the low-alloy wear-resistant steel, rare earth oxide and silicon oxide are added into the refining slag,the traditional CaO-SiO is prepared 2 -Al 2 O 3 MgO slag system is modified into CaO-SiO 2 -Al 2 O 3 -MgO-REO slag system; adding rare earth-iron alloy into molten steel after finishing modification of refining slag; RE in molten steel and SiO in refining slag are inhibited by adding REO (rare earth oxide) in refining slag 2 The reaction of the rare earth in the molten steel is prevented from entering the slag, and the yield of the rare earth in the molten steel is improved; meanwhile, silicon oxide is added into the refining slag, so that the ratio of (calcium oxide and rare earth oxide)/silicon oxide in the refining slag is controlled to be 5-8, and the change of performances such as viscosity, surface tension and the like of the refining slag caused by the addition of the rare earth oxide is avoided; the design of the novel slag system reduces the reactivity between the refining slag and rare earth in steel, and simultaneously enhances the dissolution and absorption capacity and the desulfurization capacity of the refining slag to inclusions; finally, the rare earth content in the low alloy wear-resistant steel reaches 0.0050% -0.0300% by matching with the addition of the rare earth-iron alloy, the formation of large-size high-melting-point inclusions is inhibited, and the nozzle nodulation in the continuous casting process is avoided. The addition of the rare earth improves the thermoplasticity of the steel plate, further increases the thickness of a plastic deformation zone of the wear surface of the low-alloy wear-resistant steel under the action of impact load, increases the work hardening degree of the surface of the steel plate, enhances the microhardness of the surface of the steel plate, and remarkably improves the wear resistance of the low-alloy wear-resistant steel.
Drawings
FIG. 1 is a schematic flow chart of a rare earth treatment method of the low alloy wear resistant steel of the present invention;
fig. 2 is a schematic flow chart of LF refining of the present invention.
Detailed Description
In order that the above-described aspects may be better understood, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
Referring to fig. 1 and 2, the invention provides a rare earth treatment method for low alloy wear resistant steel, which comprises the following steps:
s100: and (3) molten iron pretreatment: the molten iron is subjected to pretreatment desulfurization by a KR (Kambara Reactor) method or a blowing method, slag skimming is carried out on the molten iron after desulfurization pretreatment, and the mass fraction of sulfur in the molten iron is ensured to be less than or equal to 0.0020 percent.
S200: smelting in a converter: decarburization, desilication and desulfurization are carried out on molten iron through a top-bottom combined blown converter, and 4-8 kg/t of lime and 1-3 kg/t of premelted refining slag are added into the first molten steel in the tapping process.
S300: LF (Ladle Furnace) refining, the LF refining in S300 includes:
s310: deoxidizing the first molten steel to make the total oxygen mass fraction in the first molten steel be 0.0018% and the dissolved oxygen mass fraction in the first molten steel be 0.0003%, so as to generate refining slag and deoxidized second molten steel; wherein, in the step S310, the first molten steel is deoxidized: adding aluminum particles into the first molten steel to deoxidize;
s320: adding rare earth oxide into the refining slag to modify the refining slag components, wherein the addition amount is 5% of the weight of the refining slag, the rare earth oxide is lanthanum oxide, and lime, quartz sand and aluminum oxide are added at the same time, so that the mass ratio of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide) in the modified refining slag is 5;
lanthanum and cerium resources in China are rich, and the prices of lanthanum oxide and cerium oxide are far lower than those of other rare earth oxides, so that the lanthanum oxide and cerium oxide are selected and used, and the cost advantage is achieved; the addition amount is 3-10% of the weight of the refining slag, and when the addition amount is lower than the control amount, RE in molten steel and SiO in slag are difficult to inhibit 2 The reaction effect, the addition amount is higher than the control amount, so that the properties such as melting point and viscosity of slag are seriously affected, and normal smelting cannot be performed; lime and premelted refining slag are added in the converter tapping process for preliminary slagging, then a proper amount of rare earth oxide, calcium oxide, silicon oxide and aluminum oxide are added in the LF refining process, so as to achieve the purpose of component regulation and control, and the slag system components are controlled at (calcium oxide+rare earth oxide)/(silicon oxide+oxygen)Aluminum melting) of 5-8, not only can ensure that the refining slag has good fluidity and sulfur capacity and realize the original metallurgical functions of isolating air, insulating heat, desulfurizing, absorbing impurities and the like, but also can inhibit SiO in the refining slag 2 The reaction with rare earth in molten steel can prevent the loss of rare earth and the deterioration of refining slag performance.
In the step S320, after finishing the modification of the refining slag, carrying out argon soft blowing in the second molten steel, wherein the argon soft blowing time is 8min;
s330: adding lanthanum-iron alloy into the second molten steel at the exposed part of the slag surface, wherein the addition amount of the lanthanum-iron alloy is 0.5kg/t steel;
in the step S330, the surface of the second molten steel is exposed by soft blowing of argon, and the diameter of the exposed surface is 9cm;
as described above, lanthanum and cerium resources in China are rich, and the prices of lanthanum-iron alloy and cerium-iron alloy are far lower than those of other rare earth-iron alloys, so that the lanthanum-iron alloy and cerium-iron alloy are selected to have cost advantages. Lanthanum-iron alloy and cerium-iron alloy are selected instead of pure lanthanum or pure cerium, because the rare earth-iron alloy reduces the activity of rare earth, the rare earth is prevented from violently reacting with air or slag at high temperature in the adding process, excessive loss of rare earth is caused, and the rare earth yield can be greatly increased.
The purpose of the exposed slag liquid surface is to smoothly add the rare earth-iron alloy into molten steel, so as to avoid the direct contact reaction of the alloy and slag. However, in order to prevent molten steel from being excessively exposed to air and causing molten steel to absorb oxygen and produce impurities, the diameter of the exposed surface should be strictly controlled to be less than or equal to 10cm.
In the step S330, the rare earth-iron alloy is a lanthanum-iron alloy, wherein the mass fraction of rare earth in the alloy is 10%.
S400: RH vacuum refining (namely, a molten steel vacuum circulation degassing method, which is an external refining method of molten steel commonly designed and developed by Germany Derulu iron and Steel Co., ltd. (Ruhrstahl) and Hereaeus (Hereeus)) is as follows: vacuum refining is carried out in an RH refining furnace with the high vacuum degree (less than or equal to 3.0 mbar) maintained for more than or equal to 25 minutes; and after RH is finished, soft argon blowing static stirring is carried out, and the static stirring time is more than or equal to 15min.
S500: continuous casting: the continuous casting long nozzle and the immersed nozzle are tightly sealed by argon, the pulling speed is controlled to be 0.70-1.00m/min, a tundish adopts a carbonless covering agent, and the casting adopts high-carbon steel covering slag.
S600: and (3) hot rolling: the heating temperature is 1200-1300 ℃, rolling is controlled by two stages, the temperature is not higher than 950 ℃ after rolling in the first stage, the target finishing temperature is not lower than 830 ℃, and air cooling is carried out after rolling.
S700: and (3) heat treatment: comprises quenching and tempering treatment, wherein the quenching heating temperature is 800-950 ℃; the tempering heating temperature is 200-280 ℃.
S800: and (5) forming a material.
After rare earth treatment, the prismatic or cluster inclusions with larger hazard in the steel are changed into Ce with relatively small size and more similar properties to the steel matrix 2 O 2 S, ceS and the like contain rare earth inclusions; the spherical rare earth oxysulfide has better pitting corrosion resistance than the strip manganese sulfide, so the addition of rare earth weakens electrochemical corrosion of a micro area, improves electrode potential of a steel matrix, and the tiny spherical inclusions can also strengthen pinning effect between a rust layer and the matrix, strengthen protection of the matrix, improve corrosion resistance of the steel, relatively high rare earth content (La mass fraction: 0.0060%) is distributed at a grain boundary, greatly refines grains and obtains a plurality of lath martensite structures which are distributed uniformly. The refined structure ensures that the crystal grains of the rust phase on the surface of the steel are fine, reduces the areas of ion channels and anodes, and can effectively prevent corrosive media from contacting with a rigid matrix. The rare earth also promotes the transformation from the unstable rust phase gamma-FeOOH to the stable alpha-FeOOH, and promotes the formation of a compact stable corrosion-resistant rust layer on the surface of the steel; the rare earth also inhibits the partial polymerization of corrosive element sulfur in the rust layer, which is beneficial to the rapid generation of the protective corrosion-resistant rust layer; the addition of the rare earth improves the thermoplasticity of the steel plate, further increases the thickness of a plastic deformation zone of the wear surface of the low-alloy wear-resistant steel under the action of impact load, increases the work hardening degree of the surface of the steel plate, enhances the microhardness of the surface of the steel plate, and remarkably improves the wear resistance of the low-alloy wear-resistant steel.
According to the mechanical industry standard JB/T7901, the low-alloy wear-resistant steel is subjected to uniform corrosion total immersion test, and compared with the traditional low-alloy wear-resistant steel without rare earth treatment, the low-alloy wear-resistant steel subjected to rare earth treatment has obviously reduced surface corrosion degree and corrosion rate of more than 15%; the MLD-10 impact abrasive wear testing machine is adopted to conduct abrasive wear test under impact load, and compared with the traditional low-alloy wear-resistant steel plate without rare earth treatment, the low-alloy wear-resistant steel plate with rare earth treatment has the advantages that the wear loss weight is reduced by more than 20%, and specific performance indexes are shown in table 1.
Example 2
Referring to fig. 1 and 2, the invention provides a rare earth treatment method for low alloy wear resistant steel, which comprises the following steps:
s100: and (3) molten iron pretreatment: the molten iron is subjected to pretreatment desulfurization by a KR (Kambara Reactor) method or a blowing method, slag skimming is carried out on the molten iron after desulfurization pretreatment, and the mass fraction of sulfur in the molten iron is ensured to be less than or equal to 0.0020 percent.
S200: smelting in a converter: decarburization, desilication and desulfurization are carried out on molten iron through a top-bottom combined blown converter, and 4-8 kg/t of lime and 1-3 kg/t of premelted refining slag are added into the first molten steel in the tapping process.
S300: LF (Ladle Furnace) refining, the LF refining in S300 includes:
s310: deoxidizing the first molten steel to make the total oxygen mass fraction in the first molten steel be 0.0015% and the dissolved oxygen mass fraction in the first molten steel be 0.0002%, so as to generate refining slag and deoxidized second molten steel; wherein, in the step S310, the first molten steel is deoxidized: adding aluminum powder into the first molten steel to deoxidize;
s320: adding rare earth oxide into the refining slag to modify the refining slag components, wherein the addition amount is 8% of the weight of the refining slag, the rare earth oxide is cerium oxide, and lime, quartz sand and aluminum oxide are added at the same time, so that the mass ratio of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide) in the modified refining slag is 7;
lanthanum and cerium resources in China are rich, and the prices of lanthanum oxide and cerium oxide are far lower than those of other rare earth oxides, so that the lanthanum oxide and cerium oxide are selected to have the costAdvantages are that; the addition amount is 3-10% of the weight of the refining slag, and when the addition amount is lower than the control amount, RE in molten steel and SiO in slag are difficult to inhibit 2 The reaction effect, the addition amount is higher than the control amount, so that the properties such as melting point and viscosity of slag are seriously affected, and normal smelting cannot be performed; lime and premelted refining slag are added in the converter tapping process for preliminary slagging, then a proper amount of rare earth oxide, calcium oxide, silicon oxide and aluminum oxide are added in the LF refining process, so that the purpose of component regulation is achieved, slag components are controlled to be 5-8 in terms of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide), the refining slag can be ensured to have good fluidity and sulfur capacity, the original metallurgical functions of isolating air, insulating heat, desulfurizing, absorbing impurities and the like are realized, and SiO in the refining slag can be inhibited 2 The reaction with rare earth in molten steel can prevent the loss of rare earth and the deterioration of refining slag performance.
In the step S320, after finishing modification of the refining slag, carrying out argon soft blowing in the second molten steel, wherein the argon soft blowing time is 10min;
s330: adding cerium-iron alloy into the second molten steel at the exposed position of the slag surface, wherein the addition amount is 1kg/t of steel;
in the step S330, the surface of the second molten steel is exposed by soft blowing of argon, and the diameter of the exposed second molten steel is 8cm;
as described above, lanthanum and cerium resources in China are rich, and the prices of lanthanum-iron alloy and cerium-iron alloy are far lower than those of other rare earth-iron alloys, so that the lanthanum-iron alloy and cerium-iron alloy are selected to have cost advantages. Lanthanum-iron alloy and cerium-iron alloy are selected instead of pure lanthanum or pure cerium, because the rare earth-iron alloy reduces the activity of rare earth, the rare earth is prevented from violently reacting with air or slag at high temperature in the adding process, excessive loss of rare earth is caused, and the rare earth yield can be greatly increased.
The purpose of the exposed slag liquid surface is to smoothly add the rare earth-iron alloy into molten steel, so as to avoid the direct contact reaction of the alloy and slag. However, in order to prevent molten steel from being excessively exposed to air and causing molten steel to absorb oxygen and produce impurities, the diameter of the exposed surface should be strictly controlled to be less than or equal to 10cm.
In the step S330, the rare earth-iron alloy is a lanthanum-iron alloy, wherein the mass fraction of rare earth in the alloy is 20%.
S400: RH vacuum refining (namely, a molten steel vacuum circulation degassing method, which is an external refining method of molten steel commonly designed and developed by Germany Derulu iron and Steel Co., ltd. (Ruhrstahl) and Hereaeus (Hereeus)) is as follows: vacuum refining is carried out in an RH refining furnace with the high vacuum degree (less than or equal to 3.0 mbar) maintained for more than or equal to 25 minutes; and after RH is finished, soft argon blowing static stirring is carried out, and the static stirring time is more than or equal to 15min.
S500: continuous casting: the continuous casting long nozzle and the immersed nozzle are tightly sealed by argon, the pulling speed is controlled to be 0.70-1.00m/min, a tundish adopts a carbonless covering agent, and the casting adopts high-carbon steel covering slag.
S600: and (3) hot rolling: the heating temperature is 1200-1300 ℃, rolling is controlled by two stages, the temperature is not higher than 950 ℃ after rolling in the first stage, the target finishing temperature is not lower than 830 ℃, and air cooling is carried out after rolling.
S700: and (3) heat treatment: comprises quenching and tempering treatment, wherein the quenching heating temperature is 800-950 ℃; the tempering heating temperature is 200-280 ℃.
S800: and (5) forming a material.
After rare earth treatment, the prismatic or cluster inclusions with larger hazard in the steel are changed into Ce with relatively small size and more similar properties to the steel matrix 2 O 2 S, ceS and the like contain rare earth inclusions; the spherical rare earth oxysulfide has better pitting corrosion resistance than the strip manganese sulfide, so the addition of rare earth weakens electrochemical corrosion of a micro area, improves electrode potential of a steel matrix, and the tiny spherical inclusions can also strengthen pinning effect between a rust layer and the matrix, strengthen protection of the matrix, improve corrosion resistance of the steel, and enable relatively high rare earth content (Ce mass fraction is 0.0155%) to be distributed at a grain boundary, greatly refine grains and obtain a plurality of lath martensite structures which are distributed uniformly. The refined structure ensures that the crystal grains of the rust phase on the surface of the steel are fine, reduces the areas of ion channels and anodes, and can effectively prevent corrosive media from contacting with a rigid matrix. The rare earth also promotes the stable gamma-FeOOH of the unstable rust phaseThe fixed alpha-FeOOH is converted, so that a compact and stable corrosion-resistant rust layer is generated on the surface of the steel; the rare earth also inhibits the partial polymerization of corrosive element sulfur in the rust layer, which is beneficial to the rapid generation of the protective corrosion-resistant rust layer; the addition of the rare earth improves the thermoplasticity of the steel plate, further increases the thickness of a plastic deformation zone of the wear surface of the low-alloy wear-resistant steel under the action of impact load, increases the work hardening degree of the surface of the steel plate, enhances the microhardness of the surface of the steel plate, and remarkably improves the wear resistance of the low-alloy wear-resistant steel.
According to the mechanical industry standard JB/T7901, the low-alloy wear-resistant steel is subjected to uniform corrosion total immersion test, and compared with the traditional low-alloy wear-resistant steel without rare earth treatment, the low-alloy wear-resistant steel subjected to rare earth treatment has obviously reduced surface corrosion degree and corrosion rate of more than 15%; and an MLD-10 impact abrasive wear testing machine is adopted to conduct abrasive wear test under impact load, and compared with a traditional low-alloy wear-resistant steel plate without rare earth treatment, the low-alloy wear-resistant steel plate with rare earth treatment has the advantages that the wear loss weight is reduced by more than 20%. The specific performance indexes are shown in Table 1.
Example 3
Referring to fig. 1 and 2, the invention provides a rare earth treatment method for low alloy wear resistant steel, which comprises the following steps:
s100: and (3) molten iron pretreatment: the molten iron is subjected to pretreatment desulfurization by a KR (Kambara Reactor) method or a blowing method, slag skimming is carried out on the molten iron after desulfurization pretreatment, and the mass fraction of sulfur in the molten iron is ensured to be less than or equal to 0.0020 percent.
S200: smelting in a converter: decarburization, desilication and desulfurization are carried out on molten iron through a top-bottom combined blown converter, and 4-8 kg/t of lime and 1-3 kg/t of premelted refining slag are added into the first molten steel in the tapping process.
S300: LF (Ladle Furnace) refining, the LF refining in S300 includes:
s310: deoxidizing the first molten steel to make the total oxygen mass fraction in the first molten steel be 0.0012% and the dissolved oxygen mass fraction in the first molten steel be 0.0002%, so as to generate refining slag and deoxidized second molten steel; wherein, in the step S310, the first molten steel is deoxidized: adding aluminum wires into the first molten steel to deoxidize;
s320: adding rare earth oxide into the refining slag to carry out refining slag component modification, wherein the addition amount is 10% of the weight of the refining slag, the rare earth oxide is lanthanum oxide and cerium oxide, and lime, quartz sand and aluminum oxide are added at the same time, so that the mass ratio of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide) in the modified refining slag is 8;
lanthanum and cerium resources in China are rich, and the prices of lanthanum oxide and cerium oxide are far lower than those of other rare earth oxides, so that the lanthanum oxide and cerium oxide are selected and used, and the cost advantage is achieved; the addition amount is 3-10% of the weight of the refining slag, and when the addition amount is lower than the control amount, RE in molten steel and SiO in slag are difficult to inhibit 2 The reaction effect, the addition amount is higher than the control amount, so that the properties such as melting point and viscosity of slag are seriously affected, and normal smelting cannot be performed; lime and premelted refining slag are added in the converter tapping process for preliminary slagging, then a proper amount of rare earth oxide, calcium oxide, silicon oxide and aluminum oxide are added in the LF refining process, so that the purpose of component regulation is achieved, slag components are controlled to be 5-8 in terms of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide), the refining slag can be ensured to have good fluidity and sulfur capacity, the original metallurgical functions of isolating air, insulating heat, desulfurizing, absorbing impurities and the like are realized, and SiO in the refining slag can be inhibited 2 The reaction with rare earth in molten steel can prevent the loss of rare earth and the deterioration of refining slag performance.
In the step S320, after finishing the modification of the refining slag, carrying out argon soft blowing in the second molten steel, wherein the argon soft blowing time is 12min;
s330: adding lanthanum-iron alloy and cerium-iron alloy into the second molten steel at the exposed position of the slag surface, wherein the addition amount of the lanthanum-iron alloy and the cerium-iron alloy is 1.5kg/t steel;
in the step S330, the surface of the second molten steel is exposed by soft blowing of argon, and the diameter of the exposed surface is 7cm;
as described above, lanthanum and cerium resources in China are rich, and the prices of lanthanum-iron alloy and cerium-iron alloy are far lower than those of other rare earth-iron alloys, so that the lanthanum-iron alloy and cerium-iron alloy are selected to have cost advantages. Lanthanum-iron alloy and cerium-iron alloy are selected instead of pure lanthanum or pure cerium, because the rare earth-iron alloy reduces the activity of rare earth, the rare earth is prevented from violently reacting with air or slag at high temperature in the adding process, excessive loss of rare earth is caused, and the rare earth yield can be greatly increased.
The purpose of the exposed slag liquid surface is to smoothly add the rare earth-iron alloy into molten steel, so as to avoid the direct contact reaction of the alloy and slag. However, in order to prevent molten steel from being excessively exposed to air and causing molten steel to absorb oxygen and produce impurities, the diameter of the exposed surface should be strictly controlled to be less than or equal to 10cm.
In the step S330, the rare earth-iron alloy is a lanthanum-iron alloy, wherein the mass fraction of rare earth in the alloy is 20%.
S400: RH vacuum refining (namely, a molten steel vacuum circulation degassing method, which is an external refining method of molten steel commonly designed and developed by Germany Derulu iron and Steel Co., ltd. (Ruhrstahl) and Hereaeus (Hereeus)) is as follows: vacuum refining is carried out in an RH refining furnace with the high vacuum degree (less than or equal to 3.0 mbar) maintained for more than or equal to 25 minutes; and after RH is finished, soft argon blowing static stirring is carried out, and the static stirring time is more than or equal to 15min.
S500: continuous casting: the continuous casting long nozzle and the immersed nozzle are tightly sealed by argon, the pulling speed is controlled to be 0.70-1.00m/min, a tundish adopts a carbonless covering agent, and the casting adopts high-carbon steel covering slag.
S600: and (3) hot rolling: the heating temperature is 1200-1300 ℃, rolling is controlled by two stages, the temperature is not higher than 950 ℃ after rolling in the first stage, the target finishing temperature is not lower than 830 ℃, and air cooling is carried out after rolling.
S700: and (3) heat treatment: comprises quenching and tempering treatment, wherein the quenching heating temperature is 800-950 ℃; the tempering heating temperature is 200-280 ℃.
S800: and (5) forming a material.
After rare earth treatment, the prismatic or cluster inclusions with larger hazard in the steel are changed into Ce with relatively small size and more similar properties to the steel matrix 2 O 2 S, ceS and the like contain rare earth inclusions; the pitting corrosion resistance of the spherical rare earth oxysulfide is better than that of the strip manganese sulfide, so that the addition of rare earth is weakenedThe electrochemical corrosion of the micro-area is improved, the electrode potential of the steel matrix is improved, the pinning effect between the rust layer and the matrix can be enhanced by the tiny spherical inclusions, the protection of the matrix is enhanced, the corrosion resistance of the steel can be improved, the relatively high rare earth content (Ce mass fraction: 0.0226%) is distributed at the grain boundary, the grains are greatly refined, and a more uniform lath martensitic structure is obtained. The refined structure ensures that the crystal grains of the rust phase on the surface of the steel are fine, reduces the areas of ion channels and anodes, and can effectively prevent corrosive media from contacting with a rigid matrix. The rare earth also promotes the transformation from the unstable rust phase gamma-FeOOH to the stable alpha-FeOOH, and promotes the formation of a compact stable corrosion-resistant rust layer on the surface of the steel; the rare earth also inhibits the partial polymerization of corrosive element sulfur in the rust layer, which is beneficial to the rapid generation of the protective corrosion-resistant rust layer; the addition of the rare earth improves the thermoplasticity of the steel plate, further increases the thickness of a plastic deformation zone of the wear surface of the low-alloy wear-resistant steel under the action of impact load, increases the work hardening degree of the surface of the steel plate, enhances the microhardness of the surface of the steel plate, and remarkably improves the wear resistance of the low-alloy wear-resistant steel.
According to the mechanical industry standard JB/T7901, the low-alloy wear-resistant steel is subjected to uniform corrosion total immersion test, and compared with the traditional low-alloy wear-resistant steel without rare earth treatment, the low-alloy wear-resistant steel subjected to rare earth treatment has obviously reduced surface corrosion degree and corrosion rate of more than 15%; the MLD-10 impact abrasive wear testing machine is adopted to conduct abrasive wear test under impact load, and compared with the traditional low-alloy wear-resistant steel plate without rare earth treatment, the low-alloy wear-resistant steel plate with rare earth treatment has the advantages that the wear loss weight is reduced by more than 20%, and specific performance indexes are shown in table 1.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., refer to particular features, structures, materials, or characteristics described in connection with the embodiment or example as being included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.
Claims (7)
1. A method of rare earth treatment of low alloy wear resistant steel, the method comprising: s100: molten iron pretreatment, S200: converter smelting, S300: LF refining, S400: RH vacuum refining, S500: continuous casting, S600: hot rolling, S700: heat treatment; s800: forming a material; the method is characterized in that: the LF refining in S300 includes:
s310: deoxidizing the first molten steel to ensure that the total oxygen mass fraction in the first molten steel is less than or equal to 0.0020 percent, and the dissolved oxygen mass fraction in the first molten steel is less than or equal to 0.0003 percent, so as to generate refining slag and deoxidized second molten steel;
s320: adding rare earth oxide into the refining slag to modify the refining slag components, and simultaneously adding lime, quartz sand or alumina to enable the mass ratio of (calcium oxide+rare earth oxide)/(silicon oxide+aluminum oxide) in the modified refining slag to be 5-8;
s330: and adding rare earth-iron alloy into the second molten steel at the exposed position of the slag surface, wherein the addition amount of the rare earth-iron alloy is 0.5-2 kg/t of steel.
2. The rare earth treatment method for low alloy wear resistant steel according to claim 1, wherein: in step S310, the deoxidizing treatment step for the first molten steel includes:
and adding aluminum particles, aluminum powder or aluminum wires into the first molten steel to deoxidize.
3. The rare earth treatment method for low alloy wear resistant steel according to claim 1, wherein: in the step S320, after finishing the modification of the refining slag, argon soft blowing is carried out in the second molten steel, wherein the argon soft blowing time is more than or equal to 8min.
4. The rare earth treatment method for low alloy wear resistant steel according to claim 1, wherein: in the step S330, the surface of the second molten steel is exposed by soft blowing of argon, and the diameter of the exposed surface is less than or equal to 10cm.
5. The rare earth treatment method for low alloy wear resistant steel according to claim 1, wherein:
in the step S330, the rare earth-iron alloy includes one or more of lanthanum-iron alloy, cerium-iron alloy and lanthanum-cerium-iron alloy, wherein the mass fraction of rare earth in the alloy is 10-30%.
6. The rare earth treatment method for low alloy wear resistant steel according to claim 1, wherein:
in the step S320, rare earth oxide is added into the refining slag to modify the refining slag components, wherein the addition amount is 3-10% of the weight of the refining slag.
7. The rare earth treatment method for low alloy wear resistant steel according to claim 6, wherein:
the rare earth oxide comprises lanthanum oxide and/or cerium oxide.
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| CN102002556A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Rare earth oxide-containing steelmaking refining slag, and preparation method and using method thereof |
| CN114672611A (en) * | 2022-03-11 | 2022-06-28 | 钢铁研究总院有限公司 | Method for improving rare earth yield in rare earth steel smelting process |
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| SU1548216A1 (en) * | 1988-05-24 | 1990-03-07 | Центральный научно-исследовательский институт черной металлургии им.И.П.Бардина | Silica material for melting steel-refining slag |
| CN102002556A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Rare earth oxide-containing steelmaking refining slag, and preparation method and using method thereof |
| CN114672611A (en) * | 2022-03-11 | 2022-06-28 | 钢铁研究总院有限公司 | Method for improving rare earth yield in rare earth steel smelting process |
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