CN111020358A - Rare earth silicon-nitrogen alloy and preparation method and application thereof - Google Patents

Rare earth silicon-nitrogen alloy and preparation method and application thereof Download PDF

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CN111020358A
CN111020358A CN201911389270.5A CN201911389270A CN111020358A CN 111020358 A CN111020358 A CN 111020358A CN 201911389270 A CN201911389270 A CN 201911389270A CN 111020358 A CN111020358 A CN 111020358A
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rare earth
silicon
nitrogen
nitrogen alloy
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陈漪恺
陈来祥
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Maanshan Zhongke Metallurgical Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C35/00—Master alloys for iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel
    • C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys

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Abstract

The invention belongs to the technical field of iron-based alloys and alloy additives, and particularly relates to a rare earth silicon-nitrogen alloy and a preparation method and application thereof. The rare earth silicon-nitrogen alloy provided by the invention comprises the following element components in percentage by mass: si: 9-58%, N: 6-35%, Ce: 0-19%, La: 0-15%, Pr: 0-6%, Nd: 0-12%, Sm: 0-4.5% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time. The invention obtains the rare earth silicon-nitrogen alloy by alloying a plurality of metal alloys by adopting a direct nitriding treatment process, solves the problems of overlapping and matching of the same component content in microalloying by simultaneously adding a plurality of metal alloys and unstable joint application effect, can better improve the comprehensive performance of steel, simultaneously greatly reduces the manufacturing cost of special steel, and reduces the comprehensive cost by more than 35 percent compared with equivalent alloy.

Description

Rare earth silicon-nitrogen alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of iron-based alloys and alloy additives, and particularly relates to a rare earth silicon-nitrogen alloy and a preparation method and application thereof.
Background
A special steel such as high-strength steel, anticorrosion steel and antiwear steel is prepared through adding one or more alloy elements to carbon steel to change its structure, resulting in different special properties of steel. The carbon steel is added with alloy elements, and the alloying is mainly realized by molten steel alloying and molten steel micro-alloying. At present, most of elements added during molten steel microalloying are added in a simple substance metal form, mainly play a role in solid solution strengthening, cannot fully play the functions of the elements and are far lower than the role in precipitation strengthening; when several simple substances are used together, the effect of mutual superposition or interaction of the elements on the microalloying of the molten steel is greatly influenced by the smelting process, so that the microalloying effect is unstable; the multifunctional function of the element is insufficient when the elemental element is used for micro-alloying, so that the comprehensive performance of the steel cannot be effectively improved; meanwhile, the alloying cost is increased by adopting simple substance elements for micro-alloying.
How to obtain special steel with high performance by improving the microalloying effect of molten steel on the premise of not increasing the alloy cost is a technical problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a rare earth silicon-nitrogen alloy and a preparation method thereof.
The invention provides a rare earth silicon-nitrogen alloy which comprises the following element components in percentage by mass: si: 9-58%, N: 6-35%, Ce: 0-19%, La: 0-15%, Pr: 0-6%, Nd: 0-12%, Sm: 0-4.5% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time.
Preferably, the rare earth silicon-nitrogen alloy further includes: cr: 0-19%, V: 0-9%, Ti: 0-12%, Nb: 0-6%, Mn: 0.03 to 27%, Mo: 0-7%, Ni: 0 to 6.5 percent.
The invention provides a preparation method of the rare earth silicon-nitrogen alloy in the technical scheme, which comprises the following steps:
1) mixing the raw materials of other element components except nitrogen element according to element proportion and then grinding to obtain fine powder;
2) mixing the fine powder obtained in the step 1) with a binding agent to obtain a mixture;
3) and (3) nitriding the mixture obtained in the step 2), and then cooling to obtain the rare earth silicon-nitrogen alloy.
Preferably, the nitriding treatment in step 3) is performed by sequentially subjecting the mixture to a low-temperature nitriding treatment and a high-temperature nitriding treatment.
Preferably, the temperature of the low-temperature nitriding treatment is 900-1100 ℃, and the time is 3-4 h; the temperature of the high-temperature nitriding treatment is 1350-1450 ℃, and the time is 6-7 h.
Preferably, the nitriding treatment in the step 3) is performed under a protective gas, the protective gas comprises nitrogen, and the pressure of the protective gas is 0.2-0.3 MPa; the cooling rate of the cooling treatment in the step 3) is 4-6 ℃/min, and the temperature after cooling is 200-300 ℃.
Preferably, the protective gas further comprises argon, and when the protective gas comprises argon and nitrogen, the concentration of the nitrogen is greater than or equal to 99%;
preferably, the mass of the binding agent in the step 2) is 2-3% of the total weight of the fine powder, the binding agent comprises modified phenolic resin, and the carbon content in the modified phenolic resin is greater than or equal to 65%.
Preferably, when the sources of the rare earth elements, the silicon elements, the manganese elements and the iron elements in the raw materials in the step 1) comprise oxides of corresponding elements, the reducing agent is also added in the mixing in the step 2); the dosage of the reducing agent is 10-20% of the total weight of the fine powder; the reducing agent comprises one or more of carbon powder, silicon powder and aluminum powder.
The invention also provides the application of the rare earth silicon-nitrogen alloy in the technical scheme or the rare earth silicon-nitrogen alloy obtained by the preparation method in the technical scheme as an alloy additive.
Has the advantages that: the invention alloys silicon, nitrogen, rare earth elements with other elements, replaces rare earth alloy, silicon nitride and silicon manganese nitride alloy to be applied to steel making or cast steel, does not need to simultaneously add rare earth alloy and several kinds of nitride alloys, simplifies the application process, effectively widens the application range of rare earth silicon-nitrogen alloy, solves the problems of overlapping and matching of the same component content in microalloying by simultaneously adding various metal alloys and unstable combined application effect, can better improve the inclusion deformation improvement effect of steel by directly carrying out microalloying on the rare earth silicon-nitrogen alloy obtained by adopting the invention, improves and stabilizes the steel crystal grain refinement level, and has excellent and stable steel strengthening performance effect. Meanwhile, the invention adopts the nitridation process to prepare the rare earth silicon-nitrogen alloy, thereby reducing the requirement on the purity of the raw materials.
Furthermore, the preparation method can select or add partial oxides containing rare earth, Si and Mn as raw materials, so that the manufacturing cost is greatly reduced, the comprehensive cost is reduced by more than 35 percent compared with the equivalent alloy, and the preparation process of the alloy is safe, environment-friendly and free of waste discharge.
Detailed Description
The invention provides a rare earth silicon-nitrogen alloy which comprises the following element components in percentage by mass: si: 9-58%, N: 6-35%, Ce: 0-19%, La: 0-15%, Pr: 0-6%, Nd: 0-12%, Sm: 0-4.5% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time. The invention provides a rare earth silicon-nitrogen alloy, which comprises the following components in percentage by mass: 9 to 58%, preferably 15 to 40%, and more preferably 20 to 30%.
The invention provides a rare earth silicon-nitrogen alloy, which comprises the following components in percentage by mass: 6 to 35%, preferably 15 to 25%.
The invention provides a rare earth silicon-nitrogen alloy which comprises the following components in percentage by mass: 0 to 19%, preferably 5 to 13%.
The invention provides a rare earth silicon-nitrogen alloy which comprises the following components in percentage by mass: 0 to 15%, preferably 3 to 12%.
The invention provides a rare earth silicon-nitrogen alloy which comprises the following components in percentage by mass: 0 to 6%, preferably 2 to 4%.
The invention provides a rare earth silicon-nitrogen alloy which comprises the following components in percentage by mass: 0 to 12%, preferably 1 to 9%.
The invention provides a rare earth silicon-nitrogen alloy, which comprises Sm: 0 to 4.5%, preferably 0.5 to 3%.
In the present invention, the rare earth element includes one or more elements of Ce, La, Pr, Nd, and Sm, and in the embodiment of the present invention, the rare earth element is preferably four elements of Ce, La, Pr, and Sm, three elements of Ce, Pr, and Sm, or two elements of La and Nd.
The rare earth silicon-nitrogen alloy provided by the invention further comprises the balance of Fe according to the mass content.
The rare earth silicon-nitrogen alloy provided by the invention preferably further comprises the following components in percentage by mass: cr: 0-19%, V: 0-9%, Ti: 0-12%, Nb: 0-6%, Mn: 0.03 to 27%, Mo: 0-7%, Ni: 0-6.5%, B: 0 to 8 percent. The invention limits the content of Cr, Mn, Mo, Ni and B elements in the rare earth silicon-nitrogen alloy to ensure that the alloy can improve the comprehensive mechanical property of steel, thereby being capable of applying the rare earth silicon-nitrogen alloy to the field of alloy additives.
The rare earth silicon-nitrogen alloy provided by the invention further comprises impurities according to the mass content, wherein the impurities comprise Ca: 0.01-4.5%, Al: 0.02-6%, C: 0.05-7%, P is less than or equal to 0.2%, and S is less than or equal to 0.2%.
The invention limits the content of each element in a specific range, and obtains the rare earth silicon-nitrogen alloy under the synergistic action of each element, and the rare earth silicon-nitrogen alloy can better improve the comprehensive performance of steel.
The invention also provides a preparation method of the rare earth silicon-nitrogen alloy in the technical scheme, which comprises the following steps:
1) mixing the raw materials of other element components except nitrogen element according to element proportion and then grinding to obtain fine powder;
2) mixing the fine powder obtained in the step 1) with a binding agent to obtain a mixture;
3) and (3) nitriding the mixture obtained in the step 2), and then cooling to obtain the rare earth silicon-nitrogen alloy.
The invention mixes the raw materials of other element components except nitrogen element according to the element proportion and then grinds the mixture into fine powder, wherein the particle size of the fine powder is preferably less than or equal to 0.15 mm. In the present invention, the raw material includes a simple substance of a corresponding element component or a compound containing a corresponding element component, and when the raw material includes a compound of a corresponding element component, the mass ratio of the compound to the simple substance has no particular requirement as long as the content of the corresponding element component meets the requirement. The compound is preferably an oxide of the corresponding element, the oxide preferably comprising CeO2、Sm2O3、Nd2O3、Pr6O11、La2O3、SiO2MnO and Fe2O3One or more of them.
The raw materials are preferably pretreated before being mixed, the pretreatment comprises impurity removal and moisture removal, and the impurity removal method has no special requirements and only needs a conventional method; the moisture removal is preferably carried out at 300-400 ℃.
The invention mixes the fine powder obtained by milling with a binding agent to obtain a mixture. The invention has no special requirement on the mixing mode, and adopts the mixing mode which is well known in the field as long as the mixing mode can be uniformly mixed. In the invention, the binding agent is preferably modified phenolic resin, the modified phenolic resin is preferably nano-scale, and the carbon content in the modified phenolic resin is preferably more than or equal to 65%; the dosage of the binding agent is preferably 2-3% of the total weight of the fine powder; in the invention, the modified phenolic resin is purchased from an educational chemical auxiliary factory in the consolidated city, and the model thereof is NGL-A type, and the modified phenolic resin has the following characteristics: the dispersibility is good, and the bonding strength is uniform; the sintering property in the later stage of the nitriding treatment is good, and the compactness and the strength of the rare earth silicon-nitrogen alloy can be improved; the carbon in the modified phenolic resin can be fully utilized; and few impurities are introduced into the rare earth silicon-nitrogen alloy.
In the invention, when the raw materials comprise oxides, a reducing agent is preferably added in the mixing step 2), and the using amount of the reducing agent is preferably 10-20% of the total weight of the fine powder; the reducing agent reduces the oxide to a simple substance during the nitriding treatment. In the invention, the reducing agent is preferably carbon powder, silicon powder and aluminum powder, the carbon content in the carbon powder is preferably more than or equal to 95%, the silicon content in the silicon powder is preferably more than or equal to 98%, and the aluminum content in the aluminum powder is preferably more than or equal to 96%. The carbon powder, the silicon powder and the aluminum powder can reduce oxides into simple substances of corresponding elements, and the silicon powder can reduce Sm into Sm2O3、La2O3、CeO2Reducing the aluminum powder into simple substances of corresponding elements, wherein the aluminum powder can convert CaO, MgO and Pr6O11、Nd2O3Reducing the carbon powder into a simple substance of a corresponding element, wherein the carbon powder can convert SiO into SiO2MnO and Fe2O3Reducing into simple substances of corresponding elements. Due to addition of reducing agent in rare earth silicon nitrogenCarbon and aluminum impurities are introduced into the alloy.
After the mixture is obtained, the mixture is subjected to nitriding treatment and then cooled to obtain the rare earth silicon-nitrogen alloy. In the present invention, the nitriding treatment is preferably performed under a protective gas, the protective gas preferably includes nitrogen, and the pressure of the protective gas is preferably 0.2 to 0.3MPa, and more preferably 0.24 to 0.28 MPa. In the present invention, the shielding gas preferably further includes argon; when the protective gas comprises argon and nitrogen, the concentration of the nitrogen is greater than or equal to 99%.
In the present invention, the nitriding treatment is preferably performed by a stepwise nitriding treatment, and in the present invention, the nitriding treatment preferably includes a low-temperature nitriding treatment and a high-temperature nitriding treatment which are performed in this order. In the invention, the temperature of the low-temperature nitriding treatment is preferably 900-1100 ℃, and further preferably 980-1050 ℃; the heating rate of heating to the low-temperature nitriding temperature is preferably 15-20 ℃/min; the time of the low-temperature nitriding treatment is preferably 3-4 h.
Immediately heating after low-temperature nitriding treatment, and then performing high-temperature nitriding treatment. In the invention, the temperature of the high-temperature nitriding treatment is preferably 1350-1450 ℃, and more preferably 1380-1420 ℃; the heating rate of heating to the high-temperature nitriding temperature is preferably 6-10 ℃/min; the time of the high-temperature nitriding treatment is preferably 6-7 h.
After the nitriding treatment, the obtained nitriding treatment product is cooled to obtain the rare earth silicon-nitrogen alloy, wherein the cooling rate is preferably 4-6/min, more preferably 4.5-5 ℃/min, and the temperature after cooling is preferably 200-300 ℃.
The invention also provides the application of the rare earth silicon-nitrogen alloy in the technical scheme or the rare earth silicon-nitrogen alloy prepared by the preparation method in the technical scheme as an alloy additive. In the present invention, the application is preferably applied to the improvement of molten steel inclusion deformation, the refinement of steel crystal grains and the performance reinforcement of steel, thereby improving the comprehensive performance of steel.
To further illustrate the present invention, the following examples are provided to describe the rare earth-silicon-nitrogen alloy of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
The rare earth silicon-nitrogen alloy provided by the embodiment 1 comprises the following element components in percentage by mass, Si: 9%, N: 17%, Ce: 19%, Pr: 6%, Sm: 4.5%, V: 9%, Ni: 6.5%, Ca: 0.01%, Al: 6%, C: 0.05%, P: 0.15%, S: 0.20% and the balance Fe.
Weighing raw materials according to the content ratio of the element components, selecting simple substance raw materials for the raw materials in the embodiment, carrying out impurity removal and moisture removal pretreatment on the weighed raw materials, and grinding the pretreated raw materials to obtain fine powder with the particle size of less than or equal to 0.15 mm; then uniformly mixing the fine powder and the modified phenolic resin to obtain a mixture, and preparing the mixture into blocks, wherein the consumption of the modified phenolic resin accounts for 2% of the total mass of the fine powder, and the carbon content in the modified phenolic resin is 67%; and putting the blocky mixture into a nitriding furnace for nitriding treatment, wherein the pressure of nitrogen in the nitriding furnace is 0.2MPa, heating to 900 ℃ at the heating rate of 15 ℃/min, preserving heat for 4h, heating to 1450 ℃ at the heating rate of 6 ℃/min, preserving heat for 6h, and then cooling to 300 ℃ at the cooling rate of 4 ℃/min to obtain the rare earth silicon-nitrogen alloy.
Example 2
The rare earth silicon-nitrogen alloy provided by the embodiment 2 comprises the following element components in percentage by mass, namely Si: 58%, N: 6%, La: 15%, Nd: 0.3%, Mo: 7.0%, B: 8%, V: 3.1%, Nb: 0.15%, Ti: 0.2%, Al: 0.1%, C: 1.8%, Mn: 0.05% and the balance of iron.
Weighing raw materials according to the content ratio of the element components, selecting simple substance raw materials for the raw materials in the embodiment, carrying out impurity removal and moisture removal pretreatment on the weighed raw materials, and grinding the pretreated raw materials to obtain powder with the particle size of less than or equal to 0.15 mm; then uniformly mixing the fine powder and modified phenolic resin to obtain a mixture, wherein the consumption of the modified phenolic resin accounts for 3% of the total mass of the fine powder, and the carbon content in the modified phenolic resin is 67%; and putting the mixture into a nitriding furnace for nitriding treatment, wherein the pressure of nitrogen in the nitriding furnace is 0.3MPa, heating to 1100 ℃ at the heating rate of 17 ℃/min, preserving heat for 3h, heating to 1350 ℃ at the heating rate of 6 ℃/min, preserving heat for 7h, and then cooling to 280 ℃ at the cooling rate of 5 ℃/min to obtain the rare earth silicon-nitrogen alloy.
Example 3
The rare earth silicon-nitrogen alloy provided in embodiment 3 includes the following element components by mass percent, Si: 11%, N: 35%, Ce: 1.15%, La: 0.30%, Pr: 0.20%, Sm: 1.2%, C: 7.5%, Cr: 0.1%, Mn: 0.15%, Ti: 12%, Nb: 6%, Ca: 4.5%, P: 0.20%, S: 0.10% and the balance Fe.
Weighing the raw materials according to the content ratio of the element components, wherein the raw materials in the embodiment are a mixture of a simple substance and a compound, and the Ce source is a simple substance Ce and CeO2The Sm source is simple substance Sm and Sm2O3The Mn source is simple substance Mn and MnO, and the Si source is simple substance Si and SiO2The Fe source is iron simple substance and Fe2O3And the other raw materials are simple substances. Carrying out impurity removal and moisture removal pretreatment on the weighed raw materials, and grinding the pretreated raw materials to obtain fine powder with the particle size of less than or equal to 0.15 mm; uniformly mixing the fine powder, modified phenolic resin and carbon powder, silicon powder and aluminum powder serving as a reducing agent to obtain a mixture, wherein the using amount of the modified phenolic resin accounts for 2% of the total mass of the fine powder, the carbon content in the modified phenolic resin is 67%, and the adding amount of the reducing agent is 17% of the total mass of the fine powder; and putting the mixture into a nitriding furnace for nitriding treatment, filling mixed gas of nitrogen and argon into the nitriding furnace, heating to 1000 ℃ at the heating rate of 20 ℃/min, preserving heat for 3.5 hours, heating to 1400 ℃ at the heating rate of 7 ℃/min, preserving heat for 6.5 hours, and then cooling to 250 ℃ at the cooling rate of 6 ℃/min to obtain the rare earth silicon-nitrogen alloy.
Example 4
The rare earth silicon-nitrogen alloy provided in embodiment 4 includes the following element components by mass percent, Si: 24%, La: 12%, Nd: 12%, Mn: 27%, N: 23%, B: 0.05%, Ca: 0.60%, Mo: 0.70%, P: 0.10%, S: 0.05% and the balance Fe.
Weighing the raw materials according to the content ratio of the element components, wherein the raw materials in the embodiment areA mixture of simple substance and compound, wherein the La source is simple substance La and La2O3The Nd source is elementary Nd and Nd2O3The Mn source is simple substance Mn and MnO, the Fe source is iron simple substance and Fe2O3And the other raw materials are simple substances. Carrying out impurity removal and moisture removal pretreatment on the weighed raw materials, and grinding the pretreated raw materials to obtain fine powder with the particle size of less than or equal to 0.15 mm; uniformly mixing the fine powder, modified phenolic resin and carbon powder, silicon powder and aluminum powder serving as a reducing agent to obtain a mixture, wherein the using amount of the modified phenolic resin accounts for 3% of the total mass of the fine powder, the carbon content in the modified phenolic resin is 65%, and the adding amount of the reducing agent is 13% of the total mass of the fine powder; and putting the mixture into a nitriding furnace for nitriding treatment, filling mixed gas of nitrogen and argon into the nitriding furnace, heating to 1050 ℃ at the heating rate of 20 ℃/min, preserving the heat for 4h, heating to 1450 ℃ at the heating rate of 9 ℃/min, preserving the heat for 6h, and then reducing the temperature to 200 ℃ at the cooling rate of 4 ℃/min to obtain the rare earth silicon-nitrogen alloy.
Example 5
The rare earth silicon-nitrogen alloy provided in embodiment 5 includes the following element components, by mass, Si: 43%, Cr: 19%, C: 0.8%, N: 21%, Al: 0.45%, Ce: 0.10%, La: 3.2%, Pr: 1.71%, P: 0.11%, S: 0.13%, Ca: 1.05 percent and the balance of Fe.
Weighing raw materials according to the content ratio of the element components, selecting simple substance raw materials for the raw materials in the embodiment, carrying out impurity removal and moisture removal pretreatment on the weighed raw materials, and grinding the pretreated raw materials to obtain fine powder with the particle size of less than or equal to 0.15 mm; then uniformly mixing the fine powder and the modified phenolic resin to obtain a mixture, and preparing the mixture into pellets, wherein the use amount of the modified phenolic resin accounts for 2% of the total mass of the fine powder, and the carbon content in the modified phenolic resin is 67%; and (3) putting the mixture of the pellets into a nitriding furnace for nitriding treatment, wherein the pressure of nitrogen in the nitriding furnace is 0.25MPa, heating to 950 ℃ at the heating rate of 19 ℃/min, preserving heat for 3.5h, heating to 1400 ℃ at the heating rate of 10 ℃/min, preserving heat for 7h, and then cooling to 300 ℃ at the cooling rate of 6 ℃/min to obtain the rare earth silicon-nitrogen alloy.
Comparative example 1
The experimental group 1 used the rare earth-silicon-nitrogen alloy of example 1 as an alloy additive, and the control group 1 used the rare earth alloy and silicon-nitrogen alloy as alloy additives, wherein the rare earth alloy includes La: 14%, Ce: 19%, Si: 36% and the balance being Fe, the silicon nitrogen alloy comprising Si: 9%, N: 17 percent. The alloy additives of the experimental group 1 and the control group 1 are respectively applied to the improvement of molten steel inclusion deformation, the refinement of steel crystal grains and the performance strengthening of steel, the improvement effect of the inclusion deformation of the experimental group 1 is good, the refinement level of the steel crystal grains is improved and stable, and the comprehensive performance strengthening effect of the steel is excellent and stable. Specific results are shown in table 1, and the data in table 1 are the average values obtained from two parallel tests.
TABLE 1 COMPARATIVE TABLE OF STEEL PERFORMANCE OF EXPERIMENTAL GROUP 1 AND COMPARATIVE GROUP 1
Figure BSA0000198861370000091
Comparative example 2
The experimental group 2 used the rare earth-silicon-nitrogen alloy of example 4 as an alloy additive, and the control group 2 used the rare earth alloy and the silicon-nitrogen alloy as alloy additives, wherein the rare earth alloy includes La: 14%, Ce: 19%, Si: 36% and the balance being Fe, the silicon nitrogen alloy comprising Si: 48.6%, N: 29.3 percent and the balance of Fe. The alloy additives of the experimental group 2 and the control group 2 are respectively applied to the improvement of molten steel inclusion deformation, the refinement of steel crystal grains and the performance strengthening of steel, the improvement effect of the inclusion deformation of the experimental group 2 is good, the refinement level of the steel crystal grains is improved and stable, and the comprehensive performance strengthening effect of the steel is excellent and stable. Specific results are shown in table 2, and the data in table 2 are the average values obtained from two parallel tests.
TABLE 2 comparison table of Steel Performance between Experimental group 2 and control group 2
Figure BSA0000198861370000092
Figure BSA0000198861370000101
From the results in tables 1 and 2, it can be seen that the rare earth silicon-nitrogen alloy provided by the invention as an alloy additive can better improve the comprehensive performance of steel than the rare earth alloy and multiple alloys of silicon-nitrogen alloy as alloy additives. And the compound of the element component can be selected as the raw material when the rare earth silicon-nitrogen alloy is prepared, so that the cost of the alloy additive is reduced.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. The rare earth silicon-nitrogen alloy comprises the following element components in percentage by mass: si: 9-58%, N: 6-35%, Ce: 0-19%, La: 0-15%, Pr: 0-6%, Nd: 0-12%, Sm: 0-4.5% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time.
2. The rare earth-silicon-nitrogen alloy of claim 1, further comprising: cr: 0-19%, V: 0-9%, Ti: 0-12%, Nb: 0-6%, Mn: 0.03 to 27%, Mo: 0-7%, Ni: 0-6.5%, B: 0 to 8 percent.
3. The method for preparing rare earth silicon nitrogen alloy of any one of claims 1 to 2, characterized by comprising the following steps:
1) mixing raw materials of other element components except nitrogen according to element proportion, and grinding to obtain fine powder;
2) mixing the fine powder obtained in the step 1) with a binding agent to obtain a mixture;
3) and (3) nitriding the mixture obtained in the step 2), and then cooling to obtain the rare earth silicon-nitrogen alloy.
4. The method for preparing a rare-earth silicon-nitrogen alloy according to claim 3, wherein the nitriding treatment in the step 3) is a low-temperature nitriding treatment and a high-temperature nitriding treatment which are sequentially performed on the mixture.
5. The method for preparing rare earth silicon nitrogen alloy according to claim 4, wherein the temperature of the low-temperature nitriding treatment is 900-1100 ℃ and the time is 3-4 h; the temperature of the high-temperature nitriding treatment is 1350-1450 ℃, and the time is 6-7 h.
6. The method for preparing a rare earth-silicon-nitrogen alloy according to any one of claims 3 to 5, wherein the nitriding treatment in the step 3) is performed under a protective gas, the protective gas comprises nitrogen, and the pressure of the protective gas is 0.2 to 0.3 MPa;
the cooling rate of the cooling in the step 3) is 4-6 ℃/min, and the temperature after the cooling is 200-300 ℃.
7. The method of claim 6, wherein the protective gas further comprises argon, and when the protective gas comprises argon and nitrogen, the nitrogen has a concentration of 99% or more.
8. The preparation method of the rare earth silicon-nitrogen alloy according to claim 3, wherein the mass of the binding agent in the step 2) is 2-3% of the total weight of the fine powder, the binding agent comprises modified phenolic resin, and the carbon content in the modified phenolic resin is greater than or equal to 65%.
9. The method for preparing a rare-earth-silicon-nitrogen alloy according to claim 3, wherein when the source of the raw material in step 1) includes a simple substance and an oxide, and when the source of the rare-earth element, the silicon element, the manganese element, and the iron element includes an oxide of the corresponding element, the mixing in step 2) further adds a reducing agent; the dosage of the reducing agent is 10-20% of the total weight of the fine powder; the reducing agent comprises one or more of carbon powder, silicon powder and aluminum powder.
10. Use of a rare earth-silicon-nitrogen alloy according to any one of claims 1 to 2 or a rare earth-silicon-nitrogen alloy obtained by the preparation method according to any one of claims 3 to 9 as an alloying additive.
CN201911389270.5A 2019-12-30 2019-12-30 Rare earth silicon-nitrogen alloy and preparation method and application thereof Pending CN111020358A (en)

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