CN111041333A - Rare earth silicon-nitrogen-niobium alloy and preparation method and application thereof - Google Patents
Rare earth silicon-nitrogen-niobium alloy and preparation method and application thereof Download PDFInfo
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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-niobium alloy and a preparation method and application thereof. The rare earth silicon nitrogen niobium alloy provided by the invention comprises the following element components in percentage by mass: si: 5.5-50%, N: 4-29%, Ce: 0-21%, La: 0-16%, Pr: 0-6%, Nd: 0-12%, Sm: 0-5%, Nb: 3-37%, B: 0-6% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time. The invention adopts the nitriding treatment process to prepare the rare earth silicon-nitrogen-niobium alloy, wherein the niobium can dissolve C, N atoms in the steel, so that the anti-aging property of the steel is improved, and meanwhile, the invention obviously improves the comprehensive mechanical property of the steel under the synergistic action of the niobium, the silicon, the nitrogen and the rare earth elements.
Description
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-niobium alloy and a preparation method and application thereof.
Background
The special steel is different from the traditional steel, mainly comprises an alloy form, generally has the characteristics of good oxidation resistance, corrosion resistance, high temperature resistance and the like, can be used in extremely harsh environment, and is mainly used in special industries. Alloying is an important part in the production process flow of special steel, and mainly comprises molten steel alloying and molten steel microalloying, wherein molten steel microalloying elements generally refer to adding trace metal carbonitride forming elements, rare earth elements and the like on the basis of original main alloying elements, so that the alloying has influence on mechanical properties or plays a role in corrosion resistance and heat resistance; in the microalloying process of molten steel, required elements are directly added in the steelmaking stage of a converter, but because the melting points of various metals are different, metal loss is easily caused in the production process, the functions of the elements cannot be fully exerted, and the performance of steel is further influenced. Meanwhile, 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-niobium alloy, and a preparation method and application thereof.
The invention provides a rare earth silicon nitrogen niobium alloy which comprises the following element components in percentage by mass: si: 5.5-50%, N: 4-29%, Ce: 0-21%, La: 0-16%, Pr: 0-6%, Nd: 0-12%, Sm: 0-5%, Nb: 3-37%, B: 0-6% 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 niobium alloy further comprises: further comprising: cr: 0-19%, Mn: 0.03-21%, Mo: 0-7%, Ni: 0-6.5%, V: 0-8.5%, Ti: 0 to 13 percent.
The invention provides a preparation method of the rare earth silicon nitrogen niobium alloy in the technical scheme, which comprises 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 in the step 2) to obtain the rare earth silicon-nitrogen-niobium 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 in the step 3) is 3-5 ℃/min, and the temperature after the cooling is 200-300 ℃.
Preferably, the protective gas further comprises argon, and when the protective gas is argon or 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, the sources of the raw materials in the step 1) comprise simple substances and oxides, and when the sources of the rare earth elements, the silicon elements, the manganese elements, the niobium elements and the iron elements 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-niobium alloy in the technical scheme or the rare earth silicon-nitrogen-niobium alloy obtained by the preparation method in the technical scheme in an alloy additive.
Has the advantages that: the invention provides a rare earth silicon nitrogen niobium alloy which comprises the following element components in percentage by mass: si: 5.5-50%, N: 4-29%, Ce: 0-21%, La: 0-16%, Pr: 0-6%, Nd: 0-12%, Sm: 0-5%, Nb: 3-37%, B: 0-6% and the balance of Fe, wherein the contents of Ce, La, Pr, Nd and Sm are not 0 at the same time. Among them, niobium can dissolve C, N atoms in the steel material in a solid state, and the anti-aging property of the steel is improved. And the invention obviously improves the comprehensive mechanical property of the steel under the synergistic action of niobium, silicon, nitrogen and rare earth elements.
Furthermore, the invention alloys niobium, silicon, nitrogen, rare earth elements and other elements to replace rare earth alloy, silicon nitride and silicon nitride manganese alloy to be applied to steel making or steel casting, does not need to add rare earth alloy and several kinds of nitride alloy simultaneously, simplifies the application process and effectively widens the application range of the rare earth silicon nitrogen niobium alloy. The preparation method can select or add partial oxides containing rare earth, Si, Mn and Nb as raw materials, greatly reduce the manufacturing cost, reduce the comprehensive cost by more than 35 percent compared with equivalent alloy, improve the comprehensive mechanical property of steel, and simultaneously realize safe, environment-friendly and no waste discharge in the production process.
Detailed Description
The invention provides a rare earth silicon nitrogen niobium alloy which comprises the following element components in percentage by mass: si: 5.5-50%, N: 4-29%, Ce: 0-21%, La: 0-16%, Pr: 0-6%, Nd: 0-12%, Sm: 0-5%, Nb: 3-37%, B: 0-6% 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 niobium alloy, which comprises the following components in percentage by mass: 5.5 to 50%, preferably 8 to 38%, and more preferably 11 to 20%.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises the following components in percentage by mass: 4 to 29%, preferably 5 to 20%, and more preferably 13 to 18%.
The rare earth silicon-nitrogen-niobium alloy comprises, by mass, 3-37% of Nb, preferably 10-25% of Nb, and further preferably 15-20% of Nb, wherein the Nb can prevent the recrystallization of deformed austenite of steel, improves the plasticity of steel, obtains very fine ferrite grains after gamma- α phase transformation, improves the anti-aging property of the steel, and simultaneously can dissolve C, N atoms in the steel to improve the anti-aging property of the steel.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises the following components in percentage by mass: 0 to 21%, preferably 0.2 to 1.0%, and more preferably 5 to 10%.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises La: 0 to 16%, preferably 0.1 to 2%, and more preferably 10 to 16%.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises the following components in percentage by mass: 0 to 6%, preferably 0.1 to 0.5%, and more preferably 3 to 5%.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises the following components in percentage by mass: 0 to 12%, preferably 2 to 10%, and more preferably 5 to 8.5%.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises Sm: 0 to 5%, preferably 0.3 to 3.2%, and more preferably 0.4 to 2.5%.
In the present invention, the rare earth element includes one or more elements of Ce, La, Pr, Nd, and Sm, and in an embodiment of the present invention, the rare earth element is preferably four elements of Sm, La, Pr, and Nd, Ce, La, Pr, and Sm, or La, Ce, Pr, and Nd.
The invention provides a rare earth silicon nitrogen niobium alloy, which comprises the following components in percentage by mass: 0 to 6%, preferably 0.1 to 5%, and more preferably 0.2 to 2%. In the invention, B and Nb are cooperated, so that the reinforcing effect of the steel is obviously improved.
The rare earth silicon-nitrogen-niobium alloy comprises the balance of Fe according to mass content.
The rare earth silicon-nitrogen-niobium alloy provided by the invention preferably further comprises the following components in percentage by mass: cr: 0-19%, Mn: 0.03-21%, Mo: 0-7%, Ni: 0-6.5%, V: 0-8.5%, Ti: 0 to 13 percent. The invention limits the content of Cr, Mn, Mo and Ni elements in the rare earth silicon-nitrogen-niobium alloy to ensure that the alloy improves the comprehensive performance of steel, thereby being capable of applying the rare earth silicon-nitrogen-niobium alloy to the field of alloy additives.
The rare earth silicon-nitrogen-niobium alloy provided by the invention further comprises impurities according to the mass content, wherein the impurities comprise Ca: 0.01-6.5%, Mg: 0-4.5%, Al: 0.02-8%, C: 0.05-7.5%, P is less than or equal to 0.20%, and S is less than or equal to 0.20%.
The invention limits the content of each element within a specific range, and obtains the rare earth silicon-nitrogen-niobium alloy under the synergistic action of each element, and the rare earth silicon-nitrogen-niobium alloy can better improve the comprehensive mechanical property of steel and enables the steel to have higher anti-aging performance.
The invention also provides a preparation method of the rare earth silicon-nitrogen-niobium alloy in the technical scheme, which comprises 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 in the step 2) to obtain the rare earth silicon-nitrogen-niobium alloy.
The raw materials of other element components except nitrogen are mixed according to the element proportion and then ground into fine powder, and the particle size of the fine powder is preferably less than or equal to 0.2 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, and the oxide preferably comprises CeO, SmO, NdO and La2O3、SiO2、Nb2O5MnO and Fe2O3One or more of。
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 carbon content in the modified phenolic resin is preferably more than or equal to 65%, and 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 the Ministry of education and chemical industry in the consolidated city, and the model is NGL-A. In the invention, 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-niobium 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-niobium alloy.
In the invention, when the raw materials comprise compounds, a reducing agent is preferably added in the mixing process, the reducing agent can reduce the compounds into simple substances in the nitriding treatment process, and the reducing agent is preferably one or more of carbon powder, silicon powder and aluminum powder; the carbon content in the carbon powder is preferably equal to or more than 95%, the silicon content in the silicon powder is preferably equal to or more than 98%, and the aluminum content of the aluminum powder is preferably equal to or more than 96%. The carbon powder, the silicon powder and the aluminum powder can reduce oxides in the materials into simple substances of corresponding elements. The addition of the reducing agent introduces carbon and aluminum impurities into the rare earth silicon-nitrogen-niobium alloy.
In the invention, the Nb source is preferably one or more of metal niobium, niobium pentoxide and niobium concentrate, and the production cost of the rare earth silicon-nitrogen-niobium is remarkably reduced while the performance of the rare earth silicon-nitrogen-niobium is ensured by enlarging the niobium source.
After the mixture is obtained, the mixture is subjected to nitriding treatment to obtain the rare earth silicon-nitrogen-niobium 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 protective gas preferably further includes argon, and when the protective gas is argon or 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. The staged nitridation process of the present invention is preferably performed in a continuous process in the same nitridation furnace. In the invention, the temperature of the low-temperature nitriding treatment is preferably 900-1100 ℃, and further preferably 1000-1060 ℃; the heating rate of heating to the low-temperature nitriding temperature is preferably 15-20 ℃/min; the heat preservation 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 is further preferably 1375-1435 ℃; 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 preferably cooled to obtain the rare earth silicon-nitrogen-niobium alloy, wherein the cooling rate is preferably 5.5-6.5 ℃/min, and the temperature after cooling is preferably 200-300 ℃.
The invention also provides the application of the rare earth silicon-nitrogen-niobium alloy in the technical scheme or the rare earth silicon-nitrogen-niobium alloy prepared by the preparation method in the technical scheme in 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, the performance reinforcement of steel and the anti-aging property of steel, thereby improving the comprehensive mechanical properties of steel.
To further illustrate the present invention, the following examples are provided to describe the rare earth-silicon-nitrogen-niobium 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 niobium alloy provided by the embodiment 1 comprises the following element components in percentage by mass, Si: 7.1%, N: 29%, Ce: 21%, La: 1.7%, Pr: 0.2%, Nd: 2.2%, Ti: 0.7%, Nb: 24.1%, B: 0.34%, Ni: 6.5%, Ca: 6.5%, Mg: 0.12%, Mo: 0.27%, Mn: 0.03%, Al: 0.02%, C: 0.71%, P: 0.06%, S: 0.05% 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 powder with the particle size of less than or equal to 0.2 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 65%; 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 3 ℃/min to obtain the rare earth silicon-nitrogen-niobium alloy.
Example 2
The rare earth silicon nitrogen niobium alloy provided by the embodiment 2 comprises the following element components in percentage by mass, namely Si: 9%, N: 16%, La: 16%, Nd: 9.2%, Pr: 3.1%, Sm: 2.3%, V: 20%, Nb: 3.0%, Ni: 6.5%, Mo: 1.3%, Cr: 10.2%, Mn: 0.10%, B: 1.13%, Al: 2.7%, C: 0.05%, Ca: 1.1%, Mg: 0.6%, S: 0.03 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 powder with the particle size of less than or equal to 0.2 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 66%; 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 16 ℃/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-niobium alloy.
Example 3
The rare earth silicon-nitrogen-niobium alloy provided in embodiment 3 includes the following element components by mass percent, Si: 5.5%, N: 4%, Ce: 8.3%, Nd: 6.1%, Pr: 6.0%, Sm: 0.4%, Nb: 37%, C: 1.17%, Al: 8.1%, Cr: 1.36%, Mn: 1.09%, Mo: 7%, Ni: 0.2%, Ca: 0.26%, Mg: 4.5%, P: 0.20%, Ti: 1.27%, V: 3.3 percent and the balance of Fe.
The raw materials are weighed according to the content ratio of the element components, and the raw materials of the embodiment are a mixture of a simple substance and a compound, wherein the Ce source is a simple substance Ce and CeO, the Sm source is a simple substance Sm and SmO, and the Nb source is a simple substance Nb and Nb2O5The Fe source is the 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 powder with the particle size of less than or equal to 0.2 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 a mixed gas of nitrogen and argon into the nitriding furnace, heating to 1000 ℃ at a heating rate of 19 ℃/min, preserving heat for 3.5 hours, heating to 1400 ℃ at a heating rate of 7 ℃/min, preserving heat for 6.5 hours, and then cooling to 250 ℃ at a cooling rate of 4 ℃/min to obtain the rare earth silicon-nitrogen-niobium alloy.
Example 4
The rare earth silicon-nitrogen-niobium alloy provided in embodiment 4 includes the following element components by mass percent, Si: 11.2%, La: 0.2%, Ce: 0.3%, Sm: 0.31%, Nd: 12%, Mn: 21%, N: 5.2%, Nb: 15.1%, V: 0.4%, Ti: 23%, B: 0.17%, Ca: 0.01%, Mg: 0.13%, Ni: 0.11%, Cr: 0.3%, Al: 0.3%, C: 7.5%, P: 0.04%, S: 0.20% and the balance Fe.
Weighing the raw materials according to the content ratio of the element components, wherein the raw materials of the embodiment are a mixture of a simple substance and a compound, the La source is a simple substance La and LaO, the Nd source is a simple substance Nd and NdO, and the Nb source is a simple substance Nb and Nb2O5And niobium concentrate, wherein 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 powder with the particle size of less than or equal to 0.2 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-niobium alloy.
Example 5
The rare earth silicon-nitrogen-niobium alloy provided in embodiment 5 includes the following element components by mass percent, Si: 50% of Cr: 19%, V: 0.6%, Ti: 0.20%, Nb: 10.2%, B: 6.5%, C: 0.16%, N: 4.7%, Al: 0.21%, Ce: 0.50%, La: 0.40%, Pr: 0.10%, Sm: 3.2%, P: 0.03%, S: 0.02%, Ca: 0.12%, Mn: 0.1%, Mo: 0.05%, Ni: 0.01 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 powder with the particle size of less than or equal to 0.2 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 5 ℃/min to obtain the rare earth silicon-nitrogen-niobium alloy.
Comparative example 1
The experimental group 1 uses the rare earth silicon nitrogen niobium alloy of the embodiment 1 as an experimental group, and the comparison group 1 uses rare earth alloy, silicon nitrogen alloy and niobium alloy as alloy additives, wherein the rare earth alloy comprises RE: 31.26%, Si: 32.77%, Mn: 2.65%, Ca: 3.25%, Ti: 2.16%, and the balance of Fe, wherein the silicon-nitrogen alloy comprises Si: 51.76%, N: 29.37%, Al: 0.73%, and the balance of Fe, wherein the niobium alloy comprises Nb: 66.12%, Al: 0.53%, Si: 1.83 percent and the balance of Fe. 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, the performance strengthening and the anti-aging performance 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 steel has better anti-aging performance. 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
Comparative example 2
The experimental group 2 used the rare earth silicon-nitrogen-niobium alloy of example 3 as an alloy additive, and the control group 2 used the rare earth alloy, silicon-nitrogen alloy and niobium alloy as an alloy additive, wherein the rare earth alloy comprises: RE: 18.64%, Mg: 9.03%, Si: 34.27%, Mn: 2.33%, Ca: 3.76%, Ti: 1.86%, the balance being Fe, the silicon-nitrogen alloy comprising: si: 4.76%, N: 28.65%, Al: 0.58%, the balance being Fe, the niobium alloy comprising: nb: 65.37%, Al: 0.69%, Si: 1.42 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, the performance strengthening and the anti-aging performance 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 steel has better anti-aging performance. 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
As can be seen from the results in tables 1 and 2, the rare earth-silicon-nitrogen-niobium alloy provided by the present invention as an alloy additive can improve the anti-aging property of steel better than rare earth alloys, silicon-nitrogen alloys and niobium alloys as an alloy additive, and the improvement rate in yield strength is 1.9 to 4.9%, and the improvement rate in tensile strength is 4.2 to 10.3%. And when the rare earth silicon nitrogen niobium alloy is prepared, a compound of an element component can be selected as a raw material, so that the cost of the alloy additive is reduced.
Compared with rare earth alloy, silicon-nitrogen alloy and niobium alloy which are used as alloy additives, the rare earth silicon-nitrogen-niobium alloy provided by the invention can better improve the comprehensive performance of steel.
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 niobium alloy comprises the following element components in percentage by mass: si: 5.5-50%, N: 4-29%, Ce: 0-21%, La: 0-16%, Pr: 0-6%, Nd: 0-12%, Sm: 0-5%, Nb: 3-37%, B: 0-6% 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-niobium alloy as claimed in claim 1, further comprising: cr: 0-19%, Mn: 0.03-21%, Mo: 0-7%, Ni: 0-6.5%, V: 0-8.5%, Ti: 0 to 13 percent.
3. The method for preparing the rare earth silicon nitrogen niobium alloy according to 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) nitriding the mixture obtained in the step 2) to obtain the rare earth silicon nitrogen niobium alloy.
4. The method for preparing a rare earth-silicon-nitrogen-niobium alloy as claimed in claim 3, wherein the nitriding treatment in step 3) is a step of subjecting the mixture to a low temperature nitriding treatment and a high temperature nitriding treatment in this order.
5. The method for preparing the rare earth silicon nitrogen niobium alloy as claimed in claim 4, wherein the temperature of the low-temperature nitridation 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-niobium 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 3-5 ℃/min, and the temperature after the cooling is 200-300 ℃.
7. The method for producing a rare earth-silicon-nitrogen-niobium alloy according to claim 6, wherein the protective gas further comprises argon, and when the protective gas is argon or nitrogen, the concentration of nitrogen is 99% or more.
8. The preparation method of the rare earth silicon-nitrogen-niobium alloy as claimed in claim 3, wherein the mass of the binding agent in the step 2) is 2-3% of the total weight of the fine powder, and 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-niobium alloy as claimed in claim 3, wherein the source of the raw material in step 1) comprises simple substances and oxides, and when the source of the rare earth element, the silicon element, the manganese element, the niobium element and the iron element comprises oxides of the corresponding elements, the mixing in step 2) is further added with 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 the rare earth silicon-nitrogen-niobium alloy of any one of claims 1 to 2 or the rare earth silicon-nitrogen-niobium alloy obtained by the preparation method of any one of claims 3 to 9 as an alloy additive.
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