CN113088788B - Method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel - Google Patents
Method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel Download PDFInfo
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Abstract
The invention provides a method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel. The method comprises the steps of pre-melting industrial pure iron and a graphite rod, and then sequentially adding a manganese-containing raw material and an aluminum-containing raw material for smelting; after the manganese-containing raw material and the aluminum-containing raw material are completely melted down, adding a predetermined amount of sulfur-containing raw material to obtain molten steel; and then casting the molten steel into the model to obtain the high-aluminum steel with low harmfulness of aluminum nitride inclusions. Through the mode, the method can realize the full wrapping of the brittle aluminum nitride inclusions by the plastic manganese sulfide inclusions by regulating and controlling the sulfur content in the high-aluminum steel and utilizing the higher deformability of the formed manganese sulfide inclusions, thereby reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel. The method provided by the invention is simple to operate, has a wide application range, can effectively reduce the number of pure aluminum nitride inclusions in the high-aluminum steel, improves the hardness and tensile strength of the high-aluminum steel, and has a high practical application value.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy, in particular to a method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel.
Background
High-aluminum steels generally have high surface hardness, wear resistance, excellent plasticity, toughness and other mechanical properties, the aluminum content of the high-aluminum steels is usually more than 1%, and the high-aluminum steels comprise high-manganese high-aluminum low-density steels, TRIP steels, TWIP steels, electrical steels, iron-chromium-aluminum stainless steels and the like. In recent years, in order to meet the requirement of lightweight in the field of automobile manufacturing, high-manganese high-aluminum steel with high strength-plasticity product and low density is a hot steel type, the aluminum content in the steel is up to 10%, and the steel also shows huge application potential in the fields of ocean engineering and military industry.
However, high levels of aluminum tend to combine with nitrogen during the smelting process to form aluminum nitride inclusions. And the aluminum nitride belongs to hard brittle inclusion, is in a polygonal structure and is difficult to remove in the smelting process. The residual aluminum nitride inclusions in the steel have low thermal expansion coefficient, and stress concentration is often generated in the process of processing deformation to become the origin of cracks, thereby seriously affecting the service performance of the steel. Therefore, it is necessary to reduce the damage of the aluminum nitride inclusions to the high-aluminum steel to improve the usability of the high-aluminum steel.
At present, if the harm effect of aluminum nitride inclusions on the performance of steel is to be reduced, the quantity of the aluminum nitride inclusions is reduced by controlling the nitrogen content in molten steel. For example, patent publication No. CN102051439A provides a method for smelting high-alumina steel, in which the production of inclusions is reduced by performing electric arc furnace smelting, external refining and vacuum furnace smelting in this order, and extracting gas in the vacuum furnace by using the vacuum furnace smelting process to remove gas such as hydrogen, nitrogen, oxygen and the like from molten steel. However, in this method, vacuum smelting equipment needs to be added, the cost is high, and nitrogen increase in molten steel cannot be avoided in the casting process after smelting is completed, so that the problem caused by aluminum nitride inclusions is difficult to be fundamentally solved. Moreover, although the performance of various smelting equipment has been improved in recent years, the control of nitrogen element in molten steel reaches a limit value under the existing equipment and smelting level, and how to reduce the hazard of aluminum nitride inclusions in a simple and effective manner under the condition of not changing the existing smelting equipment still remains a problem to be solved at present.
In view of the above, it is necessary to research a method for reducing the harmfulness of the aluminum nitride inclusions in the high aluminum steel, so as to solve the problems caused by the aluminum nitride inclusions in the high aluminum steel.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a method for reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel. The sulfur content in the high-aluminum steel is regulated and controlled, and the high deformability of the formed manganese sulfide inclusion is utilized to realize the full wrapping of the brittle aluminum nitride inclusion by the plastic manganese sulfide inclusion, so that the harmfulness of the aluminum nitride inclusion in the high-aluminum steel is reduced.
In order to achieve the purpose, the invention provides a method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel, which comprises the following steps:
s1, preparing materials according to preset high-aluminum steel components;
s2, pre-melting the industrial pure iron and the graphite rod, and then sequentially adding a manganese-containing raw material and an aluminum-containing raw material for smelting; after the manganese-containing raw material and the aluminum-containing raw material are completely melted down, adding a sulfur-containing raw material to obtain molten steel;
and S3, casting the molten steel obtained in the step S2 into a model to obtain the high-aluminum steel.
As a further improvement of the invention, in step S1, the manganese content in the preset high-aluminum steel composition is more than 3%.
As a further improvement of the present invention, in step S1, the predetermined high aluminum steel composition contains 0.01% to 0.03% of sulfur.
As a further improvement of the present invention, in step S2, the smelting device used in the smelting process includes, but is not limited to, one of an induction furnace, an electric arc furnace and a ladle furnace.
As a further improvement of the method, in step S2, when the smelting equipment is an induction furnace, the induction furnace is vacuumized and heated to 1500-1700 ℃, after the industrial pure iron and the graphite rod are melted, an inert gas is introduced into the induction furnace, and then the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material are sequentially added.
As a further improvement of the present invention, in step S2, the commercially pure iron and graphite rod are put into a crucible in advance; and putting the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material into a storage bin.
As a further improvement of the invention, the crucible is a magnesium oxide prefabricated crucible with the mass purity of more than 95% or an aluminum oxide prefabricated crucible with the mass purity of more than 95%.
As a further improvement of the present invention, in step S2, after the manganese-containing raw material is added, the aluminum-containing raw material is added after the manganese-containing raw material is completely melted.
As a further improvement of the invention, the sulfur-containing raw material comprises one or more of but not limited to sulfur iron, pyrite and sulfur powder.
As a further improvement of the invention, the manganese-containing raw material is electrolytic manganese or manganese-containing alloy; the aluminum-containing raw material is aluminum particles, aluminum ingots or aluminum-containing alloys.
The invention has the beneficial effects that:
(1) according to the invention, the sulfur-containing raw material is added in the smelting process of the high-aluminum steel, so that the manganese sulfide inclusion can be generated by the reaction of the sulfur element in the sulfur-containing raw material and the manganese element in the high-aluminum steel. Because the manganese sulfide inclusion has a thermal expansion coefficient far higher than that of a steel matrix and aluminum nitride inclusion, the shape of the manganese sulfide inclusion is easy to change in the steel processing deformation process, and the defects of microcracks and the like are not easy to generate. On the basis, the method utilizes the great difference of the processing deformability of the manganese sulfide inclusion and the aluminum nitride inclusion, and regulates and controls the sulfur content in the high-aluminum steel component to promote the manganese sulfide to take the aluminum nitride inclusion as a precipitation core in the solidification process, so that the fragile aluminum nitride inclusion is completely coated by the easily deformed plastic manganese sulfide inclusion, thereby effectively reducing the hazard of the aluminum nitride inclusion in the high-aluminum steel and improving the hardness and tensile strength of the high-aluminum steel.
(2) According to the invention, by controlling the adding sequence of the raw materials, carbon monoxide bubbles can be formed and float upwards by utilizing the reaction of the graphite rods added in advance and oxygen in the molten steel under vacuum, so that oxygen in the molten steel is consumed, and the formation of alumina inclusions is avoided; meanwhile, the manganese-containing raw material is added before the aluminum-containing raw material, so that the manganese element is pre-deoxidized, and the formation of alumina impurities is reduced; in addition, the sulfur-containing raw material is added at last, and beneficial conditions can be provided for accurate wrapping and modification of aluminum nitride inclusions.
(3) Compared with the mode of reducing the quantity of the aluminum nitride inclusions by controlling the nitrogen content in the molten steel in the prior art, the method provided by the invention utilizes the manganese sulfide inclusions which do not influence the performance of the aluminum steel to coat the aluminum nitride inclusions, is simple and convenient to operate, is not limited to vacuum smelting equipment, and has low implementation cost and wider application range. Based on the method provided by the invention, the number of pure aluminum nitride inclusions in the high-aluminum steel can be obviously reduced, the hardness and tensile strength of the high-aluminum steel are improved, the harmfulness of the aluminum nitride inclusions is effectively reduced, and the method has high practical application value.
Drawings
FIG. 1 is a topographical view of manganese sulfide coated aluminum nitride inclusions formed in example 1.
FIG. 2 is a morphology of a pure aluminum nitride inclusion formed in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel, which comprises the following steps of:
s1, preparing materials according to preset high-aluminum steel components;
s2, pre-melting the industrial pure iron and the graphite rod, and then sequentially adding a manganese-containing raw material and an aluminum-containing raw material for smelting; after the manganese-containing raw material and the aluminum-containing raw material are completely melted down, adding a sulfur-containing raw material to obtain molten steel;
and S3, casting the molten steel obtained in the step S2 into a model to obtain the high-aluminum steel.
In step S1, the predetermined high-aluminum steel composition contains manganese of more than 3% and sulfur of 0.01% to 0.03%.
In step S2, the commercially pure iron and graphite rod are placed in advance in a crucible; putting the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material into a storage bin; after the manganese-containing raw material is added, adding the aluminum-containing raw material after the manganese-containing raw material is completely melted; the crucible is a magnesium oxide prefabricated crucible with the mass purity of more than 95 percent or an aluminum oxide prefabricated crucible with the mass purity of more than 95 percent.
In step S2, the smelting process uses a smelting device including, but not limited to, one of an induction furnace, an electric arc furnace, and a ladle furnace. When the smelting equipment is an induction furnace, firstly vacuumizing the induction furnace, heating to 1500-1700 ℃, introducing inert gas into the induction furnace after the industrial pure iron and the graphite rod are melted, and then sequentially adding the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material.
The sulfur-containing raw material comprises but is not limited to one or more of sulfur iron, pyrite and sulfur powder; the manganese-containing raw material is electrolytic manganese or manganese-containing alloy; the aluminum-containing raw material is aluminum particles, aluminum ingots or aluminum-containing alloys.
The method for reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel provided by the invention is described below by combining specific examples and comparative examples.
Example 1
The embodiment provides a method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel, which comprises the following steps of:
s1, preparing 35kg of industrial pure iron, 360g of graphite rod, 10.64kg of electrolytic manganese, 5.3kg of aluminum particles and 10g of pyrite as raw materials for preparing high-aluminum steel; wherein the manganese content is about 20.74% and the sulfur content is about 0.01%.
S2, putting the industrial pure iron and the graphite rod into a prefabricated magnesium oxide crucible, and putting the electrolytic manganese, the aluminum particles and the ferro-sulphur into a storage bin. Vacuumizing the induction furnace to 6Pa, heating to 1600 ℃, completely melting the industrial pure iron and the graphite rod, introducing argon into the induction furnace, adding electrolytic manganese through a storage bin, and adding aluminum particles through the storage bin after the electrolytic manganese is completely melted. Refining for 10min, and then adding 12g of pyrite through a feed bin to obtain molten steel.
S3, casting the molten steel obtained in the step S2 into a prepared ingot mold, finally adjusting the power of the induction furnace to 0, and taking out a steel ingot after pressure relief to obtain a final product; the final product is high-aluminum steel with low harmfulness of aluminum nitride inclusions.
Examples 2 to 3 and comparative examples 1 to 2
Examples 2-3 and comparative examples 1-2 respectively provide a method for reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel, and compared with example 1, the method is different in that the addition amount of ferro-sulphur is changed, and the rest steps are the same as those in example 1, and are not repeated herein. The amount of added pyrite and the amount of sulfur contained in the high-aluminum steel in each of the examples and comparative examples are shown in Table 1.
TABLE 1S-Fe addition and S-content in high-Al steels for examples 2-3 and comparative examples 1-2
| Examples/comparative examples | Amount of pyrite added (g) | Sulphur content in high-aluminium steels (%) |
| Example 2 | 20 | 0.02 |
| Example 3 | 30 | 0.03 |
| Comparative example 1 | 3 | 0.003 |
| Comparative example 2 | 40 | 0.04 |
In order to test the degree of harm reduction of the method provided by each embodiment and comparative example to the aluminum nitride inclusion in the high-aluminum steel, samples are respectively taken from the central parts of the final products obtained in the embodiments 1-3 and the comparative examples 1-2, the shapes and the quantity of the aluminum nitride inclusion and the manganese sulfide wrapped aluminum nitride inclusion in each sample are observed and counted by adopting a scanning electron microscope, the hardness value is measured by adopting a Brinell hardness measuring instrument, and the tensile strength is measured by adopting a universal testing machine after each sample is treated at 530 ℃ for 10 hours.
In the above manner, it was observed that the morphology of the manganese sulfide-coated aluminum nitride inclusion formed in example 1 and the pure aluminum nitride inclusion formed in comparative example 1 are shown in fig. 1 and 2, respectively. The results of measuring the number of inclusions in the final products corresponding to examples 1 to 3 and comparative examples 1 to 2 and the hardness and tensile strength thereof are shown in Table 2.
TABLE 2 amount of inclusions in final products obtained in examples 1 to 3 and comparative examples 1 to 2, and hardness and tensile strength thereof
It can be seen from table 2 that the type and structure of inclusions formed can be controlled by controlling the sulfur content in the high-aluminum steel, thereby affecting the hardness and tensile strength of the high-aluminum steel product.
Compared with comparative examples 1-2, in examples 1-3, the amount of hard brittle pure aluminum nitride inclusions can be significantly reduced and the amount of manganese sulfide-coated aluminum nitride inclusions can be increased by controlling the sulfur content in the range of 0.01% -0.03%. Wherein, the too low sulfur content in comparative example 1 results in insufficient manganese sulfide, difficulty in effective coating of aluminum nitride, and significantly lower hardness and tensile strength; while the excessive sulfur content in the comparative example 2 can realize more manganese sulfide coated aluminum nitride inclusions, the excessive sulfur content is easy to form low-melting-point iron sulfide with iron elements and form eutectic with a metal matrix, so that the mechanical property of the steel is deteriorated.
As can be seen from fig. 1 and 2, the inclusion of aluminum nitride is coated by manganese sulfide, so that the inclusion of aluminum nitride can be completely coated in manganese sulfide, the effect of modifying the inclusion of aluminum nitride is achieved, and the harm caused by pure inclusion of aluminum nitride is effectively eliminated. Meanwhile, according to the hardness and tensile strength data in table 2, it can be seen that the reduction of the amount of pure aluminum nitride inclusions effectively improves the hardness and tensile strength of the high-aluminum steel, and further proves that the method provided by the invention can effectively reduce the harmfulness of the aluminum nitride inclusions.
Comparative example 3
Comparative example 3 provides a method for reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel, which is different from example 1 in that the addition sequence of the raw materials is changed, and the rest steps are the same as those in example 1, and are not repeated herein.
In comparative example 3, the order of addition of the raw materials was: putting industrial pure iron, graphite rods, electrolytic manganese, aluminum particles and ferro-sulphur into a magnesium oxide crucible together, and heating along with the furnace.
The amounts of various inclusions in the final product obtained in comparative example 3 and the hardness and tensile strength of the high aluminum steel were measured as shown in table 3.
TABLE 3 number of inclusions in the final product obtained in comparative example 3 and their hardness and tensile strength
Comparing the test result of comparative example 3 with example 1, it can be seen that the change of the order of addition of the raw materials has a great influence on the kind of inclusions, thereby affecting the hardness and tensile strength of the high aluminum steel product. Comparative example 3 when the raw materials are put into a magnesium oxide crucible together and heated along with the furnace, more pure aluminum nitride inclusions are formed, and the quantity of the manganese sulfide wrapping the aluminum nitride inclusions is small, so that the hardness and tensile strength of the steel cannot be effectively improved.
Therefore, the adding sequence of the raw materials provided by the invention can utilize the graphite rods added in advance to react with oxygen in the molten steel under vacuum to form carbon monoxide bubbles and float upwards, thereby consuming the oxygen in the molten steel and avoiding the formation of alumina inclusions; meanwhile, the manganese-containing raw material is added before the aluminum-containing raw material, so that the manganese element is pre-deoxidized, and the formation of alumina impurities is reduced; in addition, the sulfur-containing raw material is added at last, and beneficial conditions can be provided for accurate wrapping and modification of aluminum nitride inclusions.
It should be noted that, those skilled in the art should understand that the method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel provided by the present invention is not only suitable for smelting process in a vacuum induction smelting furnace, but also suitable for smelting process in smelting furnaces such as an electric arc furnace, a ladle furnace, etc.; meanwhile, the crucible used can be a magnesium oxide prefabricated crucible with the mass purity of more than 95 percent or an aluminum oxide prefabricated crucible with the mass purity of more than 95 percent; the sulfur-containing raw material comprises one or more of but not limited to sulfur iron, pyrite and sulfur powder, and the manganese-containing raw material can be electrolytic manganese or manganese-containing alloy; the aluminum-containing raw material can be aluminum particles, aluminum ingots or aluminum-containing alloys, and can achieve the effect of reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel so as to meet the requirements of practical application.
In conclusion, the invention provides a method for reducing the harmfulness of aluminum nitride inclusions in high-aluminum steel. The method comprises the steps of pre-melting industrial pure iron and a graphite rod, and then sequentially adding a manganese-containing raw material and an aluminum-containing raw material for smelting; after the manganese raw material and the aluminum-containing raw material are completely melted down, adding a predetermined amount of sulfur-containing raw material to obtain molten steel; and then casting the molten steel into the model to obtain the high-aluminum steel with low harmfulness of aluminum nitride inclusions. Through the mode, the method can realize the full wrapping of the brittle aluminum nitride inclusions by the plastic manganese sulfide inclusions by regulating and controlling the sulfur content in the high-aluminum steel and utilizing the higher deformability of the formed manganese sulfide inclusions, thereby reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel. The method provided by the invention is simple to operate, has a wide application range, can effectively reduce the number of pure aluminum nitride inclusions in the high-aluminum steel, improves the hardness and tensile strength of the high-aluminum steel, and has a high practical application value.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (7)
1. A method for reducing harmfulness of aluminum nitride inclusions in high-aluminum steel is characterized by comprising the following steps:
s1, preparing materials according to preset high-aluminum steel components; in the preset high-aluminum steel components, the sulfur content is 0.01-0.03%, and the manganese content is more than 3%;
s2, pre-melting the industrial pure iron and the graphite rod, adding a manganese-containing raw material, and adding an aluminum-containing raw material for melting after the manganese-containing raw material is completely melted; after the manganese-containing raw material and the aluminum-containing raw material are completely melted down, adding a sulfur-containing raw material to obtain molten steel;
and S3, casting the molten steel obtained in the step S2 into a model to obtain the high-aluminum steel.
2. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to claim 1, wherein the method comprises the following steps: in step S2, the smelting process uses a smelting device including, but not limited to, one of an induction furnace, an electric arc furnace, and a ladle furnace.
3. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to claim 2, wherein the method comprises the following steps: in step S2, when the smelting device is an induction furnace, the induction furnace is first vacuumized and then heated to 1500-1700 ℃, and after the industrial pure iron and the graphite rod are melted, an inert gas is introduced into the induction furnace, and then the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material are sequentially added.
4. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to claim 1, wherein the method comprises the following steps: in step S2, the commercially pure iron and graphite rod are placed in advance in a crucible; and putting the manganese-containing raw material, the aluminum-containing raw material and the sulfur-containing raw material into a storage bin.
5. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to claim 4, wherein the method comprises the following steps: the crucible is a magnesium oxide prefabricated crucible with the mass purity of more than 95 percent or an aluminum oxide prefabricated crucible with the mass purity of more than 95 percent.
6. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to any one of claims 1 to 5, wherein the method comprises the following steps: the sulfur-containing raw material comprises one or more of but not limited to sulfur iron, pyrite and sulfur powder.
7. The method for reducing the harmfulness of the aluminum nitride inclusions in the high-aluminum steel according to any one of claims 1 to 5, wherein the method comprises the following steps: the manganese-containing raw material is electrolytic manganese or manganese-containing alloy; the aluminum-containing raw material is aluminum particles, aluminum ingots or aluminum-containing alloys.
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