CN111876668B - High-hardness wear-resistant corrosion-resistant hypereutectoid steel and preparation method thereof - Google Patents
High-hardness wear-resistant corrosion-resistant hypereutectoid steel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-hardness wear-resistant corrosion-resistant hypereutectoid steel and a preparation method thereof, wherein the chemical components of the hypereutectoid steel comprise the following components in percentage by mass: c: 0.90-1.05%, Si: 0.21-0.30%, Mn: 0.90-1.25%, Cr: 0.70-0.90%, Nb: 0.030 to 0.050%, Ti: 0.012 to 0.025%, Al: 0.01-0.04%, Cu is less than or equal to 0.30%, Sn is less than or equal to 0.10%, Ni is less than or equal to 0.30%, Mo is less than or equal to 0.040%, P is less than or equal to 0.030%, S is less than or equal to 0.030%, and the balance is Fe and other inevitable impurity elements; the preparation method comprises the processes of electric furnace smelting, LF refining, VD vacuum degassing, continuous casting, bar rolling and the like. The invention adds Cr, Nb and Ti elements into high-carbon steel, and improves the hardness, wear resistance and acid-base environment corrosion resistance of steel.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to hypereutectoid steel with high hardness, wear resistance and corrosion resistance and a production method thereof.
Background
The steel for the wear-resistant ball is widely applied to production of various industries such as metallurgical mines, building materials, chemical industry, electric power, pharmacy and the like as a wear-resistant part. The repeated friction, extrusion and impact action of the grinding ball crush the materials, so that the grinding ball is required to have higher hardness and wear resistance, and the grinding ball also has good corrosion resistance under severe working environment.
At present, there are many patents related to steel for grinding balls, which generally have the disadvantages of higher alloy content, low wear resistance, and no corrosion resistance, etc., and according to the relevant literature and the published latest patent technology, several existing patent applications are briefly introduced as follows:
chinese patent application CN-104762562-A discloses 'steel for a large-diameter grinding ball and a manufacturing method thereof', which relates to a steel material with lower hardness value, no mention of wear resistance and no corrosion resistance. Chinese patent application CN-108342645-A discloses 'a steel for hypereutectoid grinding balls and a preparation method thereof', which relates to a steel product only covering a continuous casting billet type and only a rolling process of a rolling material with a specification. Chinese patent application CN-108176718-A discloses a rolling method of hypereutectoid steel continuous casting billets, wherein the continuous casting billets are round billets, and the properties of steel products are not mentioned. Chinese patent application CN-106834959-A discloses a production method of steel for high-hardness wear-resistant ball material, the smelting method is converter steelmaking, and the properties of the steel are not mentioned.
Disclosure of Invention
Based on the defects, the invention provides the hypereutectoid steel with high hardness, wear resistance and corrosion resistance and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hypereutectoid steel with high hardness, wear resistance and corrosion resistance comprises the following chemical components in percentage by mass: c: 0.90-1.05%, Si: 0.21-0.30%, Mn: 0.90-1.25%, Cr: 0.70-0.90%, Nb: 0.030 to 0.050%, Ti: 0.012 to 0.025%, Al: 0.01-0.04%, Cu is less than or equal to 0.30%, Sn is less than or equal to 0.10%, Ni is less than or equal to 0.30%, Mo is less than or equal to 0.040%, P is less than or equal to 0.030%, S is less than or equal to 0.030%, and the balance is Fe and other inevitable impurity elements;
the specification of the high-hardness wear-resistant corrosion-resistant hypereutectoid steel is as follows
The hardness of the hypereutectoid steel is more than or equal to 400 HB; the austenite grain size is more than or equal to 8.0 grade; the carbon segregation rate is less than or equal to 1.10; the grade of nonmetallic inclusion is less than or equal to 1.5 in A grade, less than or equal to 1.0 in B grade, less than or equal to 1.0 in C grade, and less than or equal to 1.0 in D grade.
Preferably, the hypereutectoid steel comprises the following chemical components in percentage by mass: c: 0.95-1.05%, Si: 0.23-0.29%, Mn: 1.05-1.20%, Cr: 0.75 to 0.90%, Nb: 0.030 to 0.050%, Ti: 0.013-0.024%, Al: 0.01-0.04%, Cu is less than or equal to 0.30%, Sn is less than or equal to 0.10%, Ni is less than or equal to 0.30%, Mo is less than or equal to 0.040%, P is less than or equal to 0.030%, S is less than or equal to 0.030%, and the balance is Fe and other inevitable impurity elements; and the content of Mn + Cr is required to meet the requirement that the content of Mn + Cr is more than or equal to 1.688C +0.391Si +2.831Nb +1.669Ti and less than or equal to Mn + Cr and less than or equal to 1.704C +0.418Si +2.905Nb +1.887 Ti.
Cr: cr increases the hardenability of steel and has a secondary hardening effect, which can improve the hardness and wear resistance of carbon steel without making the steel brittle. The main function of chromium in the quenching and tempering structure is to improve hardenability, so that the steel has better comprehensive mechanical properties after quenching and tempering, and chromium-containing carbide can be formed in the carburizing steel, thereby improving the wear resistance of the surface of the material. When Cr is used in combination with Al, the wear resistance and corrosion resistance of the steel can be improved.
Nb: the niobium is partially dissolved in the solid solution to perform the solid solution strengthening function. The hardenability of the steel is significantly improved when dissolved in austenite. But in the form of carbide and oxide particles, refine the grains and reduce the hardenability of the steel. It can increase the tempering stability of steel and has secondary hardening effect. A trace amount of niobium may improve the strength of the steel without affecting the plasticity or toughness of the steel. The impact toughness of the steel can be improved and the brittle transition temperature of the steel can be reduced due to the effect of refining grains. When the Nb content reaches a certain amount, the steel has good hydrogen resistance, and intergranular corrosion of the steel by an oxidizing medium can be prevented in the austenitic steel.
Ti: has strong affinity with nitrogen, oxygen and carbon, has stronger affinity with sulfur than iron, and is a good deoxidizing and degassing agent and an effective element for fixing nitrogen and carbon. Titanium, although a strong carbide-forming element, does not combine with other elements to form a composite compound. Titanium carbide has strong binding force, is stable and not easy to decompose, and can be slowly dissolved in solid solution only by heating to more than 1000 ℃ in steel. The titanium carbide fine particles have an effect of preventing the growth of the crystal grains before the dissolution. Since the affinity between titanium and carbon is much greater than the affinity between chromium and carbon, titanium is often used in stainless steels to fix the carbon therein to eliminate depletion of chromium at grain boundaries, thereby eliminating or mitigating intergranular corrosion of the steel.
The invention also provides a preparation method of the high-hardness wear-resistant corrosion-resistant hypereutectoid steel, which comprises the processes of electric furnace smelting, LF refining, VD vacuum degassing, continuous casting, bar rolling and the like;
in the electric furnace smelting process, the raw materials of the electric furnace are selected from selected scrap steel, the baking temperature of a steel ladle is more than or equal to 800 ℃, and the content of molten iron is 60-85%. Melting down the scrap steel, and sampling and analyzing completely, wherein the full melting analysis temperature is more than or equal to 1550 ℃. The tapping temperature is 1620-1660 ℃, the end point C is more than or equal to 0.15 percent, and the P is less than or equal to 0.015 percent. When the steel tapping amount of the molten steel reaches 1/4-1/3, alloying the molten steel in a ladle, adding 10.048-15.903 Kg of high manganese alloy, 16.541-21.265 Kg of high chromium alloy, 0.543-0.906 Kg of ferroniobium alloy, 0.052-1.552 Kg of ferrosilicon alloy and 0.086-0.179 Kg of low-titanium high-chromium alloy into each ton of steel, and adding slag-making materials according to about 10-15 Kg/t.
In the refining process, the alkalinity of the slag is controlled to be more than or equal to 3, an aluminum wire is fed, and sampling and total analysis are carried out under white slag. Keeping the white slag time to be more than 20min, feeding a calcium line according to the ratio of 1.5-3.5 m/t, blowing argon gas at the flow rate of 40-80 NL/min, and tapping at 1559-1594 ℃ after blowing argon gas for 2-3 min.
In the VD vacuum degassing process, the steel feeding temperature is 1503.5-1528.3 ℃, the working pressure is 67-70 Pa, the soft blowing time is not less than 10min, and the flow (10-30)) NL/min of argon is blown during soft blowing.
In the continuous casting process, the temperature of molten steel in the tundish is controlled to be 1468.5-1478.5 ℃, the casting speed is 0.95-1.15 m/min when the section of a square billet is a billet with the size of 180mm multiplied by 220mm, and the casting speed is 0.50-0.60 m/min when the section of the billet is a billet with the size of 260mm multiplied by 300 mm.
In the rolling process, the starting rolling temperature is 1120-1200 ℃ when the section of a square billet is a billet with the size of 180mm multiplied by 220mm, and the starting rolling temperature is 1100-1180 ℃ when the section of the square billet is a billet with the size of 260mm multiplied by 300 mm. Finished steel specification
The final rolling temperature is 920-1020 ℃ in specification
The final rolling temperature is 900-1000 ℃, and the specification is
The final rolling temperature is 950-1050 ℃.
Compared with the prior art, the invention has the following positive effects:
1) the method is characterized in that a small amount of Nb element is added for solid solution strengthening; cr is added into the carburizing steel to form chromium-containing carbide, so that the decomposition of the carbide, the diffusion of carbon and the segregation of cementite can be effectively prevented, and the wear resistance of the surface of the material is improved.
2) The high-quality casting blank raw material with uniform components and high purity is produced by the technologies of smelting chemical components in an electric furnace, controlling end point, alloying a steel ladle, refining Ca in an LF furnace, controlling alloy content, removing impurities by VD vacuum degassing, continuously casting with low superheat degree, soft reduction, slow cooling of a casting blank and the like. And then, performing tissue regulation and control by setting rolling process parameters such as heating furnace temperature, heating time, initial rolling temperature, final rolling temperature and the like, performing large-reduction deformation to promote strain-induced precipitation of microalloy elements and realize refinement of austenite grains, and performing accelerated cooling after rolling to realize control of an austenite phase transformation process and finally obtain a fine grain tissue. The steel with wide specification range, high hardness, wear resistance, corrosion resistance, and good non-metallic inclusion grade and austenite grain size grade of the steel is obtained by using less alloy content and a simple process.
3) The hardness of the high-hardness wear-resistant acid-base environment corrosion-resistant hypereutectoid steel obtained by the invention reaches more than or equal to 400HB, the austenite grain size is more than or equal to 8.0 grade, and the carbon segregation rate is less than or equal to 1.10; the grade of nonmetallic inclusion is less than or equal to 1.5, the grade B is less than or equal to 1.0, the grade C is less than or equal to 1.0, the grade D is less than or equal to 1.0, the abrasion loss of the dry abrasive in unit time is less than or equal to 10mg/h, the wear resistance is realized, the quality loss of the corrosive wear of steel in an acid-base environment is less than the abrasion loss of the dry abrasive, and the corrosion resistance of the acid-base environment is realized.
4) The steel grade can well meet the requirements of high hardness, wear resistance, corrosion resistance, high cleanliness, tissue compactness and the like of steel in acid-base environments, has good surface and internal quality, and provides technical support for developing grinding ball steel products which can be widely used in acid-base environments.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The present invention will be described in further detail with reference to specific embodiments.
Example (b):
in the embodiment, the production process flow of the high-hardness wear-resistant corrosion-resistant hypereutectoid steel comprises the processes of electric furnace smelting, LF refining, VD vacuum degassing, continuous casting, bar rolling and the like.
The specific operation steps are as follows:
selecting selected waste steel as raw materials of the electric furnace, wherein the baking temperature of a steel ladle is 800-820 ℃, and the content of molten iron is 67-80%. And after the scrap steel is molten down, the total melting analysis temperature is 1540-1545 ℃, and the sampling and total analysis are carried out. Tapping when the temperature reaches 1648-1655 ℃ when the end points C is 0.16-0.18% and P is 0.011% -0.015%. Before opening a steel tapping hole, the argon pressure of the steel ladle is 0.32-0.35 MPa, and the flow of argon blowing is 20-25 NL/min; and after the steel tapping hole is opened, argon pressure is 0.7-0.9 MPa, and argon blowing flow is 420-450 NL/min. When the steel tapping amount of the molten steel reaches 1/4, alloying is carried out in a steel ladle, in three examples, 13.228Kg, 14.063Kg and 13.729Kg of high manganese alloy, 18.430Kg, 18.194Kg and 20.085Kg of high chromium alloy, 0.670Kg, 0.725Kg and 0.743Kg of ferrocolumbium alloy, 0.885Kg, 0.719Kg and 1.219Kg of ferrosilicon alloy, and 0.150Kg, 0.136Kg and 0.114Kg of low-titanium high-chromium alloy are added into each ton of steel. And adding 12-14 kg of slagging material per ton of steel.
In the LF refining process, when the temperature of molten steel in an LF furnace reaches 1505-1510 ℃, the flow of argon is adjusted during heating, the flow of argon is blown at 40-50 NL/min, the stability of electric arc is ensured, the slag surface is slightly moved, and the liquid level of the molten steel is not exposed. And ensuring the alkalinity (R) of the slag to be 3.0-4.0, stopping power supply when the slag is white, feeding an aluminum wire, fully stirring for 2min at the flow rate of 300-400 NL/min of a large argon gas, measuring the temperature, and taking a sample for full analysis. After sampling, adding a proper amount of deoxidizing agents such as silicon carbide and the like to the slag surface according to the deoxidizing condition, and keeping the white slag. Adding alloy, adding carbon, stirring at the argon blowing flow of 400-500 NL/min, measuring the temperature, taking a secondary sample, and properly adding silicon carbide. And (3) when the temperature meets the tapping requirement, power is cut off, a Ca wire is fed according to the steel grade requirement, the flow of argon is blown to be 60-70 NL/min, and after argon is blown for 2-3 min, the temperature reaches 1565-1573 ℃ for tapping.
In the VD vacuum degassing process, the steel feeding temperature is 1513-1520 ℃, the working pressure reaches 67Pa, and the argon flow is controlled at 20-25 NL/min during vacuum treatment. Removing vacuum, opening a cover, sampling, measuring temperature, adding a covering agent, and soft blowing, wherein the soft blowing time is 13-15 min, and the flow of argon is 20-28 NL/min during soft blowing.
In the continuous casting process, the temperature of molten steel in the tundish is controlled to be 1470-1475 ℃, the casting speed is 0.95-1.05 m/min when the section of the square billet is a billet with the size of 180mm multiplied by 220mm, and the casting speed is 0.55-0.60 m/min when the section of the billet is a billet with the size of 260mm multiplied by 300 mm.
In the rolling process, the starting rolling temperature is 1150-1180 ℃ when the section of the square billet is a billet of 180mm × 220mm, and the starting rolling temperature is 1140-1170 ℃ when the section of the square billet is a billet of 260mm × 300 mm. Finished steel specification
The final rolling temperature is 960-1010 ℃, and the specification is
The final rolling temperature is 920-980 ℃ in specification
The finishing temperature is 970-1020 ℃.
After the above steps, the chemical components of the obtained molten steel are listed in table 1 by weight percentage, and the balance is Fe and unavoidable impurities.
The chemical composition results of the steel material of this example are shown in Table 1.
Table 1 examples chemical composition (weight,%)
TABLE 2 Process parameters for smelting and rolling of steels according to the examples of the invention
TABLE 3 hardness, carbon segregation rate, grain size and non-metallic inclusions of steels according to examples of the present invention
TABLE 4 weight loss (mg) of corrosive wear of acid-base environment of steel materials according to examples of the present invention
In conclusion, the hardness of the high-hardness wear-resistant corrosion-resistant hypereutectoid steel obtained by the invention reaches more than or equal to 400HB, the austenite grain size is more than or equal to 8.0 grade, and the carbon segregation rate is less than or equal to 1.10; the grade of nonmetallic inclusion is less than or equal to 1.5, the grade B is less than or equal to 1.0, the grade C is less than or equal to 1.0, the grade D is less than or equal to 1.0, the abrasion loss of the dry abrasive in unit time is less than or equal to 10mg/h, the wear resistance is realized, and the quality loss of the corrosive wear of steel in an acid-base environment is less than the abrasion loss of the dry abrasive, so the steel has the acid-base environment corrosion resistance.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The hypereutectoid steel with high hardness, wear resistance and corrosion resistance is characterized by comprising the following chemical components in percentage by mass: c: 0.95-1.05%, Si: 0.23-0.29%, Mn: 1.05-1.20%, Cr: 0.75 to 0.90%, Nb: 0.030 to 0.050%, Ti: 0.013-0.024%, Al: 0.01-0.04%, Cu is less than or equal to 0.30%, Sn is less than or equal to 0.10%, Ni is less than or equal to 0.30%, Mo is less than or equal to 0.040%, P is less than or equal to 0.030%, S is less than or equal to 0.030%, and the balance is Fe and other inevitable impurity elements; and the content of Mn + Cr satisfies:
1.688C+0.391Si+2.831Nb+1.669Ti≤Mn+Cr≤1.704C+0.418Si+2.905Nb+1.887Ti；
the hypereutectoid steel specification is
The hardness of the hypereutectoid steel is more than or equal to 400 HB; the austenite grain size is more than or equal to 8.0 grade; the carbon segregation rate is less than or equal to 1.10; the grade of nonmetallic inclusion is less than or equal to 1.5 in A grade, less than or equal to 1.0 in B grade, less than or equal to 1.0 in C grade, and less than or equal to 1.0 in D grade.
2. A method for preparing the hypereutectoid steel according to claim 1, comprising the steps of:
1) electric furnace smelting: the tapping temperature is 1620-1660 ℃, the end point C is more than or equal to 0.15 percent, and the P is less than or equal to 0.015 percent; when the molten steel is discharged to 1/4-1/3, alloy is uniformly added, and each ton of steel is added with 10.048-15.903 Kg of high manganese alloy, 16.541-21.265 Kg of high chromium alloy, 0.543-0.906 Kg of ferrocolumbium, 0.052-1.552 Kg of ferrosilicon alloy and 0.086-0.179 Kg of low-titanium high-chromium alloy;
2) LF refining: controlling the alkalinity of the slag to be more than or equal to 3, feeding an aluminum wire, sampling and fully analyzing under white slag, and tapping when the temperature reaches 1559-1594 ℃ after argon blowing;
3) VD vacuum degassing: the steel feeding temperature is 1503.5-1528.3 ℃, and the working pressure is 67-70 Pa;
4) continuous casting: the temperature of molten steel in the tundish is controlled to be 1468.5-1478.5 ℃;
5) rolling: the initial rolling temperature is 1100-1200 ℃; the finishing temperature is 900-1050 ℃.
3. The preparation method of claim 2, wherein the white slag is kept for more than 20min in the step 2), a calcium wire is fed according to the speed of 1.5-3.5 m/t, the argon blowing flow is 40-80 NL/min, and the argon blowing time is 2-3 min.
4. The preparation method according to claim 2, wherein the soft blowing time in the step 3) is not less than 10min, and the flow rate of argon blown during the soft blowing is 10-30 NL/min.
5. The method according to claim 2, wherein the drawing rate in the step 4) is 0.95 to 1.15m/min for a billet having a cross section of 180mm x 220mm, and 0.50 to 0.60m/min for a billet having a cross section of 260mm x 300 mm.
6. The preparation method according to claim 2, wherein the open rolling temperature of the billet in the step 5) is 1120-1200 ℃ when the billet section is 180mm x 220mm, and the open rolling temperature of the billet in the step 5) is 1100-1180 ℃ when the billet section is 260mm x 300 mm;
the finish rolling temperature is 920-1020 ℃ when the specification of the finished steel product is not less than 120mm and not more than 310mm, 900-1000 ℃ when the specification of 50mm and not more than 120mm and 950-1050 ℃ when the specification of 12mm and not more than 50 mm.
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