CN112267064A - Martensite high-temperature wear-resistant steel and production method thereof - Google Patents
Martensite high-temperature wear-resistant steel and production method thereof Download PDFInfo
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Abstract
The martensite high-temperature wear-resistant steel comprises the following chemical components in percentage by weight: 0.18-0.24%, Si: 0.1-0.35%, Mn: 0.5-1.1%, P is less than or equal to 0.013%, S is less than or equal to 0.004%, Als: 0.03 to 0.06%, Nb: 0.025-0.055%, V: 0.02-0.04%; ti: 0.01-0.025%, Cr: 0.1-0.35%, Mo: 0.25-0.45%, B: 0.0005-0.0018%, N: 0.003-0.0045%, H is less than or equal to 1.7ppm, Ca: 0.002-0.004%, and the balance of Fe and inevitable impurities. In the production method, a temperature-control and speed-control quenching process and a sub-temperature quenching heating process are adopted; the quenching cooling process adopts interval cooling. The wear-resistant steel has good mechanical property under high-temperature service conditions.
Description
Technical Field
The invention relates to the technical field of wear-resistant steel production, in particular to martensite high-temperature wear-resistant steel and a production method thereof.
Background
The low-alloy wear-resistant steel series products have the characteristics of high strength, high hardness, high wear resistance, high low-temperature impact toughness and the like, have certain processing and forming properties, and are widely applied to the industries of engineering machinery, mining, agricultural machinery, special vehicle manufacturing, shipbuilding, construction, oil and gas conveying and the like, such as bulldozers, loaders, excavators, scraper conveyors, mining dump trucks and the like. After the low-alloy wear-resistant steel product is used, the service life of equipment under severe working conditions is prolonged, light weight, energy consumption saving, green development and cost reduction are realized.
With the rapid development of the industry in China and the expansion of the application field of low-alloy wear-resistant steel, the wear-resistant steel product still has the characteristics of good tensile strength, hardness, wear-resistant rigidity and the like under the high-temperature service condition, and becomes one of new high-performance materials emerging in recent years in the high-end industrial field at home and abroad.
The microstructure of the low alloy steel with good wear resistance is martensite to ensure the organic combination of strength, hardness, toughness and wear resistance, however, with the increase of service temperature, the boundaries of martensite laths are diffused, gathered, combined and recombined mutually through atoms, the phase interface is gradually blurred, carbides are gradually separated out from the martensite structure and coarsened, the strength, hardness and wear resistance of the steel plate in a high temperature range are seriously damaged, the service life is shortened, and especially the wear resistant steel product in high temperature service usually bears the repeated impact in a certain range, namely high temperature impact wear. How to produce martensite high-temperature wear-resistant steel with good impact wear performance is urgently needed to be developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing the martensite high-temperature wear-resistant steel which still has good impact wear performance at the temperature of 100-300 ℃ and a production method of the martensite high-temperature wear-resistant steel.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the martensite high-temperature wear-resistant steel comprises the following chemical components in percentage by weight: c: 0.18% -0.24%, Si: 0.10% -0.35%, Mn: 0.50-1.10%, P is less than or equal to 0.013%, S is less than or equal to 0.004%, Als: 0.030% -0.060%, Nb: 0.025% -0.055%, V: 0.020% -0.040%; ti: 0.010-0.025%, Cr: 0.10% -0.35%, Mo: 0.25% -0.45%, B: 0.0005% -0.0018%, N: 0.0030-0.0045%, H is less than or equal to 1.7ppm, Ca: 0.0020-0.0040 percent, and the balance of Fe and inevitable impurities.
The martensite high-temperature wear-resistant steel preferably comprises the following chemical components in percentage by weight: c: 0.19% -0.22%, Si: 0.15% -0.30%, Mn: 0.60-0.90%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, Als: 0.045% -0.055%, Nb: 0.03% -0.045%, V: 0.025% -0.040%; ti: 0.010-0.020%, Cr: 0.15% -0.30%, Mo: 0.30% -0.40%, B: 0.0009% -0.0014%, N: 0.0033% -0.0042%, H is less than or equal to 1.4ppm, Ca: 0.0030-0.0040% and the balance of Fe and inevitable impurities.
The production method of the martensite high-temperature wear-resistant steel comprises the working procedures of steel making, continuous casting, billet reheating, controlled rolling, air cooling after rolling, temperature and speed controlled quenching and low-temperature tempering, wherein the casting billet in the continuous casting working procedure comprises the following components in percentage by weight: c: 0.18% -0.24%, preferably 0.19% -0.22%; si: 0.10% -0.35%, preferably 0.15% -0.30%; mn: 0.50% -1.10%, preferably 0.60% -0.90%; p is less than or equal to 0.013%, preferably P is less than or equal to 0.012%; s is less than or equal to 0.004 percent, preferably S is less than or equal to 0.003 percent; and Als: 0.030% -0.060%, preferably 0.045% -0.055%; nb: 0.025% -0.055%, preferably 0.03% -0.045%; v: 0.020% to 0.040%, preferably 0.025% to 0.040%; ti: 0.010% -0.025%, preferably 0.010% -0.020%; cr: 0.10% -0.35%, preferably 0.15% -0.30%; mo: 0.25% -0.45%, preferably 0.30% -0.40%; b: 0.0005% -0.0018%, preferably 0.0009% -0.0014%; n: 0.0030-0.0045%, preferably 0.0033-0.0042%; h is less than or equal to 1.7ppm, preferably less than or equal to 1.4 ppm; ca: 0.0020-0.0040%, preferably 0.0030-0.0040%, and the balance of Fe and inevitable impurities.
The production method of the martensite high-temperature wear-resistant steel comprises the following steps:
controlling the quenching heating temperature: the quenching heating temperature is controlled to be Ac3+ (30-50 ℃), so that fine austenite grain size is obtained by adopting a sub-temperature quenching heating process while complete austenitizing of the steel plate is guaranteed, the strength is improved, and meanwhile, the low-temperature impact performance is good.
The quenching cooling process adopts an interval cooling method, the front area of the high-pressure rapid cooling section is opened, the rear area is closed, the front area of the low-pressure medium-low velocity cooling section is closed, and the rear area is opened.
In the above method for producing martensitic high-temperature wear-resistant steel, the front region of the high-pressure rapid cooling section is opened, and the rear region is closed, which means that: starting a cooling area 1 and an area 2, and closing a cooling area 3 and an area 4 and an area 5 and an area 6; or starting the cooling zone 1 + zone 2 + zone 3, and closing the cooling zone 4 + zone 5 + zone 6; or starting the cooling zone 1 + zone 2 + zone 3+ zone 4, and closing the cooling zone 5 + zone 6; the front area of the low-pressure medium-low speed cooling section is closed, and the rear area is opened, namely: closing a cooling 7 area +8 area +9 area +10 area +11 area +12 area, and opening a cooling 13 area +14 area +15 area; or closing the cooling zone 7 +8 +9 +10 +11 and opening the cooling zone 12 +13 +14 + 15; or closing the cooling zone 7 +8 +9 +10 and opening the cooling zone 11 +12 +13 +14 + 15; or the cooling 7 area +8 area +9 area is closed, and the cooling 10 area +11 area +12 area +13 area +14 area +15 area is opened.
According to the production method of the martensite high-temperature wear-resistant steel, in the quenching and cooling process, the opening area of the quenching and cooling high-pressure rapid cooling section is rapidly cooled to the Ms point of the martensite start phase transformation point at the cooling speed of 28-54 ℃/s, and the steel plate is air-cooled at the closed position of the cooling header; when the steel plate runs from the high-pressure rapid cooling section to the low-pressure medium-low speed cooling section, the steel plate is cooled in air for 4-9 seconds at the closed position of the cooling header, C, N compounds of fine and dispersed Nb, Mo, V and other microalloy elements are promoted to be separated out in the quenching cooling process, the fine and dispersed Nb (C, N), Mo (C, N) and V (C, N) prevent grain boundary migration, the grain growth temperature is increased, and the quenched steel plate has the advantages of fine grain size and dual effects of fine grain strengthening and precipitation strengthening. Finally, the dual effects of fine grain strengthening and precipitation strengthening are still kept in the service process of 100-300 ℃, the high-temperature tensile strength and the Brinell hardness of the steel plate are stabilized, and the high-temperature wear resistance is improved. And after air cooling the steel plate for 4-9 seconds, then entering a low-pressure medium-low speed cooling section opening area, and cooling to room temperature at a cooling speed of 20-30 ℃/s.
The invention has the main innovations that: 1. the martensite solid solution strengthening stability elements Mo, Nb and V are added, so that the high-temperature deformation resistance and the work hardening degree are improved, the tempering stability is increased, the high-temperature strengthening effect is achieved, the tensile strength and the Brinell hardness of the martensite wear-resistant steel are not reduced too much along with the temperature increase, and the martensite wear-resistant steel has good wear resistance under the high-temperature service environment. 2. A temperature-control and speed-control quenching heat treatment process is adopted to promote C, N compound precipitation of fine and dispersed micro-alloy elements such as Nb, Mo and V in the quenching cooling process, fine and dispersed Nb (C, N), Mo (C, N) and V (C, N) prevent grain boundary migration, the grain growth temperature is increased, and the quenched steel plate has the advantages of fine grain size and dual effects of fine grain strengthening and precipitation strengthening. Finally, the dual effects of fine grain strengthening and precipitation strengthening are still kept in the service process of 100-300 ℃, the high-temperature tensile strength and the Brinell hardness of the steel plate are stabilized, and the high-temperature wear resistance is improved.
The martensite solid solution strengthening stability is improved, namely, the martensite solid solution strengthening stability alloy element is added, so that the tensile strength and the Brinell hardness of the martensite wear-resistant steel are not reduced too much along with the temperature rise, and the martensite wear-resistant steel has good wear resistance under the high-temperature service environment.
C element: the carbon content determines the tensile strength and the brinell hardness of the martensitic wear-resistant steel. The carbon content is low, the hardness is low, the toughness is good, and the weldability is excellent; high carbon content, complete quenched martensite transformation, high strength, high hardness and good wear resistance, but the toughness and the weldability of the steel plate are reduced. The carbon content is controlled to be 0.18wt% -0.24 wt% based on the requirements of steel plate hardness, wear resistance and weldability.
Mo and Nb elements:
the Mo and Nb elements have the following functions in quenching heating and quenching cooling:
mo element: the element which greatly improves the hardenability of the steel is beneficial to forming full martensite during quenching, and the impact toughness of the steel plate is improved; mo is a strong carbide forming element at the same time, and the size of precipitated carbide is refined and the high-temperature tempering resistance is improved by influencing the diffusion rate of C, so that the steel plate can maintain certain strength, hardness and wear resistance in a medium-high temperature range.
Nb element: the dual strengthening effect is achieved by precipitation strengthening of fine Nb (C, N) in the ferrite matrix and grain refinement. Nb can inhibit austenite recrystallization and grain growth, and is helpful for generating fine ferrite grains; the effect is that Nb is easy to form fine and dispersed Nb (C, N) with C, N to prevent the migration of crystal boundary and raise the growth temperature of crystal grains, so as to obtain the effect of refining crystal grains.
In the quenching and heating step: a small amount of Mo can improve the solid solubility of Nb in austenite, thereby increasing the precipitation amount of quenching cooling niobium carbonitride. ② Mo can form segregation layer at the interface between Nb (C, N) and ferrite matrix, which inhibits the coarsening of Nb (C, N) grains, leads the Nb (C, N) precipitates to be more and smaller in size, and plays a good role in precipitation strengthening.
The martensite wear-resistant steel with good tensile strength, Brinell hardness and impact toughness can be obtained by Mo and Nb composite reinforcement.
The Mo and the Nb have the following functions in the high-temperature service environment of the martensite wear-resistant steel:
the added elements such as Mo and Nb have large difference with the radius of iron atoms, the martensite wear-resistant steel has large lattice distortion when in service at the high temperature of 100-300 ℃, C, N compounds of alloys such as Mo and Nb have strong interaction with dislocation at the temperature, and the interaction of C, N compounds of alloys such as Mo and Nb and dislocation promotes the martensite solid solution strengthening stability, improves the high-temperature deformation resistance and the degree of work hardening, and achieves the high-temperature strengthening effect.
Secondly, along with the temperature rise, the solid solubility of carbon atoms in the martensite is reduced, solid-soluble carbon elements are precipitated in the form of carbides, and the solid-solution strengthening effect is greatly reduced. The strong carbide forming elements Mo and Nb can block Fe to a certain extent3Precipitation of C-carbides, especially Mo solid solution strengthening and Mo2Precipitation strengthening of the C and Mo enrichment areas improves the solid solution strengthening stability of martensite, and improves the high-temperature tensile strength, the Brinell hardness and the high-temperature wear performance at 100-300 ℃.
Thirdly, according to the changes and the effects of Mo and Nb in quenching heating, quenching cooling and high-temperature service, the content of Mo is controlled to be 0.25wt% -0.45 wt%, and the content of Nb is controlled to be Nb: 0.025wt% to 0.055 wt%.
V: the compound V has relatively maximum solid solubility product in austenite, and is a precipitation strengthening element with good effect on the martensite high-temperature wear-resistant steel. The nitrogen has stronger affinity with microalloy element V, and vanadium nitride has higher solubility than vanadium carbide, so that the method greatly improves the carbonitride nucleation power of vanadium, improves the solid solution strengthening stability of martensite, improves the strength, hardness and wear resistance of the martensite wear-resistant steel at high temperature, and increases the tempering stability. The V content of the invention is within the range of 0.020wt% to 0.040 wt%.
The quenching cooling process generally comprises 3 aspects, namely, the quenching cooling process has high-strength cooling capacity and ensures that a quenching plate obtains required microstructure and mechanical properties; secondly, the quenching cooling has high uniformity, and the requirements of flatness and mechanical property uniformity of the quenching plate strip are met; and thirdly, the multifunctional high-precision quenching process is provided, and the requirements of temperature-controlled quenching and complex heat treatment are met.
The quenching cooling section of the quenching equipment commonly used at home and abroad is usually 20-30 m in length, the quenching cooling section is uniformly divided into 12-15 cooling zones according to the total length, the length of each cooling zone is the same, but the cooling process and the cooling function of each cooling zone are different.
Generally, a 1-6 cooling area is a high-pressure rapid cooling section, the cooling rate is confirmed according to a static CCT curve, the 1-6 cooling area is rapidly cooled at a cooling rate which is greater than or equal to the cooling rate formed by martensite, the cooling temperature range is Ac3+ (30-60 ℃) to the martensite phase transformation starting point, the main purpose is to avoid bainite, pearlite and other phase transformations in the rapid cooling of the steel plate in the high-temperature stage, uniform martensite structures are obtained, the hardness and the wear resistance of the steel plate are ensured, and the rapid cooling of the 1-6 cooling area in the high-pressure rapid cooling section is the guarantee of the basic microstructure and the mechanical property of the steel plate.
Generally, the 7-15 cooling area (tail area) is a low-pressure medium-low speed cooling section, the cooling temperature range is from the martensite start phase transformation point to the normal temperature or the martensite phase transformation finishing temperature, the 7-15 area (tail area) low-pressure medium-low speed cooling section is a stable martensite forming area, and the quenching cooling process can be adjusted to regulate and control the microstructure of the steel plate and obtain special performance.
FIG. 2 is a schematic view of different cooling zones of the quenching machine of the present invention; in the figure, the arrows indicate the direction of travel of the steel sheet; in the drawings, reference numerals 1 to 15 denote: a cooling 1 area, a cooling 2 area, a cooling 3 area, a cooling 4 area, a cooling 5 area, a cooling 6 area, a cooling 7 area, a cooling 8 area, a cooling 9 area, a cooling 10 area, a cooling 11 area, a cooling 12 area, a cooling 13 area, a cooling 14 area and a cooling 15 area; the mark 16 is a high-pressure rapid cooling section which comprises a cooling 1 area, a cooling 2 area, a cooling 3 area, a cooling 4 area, a cooling 5 area and a cooling 6 area; the mark 17 is a low-pressure medium-low speed cooling section which comprises a cooling 7 area, a cooling 8 area, a cooling 9 area, a cooling 10 area, a cooling 11 area, a cooling 12 area, a cooling 13 area, a cooling 14 area and a cooling 15 area; reference numeral 18 is a cooling header; the cooling water quantity of the high-pressure rapid cooling section, the opening and closing of the cooling area, the cooling water ratio, the steel plate running speed and other parameters can be adjusted and independently controlled according to the process conditions. The cooling water quantity, the opening and closing of the cooling area, the cooling water ratio, the steel plate running speed and other parameters of the low-pressure medium-low speed cooling section can be adjusted and independently controlled according to the process conditions.
The cooling rate of the quenching high-pressure rapid cooling section is about 2.0-4.0 times of that of the low-pressure medium-low speed cooling section, the high-pressure rapid cooling speed range can reach 0-300 ℃/s for a steel plate with the thickness of 10mm, the cooling speed range of the low-pressure medium-low speed cooling section can reach 0-150 ℃/s, and the functional requirements of the complex quenching cooling process of most high-end products are met.
The cooling rate of the quenching high-pressure rapid cooling section and the low-pressure medium-low speed cooling section can be accurately controlled by adjusting the flow rate, the water-to-water ratio, the speed of a roller way and the like of cooling water.
One of the core innovation points of the invention is as follows: the method adopts a temperature-controlled and speed-controlled quenching heat treatment process, and the temperature-controlled and speed-controlled quenching process adopts an interval cooling method.
The front area of the quenching cooling high-pressure rapid cooling section is opened, and the rear area is closed, namely: starting a cooling area 1 and an area 2, and closing a cooling area 3 and an area 4 and an area 5 and an area 6; or starting the cooling zone 1 + zone 2 + zone 3, and closing the cooling zone 4 + zone 5 + zone 6; or the cooling 1 area +2 area +3 area +4 area is started, and the cooling 5 area +6 area is closed.
The front area of the low-pressure and medium-low-speed cooling section of quenching cooling is closed, and the rear area is opened, namely: closing a cooling 7 area +8 area +9 area +10 area +11 area +12 area, and opening a cooling 13 area +14 area +15 area; or closing the cooling zone 7 +8 +9 +10 +11 and opening the cooling zone 12 +13 +14 + 15; or closing the cooling zone 7 +8 +9 +10 and opening the cooling zone 11 +12 +13 +14 + 15; or the cooling 7 area +8 area +9 area is closed, and the cooling 10 area +11 area +12 area +13 area +14 area +15 area is opened.
When the steel plate runs from the high-pressure rapid cooling section to the low-pressure medium-low speed cooling section, the closing position of the cooling section, namely the closing position of the cooling header can enable the steel plate to have the time of air cooling for 4-9 seconds, C, N compounds of fine and dispersed micro-alloy elements such as Nb, Mo and V in the quenching cooling process are promoted to be separated out, fine and dispersed Nb (C, N), Mo (C, N) and V (C, N) prevent the migration of crystal boundaries, the growth temperature of crystal grains is increased, and the quenched steel plate has the advantages of fine crystal grain size and dual effects of fine grain strengthening and precipitation strengthening. Finally, the dual effects of fine grain strengthening and precipitation strengthening are still kept in the service process of 100-300 ℃, the high-temperature tensile strength and the Brinell hardness of the steel plate are stabilized, and the high-temperature wear resistance is improved.
According to the production method of the martensite high-temperature wear-resistant steel, the sub-temperature quenching heating temperature is 840-880 ℃, the quenching heating heat preservation coefficient is 2.5min/mm, and the heat preservation time is 20-75 minutes.
According to the production method of the martensite high-temperature wear-resistant steel, the low-temperature tempering process has the tempering temperature of 120-180 ℃, the heat preservation time coefficient of 5.0min/mm and the heat preservation time range of 40-150 min, and the microstructure and the mechanical property are not changed while the internal stress in the steel plate is fully released; then air-cooled to room temperature.
According to the production method of the martensite high-temperature wear-resistant steel, in the casting blank reheating process, the casting blank reheating temperature ranges from 1140 ℃ to 1200 ℃, the soaking period time ranges from 30 minutes to 50 minutes, and the temperature gradient is eliminated.
According to the production method of the martensite high-temperature wear-resistant steel, the controlled rolling process adopts a double-rolling-process controlled rolling process, namely the controlled rolling of a rough rolling austenite recrystallization region and the controlled rolling of a finish rolling austenite non-recrystallization region, wherein the rolling temperature of the rough rolling austenite recrystallization region is 1100-960 ℃, and the rolling temperature of the finish rolling austenite non-recrystallization region is 920-840 ℃; and after controlled rolling, the steel grade is slowly cooled to room temperature by air cooling to obtain the original low internal stress hot rolled steel plate.
According to the production method of the martensite high-temperature wear-resistant steel, the thickness of the produced wear-resistant steel plate ranges from 8mm to 30mm, the normal-temperature Brinell hardness is 400HBW to 430HBW, and the microstructure at 100-300 ℃ is as follows: the lath martensite with clear grain boundary and the solid-solution carbon element are not precipitated in the form of carbide; the mechanical properties of the alloy at 100-300 ℃ are as follows: the tensile strength ranges from 1250MPa to 1352MPa, the Brinell hardness is 388HBW to 420HBW, and the repeated low-stress impact wear performance at the high temperature of 100-300 ℃ is improved by 2.38-6.99 times compared with that of the conventional wear-resistant steel, so that the service requirements of complex working conditions of repeated impact at the high temperature of 100-300 ℃ and high-temperature wear are met.
The basis of the core control process of the invention is: and measuring the phase change transformation rule of the component system at different isothermal times and different cooling rates by using a DIL805L phase change expander, and formulating a heat treatment process according to the detection result.
The invention has the beneficial effects that:
the thickness range of the wear-resistant steel plate produced by the invention is 8-30 mm, the normal-temperature Brinell hardness is 400 HBW-430 HBW, and the microstructure at 100-300 ℃ is as follows: lath martensite with clear grain boundary, and solid-solution carbon element is not precipitated in the form of carbide; the mechanical properties of the alloy at 100-300 ℃ are as follows: the tensile strength ranges from 1250MPa to 1352MPa, the Brinell hardness is 388HBW to 420HBW, and the high-temperature repeated low-stress impact wear performance is improved by 2.38 times to 6.99 times compared with that of conventional wear-resistant steel, so that the service requirement of complex working conditions of high-temperature repeated impact and high-temperature wear at 100 ℃ to 300 ℃ is met.
The wear-resistant steel product produced by the process still has good tensile strength, hardness and wear-resistant rigidity under the high-temperature service condition, has good impact wear resistance, improves the service life of equipment under severe working conditions, realizes light weight, saves energy consumption, develops green, reduces cost, develops a new era of high-performance new materials in domestic and foreign industries, and has great market popularization value.
Drawings
FIG. 1 shows the transformation law of high-grade wear-resistant steel phase change, namely a static CCT curve, under the composition system of the invention;
FIG. 2 is a schematic view of the various cooling zones of the quench machine of the present invention;
FIG. 3 is a microstructure diagram of normal temperature martensite morphology of the wear-resistant steel product of the present invention;
FIG. 4 is a microstructure diagram of martensite morphology in example 1 of the present invention;
FIG. 5 is a wear surface micro-topography after wear by a defined impact grit under 300 ℃ service conditions for a wear resistant steel product produced with the same hardness level, general composition system and process of the present invention;
FIG. 6 shows the micro-morphology of the wear surface of example 1 after wear by limited impact abrasive particles under 300 ℃ service conditions;
labeled as: 1 denotes a cooling 1 region, 2 denotes a cooling 2 region, 3 denotes a cooling 3 region, 4 denotes a cooling 4 region, 5 denotes a cooling 5 region, 6 denotes a cooling 6 region, 7 denotes a cooling 7 region, 8 denotes a cooling 8 region, 9 denotes a cooling 9 region, 10 denotes a cooling 10 region, 11 denotes a cooling 11 region, 12 denotes a cooling 12 region, 13 denotes a cooling 13 region, 14 denotes a cooling 14 region, 15 denotes a cooling 15 region, 16 denotes a high-pressure rapid cooling section, 17 denotes a low-pressure medium-low-speed cooling section, and 18 denotes a cooling header.
Detailed Description
The basis of the core control process of the invention is: the phase transformation law of the component system with different isothermal times and different cooling rates is measured by using a DIL805L phase transformation dilatometer, the experimental results are shown in Table 1 and figure 1, the Table 1 and figure 1 show that the temperature Ac3 of the steel plate ferrite to austenite complete transformation is 819 ℃, and in order to ensure that the steel plate complete austenitization in the thickness direction and the length direction is sufficient and uniform, the quenching heat treatment heating temperature and the heat preservation temperature are 30-50 ℃ above Ac 3; FIG. 1 shows that the temperature Ac1 at which the ferrite transformation of the steel sheet into austenite begins to occur is 764 ℃, the martensite transformation begins to occur when the cooling rate reaches 20 ℃/s, the martensite start transformation temperature is 422 ℃, the martensite start transformation temperature gradually decreases from 422 ℃ to 386 ℃ as the cooling rate increases, and the martensite transformation end temperature gradually decreases from 229 ℃ to 189 ℃, and the heat treatment process is formulated based on the above-mentioned test results.
TABLE 1 phase transition law of different isothermal times and different cooling rates of the component system
FIG. 2 is a schematic view of different cooling zones of the quenching machine of the present invention; in the figure, the arrows indicate the direction of travel of the steel sheet; in the figure, the symbols 1 to 15 indicate in sequence: cooling in a 1-15 area; the mark 16 is a high-pressure rapid cooling section which comprises a cooling 1 area, a cooling 2 area, a cooling 3 area, a cooling 4 area, a cooling 5 area and a cooling 6 area; the mark 17 is a low-pressure medium-low speed cooling section which comprises a cooling 7 area, a cooling 8 area, a cooling 9 area, a cooling 10 area, a cooling 11 area, a cooling 12 area, a cooling 13 area, a cooling 14 area and a cooling 15 area; reference numeral 18 is a cooling header; the cooling water quantity of the high-pressure rapid cooling section, the opening and closing of the cooling area, the cooling water ratio, the steel plate running speed and other parameters can be adjusted and independently controlled according to the process conditions. The cooling water quantity, the opening and closing of the cooling area, the cooling water ratio, the steel plate running speed and other parameters of the low-pressure medium-low speed cooling section can be adjusted and independently controlled according to the process conditions.
The invention is further illustrated and specifically described by the following five examples:
step 1:
the low-alloy wear-resistant steels with the thicknesses of 8mm, 12mm, 20mm, 25mm and 30mm are respectively produced in the embodiments 1 to 5, and the components and the mass percentages of the wear-resistant steels in the 5 embodiments are listed in the table 2:
table 2: composition and mass percentage content of wear-resistant steel
Step 2:
in the embodiments 1-5, the reheating temperature range of the casting blank is 1140-1200 ℃, the soaking period time is 30-50 minutes, the rough rolling temperature range is 1100-960 ℃, and the finish rolling temperature range is 920-840 ℃. And after controlled rolling, the steel grade is slowly cooled to room temperature by air cooling. Table 3 lists the process parameters of the rolling stage of the low alloy wear resistant steel of examples 1-5.
Table 3: examples 1 to 5 Process parameters of Low-alloy wear-resistant steels at Rolling stage
And step 3:
the heat treatment processes of the embodiments 1 to 5 are as follows: 1. the martensite solid solution strengthening stability elements C, Mo and V are added, so that the high-temperature deformation resistance and the work hardening degree are improved, the tempering stability is increased, the high-temperature strengthening effect is achieved, the tensile strength and the Brinell hardness of the martensite wear-resistant steel are not reduced too much along with the temperature increase, and the martensite wear-resistant steel has good wear resistance under the high-temperature service environment. 2. A temperature-control and speed-control quenching heat treatment process is adopted, C, N compounds of fine and dispersed micro-alloy elements such as Nb, Mo and V are promoted to be separated out in the quenching cooling process, fine and dispersed Nb (C, N), Mo (C, N) and V (C, N) prevent grain boundary migration, the grain growth temperature is increased, the grain refining effect is achieved, the dual effects of separation strengthening and fine grain strengthening at 100-300 ℃ are improved, the high-temperature tensile strength and the Brinell hardness are stabilized, and the high-temperature wear resistance is improved.
The sub-temperature quenching heating temperature is 840-880 ℃, the quenching heating heat preservation coefficient is 2.5min/mm, and the heat preservation time is 20-75 minutes. Table 4 shows the control parameters of the quenching heat treatment heating process of examples 1 to 5.
TABLE 4 control parameters of quenching heat treatment heating process of examples 1 to 5
The quenching cooling process adopts an interval cooling method: opening a cooling area 2-4 before the quenching cooling high-pressure rapid cooling section, and closing a subsequent cooling area 5-6; the front region 7-9 of the low-pressure medium-low speed cooling section of quenching cooling is closed, and the rear region1Opening the cooling area of 0-15 deg.C.
By adopting an interval quenching cooling process, the high-pressure rapid cooling section is rapidly cooled to 422-386 ℃ from the martensite start transformation point Ms point by cooling at 28-54 ℃/s, the steel plate is stopped at the position where the cooling header 18 is closed for air cooling, and the main purpose is to promote the precipitation of C, N compounds of microalloy such as fine grains of Nb, Mo and V and the like and improve the precipitation strengthening effect. The air cooling time of the steel plate is 4-9 seconds, and then the steel plate enters a low-pressure medium-low speed cooling section 10-15 cooling area and is cooled to room temperature at a cooling speed of 20-30 ℃/s.
Table 5 shows the control parameters of the temperature and speed controlled quenching heat treatment process of examples 1 to 5.
Table 5 control parameters of temperature and speed controlled quenching heat treatment process of examples 1 to 5
A temperature-control and speed-control quenching heat treatment process is adopted, C, N compounds of fine and dispersed micro-alloy elements such as Nb, Mo and V are promoted to be separated out in the quenching cooling process, fine and dispersed Nb (C, N), Mo (C, N) and V (C, N) prevent grain boundary migration, the grain growth temperature is increased, the grain refining effect is achieved, the dual effects of separation strengthening and fine grain strengthening at 100-300 ℃ are improved, the high-temperature tensile strength and the Brinell hardness are stabilized, and the high-temperature wear resistance is improved.
And 4, step 4:
and (2) adopting a low-temperature tempering process, wherein the tempering temperature is 120-180 ℃, the heat preservation time coefficient is 5.0min/mm, the heat preservation time range is 40-150 minutes, the low-temperature tempering process ensures that the microstructure and the mechanical property are not changed while the internal stress in the steel plate is fully released, and then air cooling is carried out to the room temperature. Table 6 shows the low temperature tempering process parameters of examples 1-5.
TABLE 6 EXAMPLES 1 TO 5 LOW-TEMPERATURE REFINING PROCESS PARAMETERS
| Examples | Thickness mm | Tempering temperature DEG C | Temperature keeping time coefficient min/mm | Holding time min |
| 1 | 8 | 120 | 5.0 | 40 |
| 2 | 12 | 135 | 5.0 | 60 |
| 3 | 20 | 150 | 5.0 | 100 |
| 4 | 25 | 165 | 5.0 | 125 |
| 5 | 30 | 180 | 5.0 | 150 |
And 5: examples 1-5 detection of high-temperature service microstructure and mechanical properties:
FIG. 3 shows the microstructure of the wear-resistant steel product produced by the process of the present invention at normal temperature, wherein the microstructure is mainly low temperature tempered martensite, and the lath size is small, so that the steel plate has good mechanical properties and formability.
FIG. 4 shows the high-temperature service microstructure of example 1, in which the microstructure of the steel plate is lath martensite with clear grain boundaries at 100-300 ℃ due to the addition of martensite high-temperature stabilizing elements such as Mo, Nb, V, etc., and when the service temperature is increased from 100 ℃ to 300 ℃, the lath boundaries of the martensite do not have obvious interdiffusion, obvious mutual aggregation, and obvious mutual combination and recombination among atoms, the grain boundaries of the martensite do not appear obvious blurring or disappearance, and solid-solution carbon elements are not precipitated in the form of carbides.
Table 7 shows the normal temperature performance and the mechanical property at 100-300 ℃ of the wear-resistant steel products produced by the method in the embodiments 1-5, and it can be seen that the normal temperature performance and the high temperature mechanical property at 100-300 ℃ in the embodiments 1-5 are good, the brinell hardness at normal temperature is 400 HBW-430 HBW, and the mechanical property at 100-300 ℃ is as follows: the tensile strength ranges from 1250MPa to 1352MPa, and the Brinell hardness ranges from 388HBW to 420 HBW. Wherein under the service condition of 100 ℃: the tensile strength ranges from 1315MPa to 1352MPa, and the Brinell hardness ranges from 405HBW to 420 HBW; wherein under the service condition of 200 ℃: the tensile strength ranges from 1278MPa to 1300MPa, and the Brinell hardness ranges from 394HBW to 409 HBW; wherein under the service condition of 300 ℃: the tensile strength ranges from 1250MPa to 1282MPa, and the Brinell hardness ranges from 388HBW to 395 HBW. The service condition from normal temperature to 300 ℃ can be seen, the mechanical property does not show obvious decline trend, and the component system and the wear-resistant steel product produced by the process scheme have good tempering stability and good high-temperature strengthening effect at the temperature of 100-300 ℃, so that the tensile strength and the Brinell hardness of the martensite wear-resistant steel are not reduced too much along with the temperature increase, and the martensite wear-resistant steel has good wear resistance under the high-temperature service environment.
Table 7 Normal temperature Properties and mechanical Properties at 100-300 ℃ of the wear-resistant Steel products produced in examples 1-5
Table 8 shows the 100-300 ℃ impact wear performance of the wear-resistant steel products produced in examples 1-5 and the wear-resistant steel products of the same grade in the common process.
Under the service condition of 100 ℃ temperature: the average weight loss of the wear-resistant steel products produced in the embodiments 1 to 5 is 0.3945g, 03854g, 0.3754g, 0.3925g and 0.3959g respectively after 60 minutes of wear by impact and abrasive wear under the condition that the applied impact pressure is 0.2 MPa; after the abrasion of the impact abrasive particles for 60min, the average weight loss of an abrasion sample of the abrasion-resistant steel product with the same grade produced by the common process is 0.9428 g. The wear-resistant steel product produced by the method has the wear resistance improved by 2.38-2.51 times compared with the wear resistance of a common product at the high temperature of 100 ℃.
Under the service condition of the temperature of 200 ℃: the average weight loss of the wear-resistant steel products produced in the embodiments 1 to 5 is 0.4586g, 0.4648g, 0.4553g, 0.4412g and 0.4762g respectively after 60min of impact abrasive wear under the condition that the applied impact pressure is 0.2 MPa; after the abrasion of the impact abrasive particles for 60min, the average weight loss of an abrasion sample of the abrasion-resistant steel product with the same grade produced by the common process is 1.7243 g. The wear-resistant steel product produced by the method has the wear resistance improved by 3.62-3.91 times compared with the wear resistance of a common product at the high temperature of 200 ℃.
Under the service condition of the temperature of 300 ℃: the average weight loss of the wear-resistant steel products produced in the embodiments 1 to 5 is 0.5612g, 0.5385g, 0.5364g, 0.5258g and 0.5537g respectively after 60min of impact abrasive wear under the condition that the applied impact pressure is 0.2 MPa; after the abrasion of the impact abrasive particles for 60min, the average weight loss of an abrasion sample of the abrasion-resistant steel product with the same grade produced by the common process is 3.6743 g. The wear-resistant steel product produced by the method has the wear resistance improved by 6.55-6.99 times compared with the wear resistance of a common product at the high temperature of 300 ℃.
TABLE 8 comparison of impact wear properties (impact pressure 0.2MPa, impact grit wear 60 minutes)
FIG. 5 is a wear surface micro-topography after wear by a defined impact grit under 300 ℃ service conditions for a wear resistant steel product produced with the same hardness level, general composition system and process of the present invention; it can be seen that after the wear-resistant steel product produced by the common component system and the process is subjected to high-temperature impact wear at 300 ℃, the surface has more peeling pits, the fatigue peeling degree is higher, the wear form is mainly oxidation wear, the oxide layer covering the material matrix forms cracks, the cracks continue to expand and gather, finally, the oxide layer peels off greatly, and the impact wear loss in the high-temperature environment is great.
FIG. 6 shows the micro-morphology of the wear surface of example 1 after wear by limited impact abrasive particles under 300 ℃ service conditions; it can be seen that the wear-resistant steel product produced by the invention mainly takes impact fatigue wear as main material, forms impact fatigue spalling, is accompanied by a small amount of oxidation and abrasive wear, and has small loss of weight due to impact wear in a high-temperature environment.
The wear-resistant steel product produced by the process still has good tensile strength, hardness and wear-resistant rigidity under the high-temperature service condition, and the martensite high-temperature wear-resistant steel has good impact wear resistance, so that the service life of equipment under severe working conditions is prolonged, the lightweight, energy-saving and green development is realized, the cost is reduced, the epoch of high-performance new materials in high-end industry at home and abroad is developed, and the martensite high-temperature wear-resistant steel has great market popularization value.
Claims (9)
1. The martensite high-temperature wear-resistant steel is characterized in that: the weight percentages of the chemical components are respectively as follows: c: 0.18% -0.24%, Si: 0.10% -0.35%, Mn: 0.50-1.10%, P is less than or equal to 0.013%, S is less than or equal to 0.004%, Als: 0.030% -0.060%, Nb: 0.025% -0.055%, V: 0.020% -0.040%; ti: 0.010-0.025%, Cr: 0.10% -0.35%, Mo: 0.25% -0.45%, B: 0.0005% -0.0018%, N: 0.0030-0.0045%, H is less than or equal to 1.7ppm, Ca: 0.0020-0.0040 percent, and the balance of Fe and inevitable impurities.
2. The martensitic high-temperature wear-resistant steel as claimed in claim 1, wherein: the weight percentage range of the chemical components is as follows: c: 0.19% -0.22%, Si: 0.15% -0.30%, Mn: 0.60-0.90%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, Als: 0.045% -0.055%, Nb: 0.03% -0.045%, V: 0.025% -0.040%; ti: 0.010-0.020%, Cr: 0.15% -0.30%, Mo: 0.30% -0.40%, B: 0.0009% -0.0014%, N: 0.0033% -0.0042%, H is less than or equal to 1.4ppm, Ca: 0.0030-0.0040% and the balance of Fe and inevitable impurities.
3. The production method of the martensite high-temperature wear-resistant steel comprises the working procedures of steel making, continuous casting, billet reheating, controlled rolling, air cooling after rolling, temperature and speed controlled quenching and low-temperature tempering, and is characterized in that: the weight percentage range of the components of the casting blank in the continuous casting procedure is as follows: c: 0.18% -0.24%; si: 0.10% -0.35%; mn: 0.50% -1.10%; p is less than or equal to 0.013 percent; s is less than or equal to 0.004 percent; and Als: 0.030% -0.060%; nb: 0.025% -0.055%; v: 0.020% -0.040%; ti: 0.010% -0.025%; cr: 0.10% -0.35%; mo: 0.25% -0.45%; b: 0.0005% -0.0018%; n: 0.0030% -0.0045%; h is less than or equal to 1.7 ppm; ca: 0.0020-0.0040 percent, and the balance of Fe and inevitable impurities.
4. A method of producing a martensitic high temperature wear resistant steel as claimed in claim 3 wherein: the temperature and speed control quenching process comprises the following steps:
controlling the quenching heating temperature: the quenching and heating temperature is controlled to be Ac3+ (30-50 ℃), and meanwhile, a sub-temperature quenching and heating process is adopted; the quenching cooling process adopts an interval cooling method, the front area of the high-pressure rapid cooling section is opened, the rear area is closed, the front area of the low-pressure medium-low velocity cooling section is closed, and the rear area is opened.
5. The method for producing a martensitic high-temperature wear-resistant steel as claimed in claim 4, wherein: the front area of the high-pressure rapid cooling section is opened, and the rear area is closed, namely: starting a cooling area 1 and an area 2, and closing a cooling area 3 and an area 4 and an area 5 and an area 6; or starting the cooling zone 1 + zone 2 + zone 3, and closing the cooling zone 4 + zone 5 + zone 6; or starting the cooling zone 1 + zone 2 + zone 3+ zone 4, and closing the cooling zone 5 + zone 6; the front area of the low-pressure medium-low speed cooling section is closed, and the rear area is opened, namely: closing a cooling 7 area +8 area +9 area +10 area +11 area +12 area, and opening a cooling 13 area +14 area +15 area; or closing the cooling zone 7 +8 +9 +10 +11 and opening the cooling zone 12 +13 +14 + 15; or closing the cooling zone 7 +8 +9 +10 and opening the cooling zone 11 +12 +13 +14 + 15; or the cooling 7 area +8 area +9 area is closed, and the cooling 10 area +11 area +12 area +13 area +14 area +15 area is opened.
6. The method for producing a martensitic high-temperature wear-resistant steel as claimed in claim 5, wherein: in the quenching cooling process, a 2-4 cooling area before a quenching cooling high-pressure rapid cooling section is rapidly cooled to a martensite start phase transformation point Ms point at a cooling speed of 28-54 ℃/s, and a steel plate is air-cooled at a position where a cooling header is closed; and (3) air cooling the steel plate for 4-9 seconds, then, entering a low-pressure medium-low speed cooling section opening area, and cooling to room temperature at a cooling speed of 20-30 ℃/s.
7. The method for producing a martensitic high-temperature wear-resistant steel as claimed in claim 4, wherein: the sub-temperature quenching heating temperature is 840-880 ℃, the quenching heating heat preservation coefficient is 2.5min/mm, and the heat preservation time is 20-75 minutes.
8. A method of producing a martensitic high temperature wear resistant steel as claimed in claim 3 wherein: in the low-temperature tempering process, the tempering temperature is 120-180 ℃, the heat preservation time coefficient is 5.0min/mm, the heat preservation time range is 40-150 min, and then the air cooling is carried out to the room temperature; in the casting blank reheating process, the reheating temperature range of the casting blank is 1140-1200 ℃, and the soaking period time is 30-50 minutes; the controlled rolling process adopts a double-rolling-process controlled rolling process, namely controlled rolling of a rough rolling austenite recrystallization region and controlled rolling of a finish rolling austenite non-recrystallization region, wherein the rolling temperature of the rough rolling austenite recrystallization region ranges from 1100 ℃ to 960 ℃ in a first rolling process, and the rolling temperature of the finish rolling austenite non-recrystallization region ranges from 920 ℃ to 840 ℃ in a second rolling process; and after controlled rolling, the steel grade is slowly cooled to room temperature by air cooling to obtain the original low internal stress hot rolled steel plate.
9. The martensitic high-temperature wear-resistant steel as claimed in claim 1 or 2, wherein the thickness of the steel plate ranges from 8mm to 30mm, the normal-temperature Brinell hardness ranges from 400HBW to 430HBW, and the microstructure ranges from 100 ℃ to 300 ℃ as follows: lath martensite with clear grain boundary; the mechanical properties of the alloy at 100-300 ℃ are as follows: the tensile strength ranges from 1250MPa to 1352MPa, the Brinell hardness is 388HBW to 420HBW, and the repeated low-stress impact wear performance at the high temperature of 100-300 ℃ is improved by 2.38-6.99 times compared with that of the conventional wear-resistant steel, so that the service requirements of complex working conditions of repeated impact at the high temperature of 100-300 ℃ and high-temperature wear are met.
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