CN115369332B - Maraging ultrahigh-strength steel and preparation method thereof - Google Patents
Maraging ultrahigh-strength steel and preparation method thereof Download PDFInfo
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Abstract
The invention relates to the technical field of alloy steel, in particular to maraging ultrahigh-strength steel and a preparation method thereof. The maraging ultra-high strength steel comprises the following raw materials in parts by weight: less than or equal to 0.005 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.05 percent of Si, less than or equal to 0.002 percent of S, less than or equal to 0.005 percent of P, 18.5 to 19.5 percent of Ni, 9.5 to 10.0 percent of Co, 5.0 to 6.0 percent of Mo, 0.7 to 0.90 percent of Ti, less than or equal to 0.20 percent of Al, less than or equal to 0.00005 percent of H, less than or equal to 0.0010 percent of O, less than or equal to 0.0010 percent of N, and the balance of Fe and other unavoidable impurities. The method uses pure iron, refined steel, intermediate alloy and pure metal material as raw materials, realizes few residual elements, and improves interaction between main elements. Through the adjustment of chemical components, the ultra-high strength steel has more martensite structure at room temperature, and the strength, plasticity and toughness of the steel are improved; the content of residual elements is reduced, so that the ultra-high strength steel has high strength and good toughness, and the crack sensitivity of the ultra-high strength steel is improved.
Description
Technical Field
The invention relates to the technical field of alloy steel, in particular to maraging ultrahigh-strength steel and a preparation method thereof.
Background
The ultra-high strength steel is steel with tensile strength exceeding 1500MPa at room temperature and yield strength exceeding 1300 MPa. The ultra-high strength steel has good plasticity and toughness, as little notch sensitivity as possible, high fatigue strength and good manufacturability besides the tensile strength of more than 1500 MPa.
In the prior art, the high alloy ultrahigh strength steel is prepared by adding Ni, co, ti, al, mo and other chemical elements into steel, and the chemical elements are reasonably proportioned, so that a large amount of martensitic structure is formed after solid solution, and intermetallic compounds are precipitated in a matrix after aging, and the pinning effect is formed on the martensitic structure similarly, so that the strength and hardness can be greatly improved. Generally, the alloy ratio of the high-alloy ultra-high-strength steel is more than 9%, and the alloy ratio of the high-end ultra-high-strength steel can reach more than 25%, and the main strengthening elements are C, ni, co, mo, al, ti, cr and the like.
However, the ultra-high strength steel of the prior art has the following problems:
the tensile strength is high, and the toughness and the plasticity are relatively poor.
Through the smelting process of vacuum induction and vacuum consumable furnaces, the smelting raw materials of the vacuum induction furnaces are all brand new high-purity metal materials, and the raw material cost is high.
Disclosure of Invention
Aiming at the technical problems, the invention provides maraging ultrahigh-strength steel and a preparation method thereof, wherein the content of impurity elements in the ultrahigh-strength steel is reduced, and the purity of the steel is improved; the hardness of the steel is improved and the toughness is slightly improved by adjusting the chemical components; the crack sensitivity is improved by the reduction of residual chemical elements and the optimization of the hot working process.
In order to solve the technical problems, the embodiment of the invention adopts the following technical scheme:
in a first aspect, an embodiment of the present invention provides a maraging ultra-high strength steel, characterized in that the raw materials for the preparation thereof comprise the following components in percentage by weight: less than or equal to 0.005 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.05 percent of Si, less than or equal to 0.002 percent of S, less than or equal to 0.005 percent of P, 18.5 to 19.5 percent of Ni, 9.5 to 10.0 percent of Co, 5.0 to 6.0 percent of Mo, 0.7 to 0.90 percent of Ti, less than or equal to 0.20 percent of Al, less than or equal to 0.00005 percent of H, less than or equal to 0.0010 percent of O, less than or equal to 0.0010 percent of N, and the balance of Fe and other unavoidable impurities.
Compared with the prior art, the ultra-high strength steel provided by the embodiment of the invention realizes few residual elements by using high-purity pure iron, refined steel, intermediate alloy and pure metal as raw materials, and improves the interaction between main elements.
Through the adjustment of chemical components, the ultra-high strength steel has more martensite structure at room temperature, and the strength, plasticity and toughness of the steel are improved; the content of residual elements is reduced, so that the ultra-high strength steel has high strength and good toughness, and the crack sensitivity of the ultra-high strength steel is improved.
In the invention, the maximum values of residual elements are summarized through multi-batch trial production in the range of production capacity, and the residual elements C, mn, si, S, P, H, O, N and the like are regarded as impurity elements, so that the purity of the ultra-high strength steel is improved and the crack sensitivity is improved as low as possible.
The addition of a large amount of Ni can enlarge elements in an austenite phase region, and in the cooling process after austenitizing, the transformation from austenite to pearlite and bainite is strongly inhibited, so that the hardenability of martensite is improved; ni reduces the temperature of transformation from supercooled austenite to martensite, reduces the transformation point of martensite, increases the content of residual austenite, and is beneficial to toughness; the stacking fault energy of the steel matrix can be improved, so that screw dislocation is easy to generate cross sliding, and the toughness is improved. Ni can form intermetallic compound Ni with Ti in the steel 3 Ti is pinned in the grain boundary to strengthen the grain boundary and greatly improve the strength of the steel. Therefore, the addition of Ni in a large amount can improve the plasticity and toughness of the steel, so that the steel has high strength and good toughness.
Co is added in large amount to reduce the solid solubility of Mo in martensite and raise the martensitic transformation point, so as to promote the transformation of Mo-containing intermetallic compound (such as Ni 3 Mo、Fe 2 Mo) precipitation; meanwhile, co can inhibit the recovery of dislocation substructure in martensite and provide more nucleation sites for the formation of subsequent precipitated phases, so that the precipitated phase particles are finer and uniformly distributed, and the precipitated phase particles are reducedSub-spacing. Meanwhile, co can also improve the Mo temperature, partially make up for the reaction of Ni, ensure that all the steel is in a martensitic structure after solid solution, and cannot be replaced by other elements. Co is added in a large amount to raise the martensitic transformation point, the martensitic content is higher in the room temperature state, and the strength of the steel can be improved without deep cooling. In addition, co is added in a large amount, so that the heat treatment process is simplified from complicating, and the deep cooling treatment is not needed.
The action of Ti in the steel is represented by Ti being the most effective strengthening alloy element, and the addition of Ti in large quantity forms Ni in the ultra-high strength steel of the invention 3 The Ti metal compound is precipitated in the grain boundary, so that the grain boundary strength is improved, the strengthening effect is achieved, and the strength of the steel is greatly improved. However, when the strength of the Ti-reinforced Fe-Ni alloy reaches a high level, the toughness and the plasticity are seriously deteriorated.
Al plays a role in the ultra-high strength steel, and is embodied in refining grains and improving toughness at low temperature. This is due to the fact that Al forms a finely dispersed distribution of the refractory compound aluminum nitride (AlN 3 ) Thereby suppressing grain growth. However, excessive Al tends to coarsen austenite grains.
Mo is an alloying element that contributes to both strength and toughness in the ultra-high strength steel of the present invention. Mo-rich precipitates precipitated in the early stage of aging play an important role in strengthening and ensuring the toughness of steel. The tissue precipitation phase is precipitated along the prior austenite grain boundary, thereby avoiding the along-grain fracture and improving the fracture toughness. However, the excessive addition of Mo (more than 10%) also produces retained austenite as in the case of the excessive addition of nickel.
If Co is not present, the interaction between Co and Mo is lost, the amount of Mo-rich precipitates is relatively reduced, and the strengthening effect is reduced.
In a second aspect, the embodiment of the invention also provides a preparation method of maraging ultrahigh-strength steel, which adopts a vacuum induction furnace and vacuum consumable furnace remelting smelting process, and mainly comprises the following steps:
the mass percentages of the components in the preparation raw materials are added into a vacuum induction furnace for casting the electrode;
remelting the electrode into steel ingots in a vacuum consumable hearth;
carrying out high-temperature diffusion annealing on the steel ingot, and forging to obtain a blank;
rolling the blank into a finished product;
and carrying out solution treatment and aging treatment on the finished product to obtain the maraging ultrahigh-strength steel.
According to the preparation method of the maraging ultrahigh-strength steel, disclosed by the embodiment of the invention, the secondary degassing of a smelting process of primary vacuum induction and consumable vacuum remelting is adopted, so that the gas content is lower, the non-metallic inclusion B-type inclusion oxides and E-type inclusion nitrides are fewer, the strength, plasticity and toughness of the steel are effectively improved, the chemical components can be precisely controlled by the smelting method, the point control requirement is met, the content of residual elements is greatly reduced, and the maraging ultrahigh-strength steel has high strength and good toughness.
Preferably, the raw materials include: pure iron or refined steel, wherein S is less than or equal to 0.002 percent and P is less than or equal to 0.005 percent in the pure iron, and S, P is less than or equal to 0.001 percent in the refined steel;
the intermediate alloy is vacuum induction, vacuum consumable remelting and a residual stub bar after blank rolling;
the pure metal material is metal Mo, metal Ni, metal Co and metal Ti (sponge Ti), wherein the purities of the metal Mo, the metal Ni, the metal Co and the metal Ti (sponge Ti) are all more than or equal to 99 percent.
In the embodiment of the invention, the raw materials comprise intermediate alloy, pure iron or refined steel and pure metal, so that the content of residual elements can be reduced, and the interaction between main elements is improved; the intermediate alloy is subjected to vacuum induction, vacuum consumable remelting and residual stub bars after hot working during blank rolling, so that the intermediate alloy can be recycled, the waste of materials is avoided, and the cost is reduced. The material head except the head and the tail of the steel ingot adopts a surface treatment method of cleaning or shot blasting to remove rust, oxidation and greasy dirt on the surface of the steel ingot, so as to clean the raw materials and reduce the impurity elements such as gas brought by the raw materials. The gas content is lower through the primary degassing of vacuum induction and the secondary degassing of vacuum consumable remelting, so that the oxides of B-type inclusions and nitrides of E-type inclusions of nonmetallic inclusions are fewer, and the strength, the plasticity and the toughness of the steel are effectively improved.
The vacuum induction furnace and the vacuum consumable furnace do not have the capabilities of S removal and P removal, so raw materials are selected from raw materials with low S, P, the pure iron is required to be less than or equal to 0.002 percent and the P is required to be less than or equal to 0.005 percent, or high-purity refined steel produced by adopting an electric furnace and LF+VD (VOD), wherein S, P is less than or equal to 0.001 percent.
The purity of the metallic molybdenum, the metallic nickel, the metallic cobalt and the titanium sponge in the pure metal material is more than or equal to 99 percent, so that the introduction of impurity elements is avoided.
In the embodiment of the invention, before charging, the surface of the raw material is checked, rust, oxidation and greasy dirt on the surface of the raw material are not allowed, and if necessary, the raw material is cleaned, so that the raw material is clean, and the raw material is prevented from bringing in impurity elements such as gas and the like.
Preferably, the raw materials except Ti are added into the vacuum induction furnace in batches, the raw materials are melted at a low speed in the melting period, and the temperature after full melting is 1520-1560 ℃. The vacuum induction furnace smelting can improve the degassing effect by increasing the exposed molten steel surface, and can achieve good degassing effect when slow low-power melting materials are adopted.
Preferably, the vacuum degree in the refining period is less than or equal to 5Pa, the holding time in the refining period is more than or equal to 30min, and the temperature in the refining period is 1530-1570 ℃. Too low a temperature does not play a refining role, and too high a temperature causes Al and Ti in the crucible to be reduced into molten steel.
Preferably, after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, the Ti with the formula amount in the raw materials is added, so that the TiO is reduced 2 And TiN, thereby reducing the content of oxide and nitride nonmetallic inclusions.
Preferably, the electrodes are cast at a casting temperature of 1540-1580 ℃. Too low a casting temperature causes the solidification casting of molten steel to be incomplete; too high a casting temperature results in an electrode that is prone to cracking.
After the electrode is required to be polished and flat-headed, vacuum consumable remelting is carried out, so that the inclusion can be effectively reduced.
Preferably, the smelting vacuum degree of the vacuum consumable electrode is less than or equal to 0.5Pa, and remelting and degassing of the electrode are realized.
Preferably, the current of the vacuum consumable electrode at the initial stage is 4.0-11.5 KA, the melting speed at the melting stage is 2.5-6.5 kg/min, and the current at the feeding stage is 2.5-6.5 KA. The vacuum consumable furnace smelting defines different melting speeds according to ingot shapes of different steels, and the melting period is based on the melting speed, so that the melting speed is as low as possible, and the segregation of chemical elements can be improved.
Preferably, under helium cooling, the cooling is accelerated, and the molten steel is solidified at the same time, so that the chemical composition segregation and the ingot segregation are improved. After remelting into ingots, the surfaces are polished or polished.
Preferably, the diffusion annealing temperature of the steel ingot for high-temperature diffusion annealing is 1230-1250 ℃, and the heat preservation time is more than or equal to 20 hours, so as to obtain the steel ingot. At this temperature range, chemical composition segregation can be improved.
Preferably, forging the steel ingot after diffusion annealing, and obtaining parameters of the blank includes: the forging temperature is 1120-1160 ℃, the forging temperature is not less than 1000 ℃, the final satin temperature is not less than 850 ℃, and the steel can be ensured to be formed in an optimal thermoplastic area within the temperature range, thereby avoiding forging cracking and effectively controlling the grain size.
Preferably, the parameters of rolling the blank into a finished product include: the heating temperature of the rolling is 1100-1140 ℃, the initial rolling temperature is more than or equal to 1000 ℃, and the final rolling temperature is more than or equal to 850 ℃.
Preferably, the solution treatment includes: the solid solution is kept at 810-840 ℃ and is air cooled according to the radius of 2.5mm/min+60 min.
Preferably, the aging treatment comprises: the aging is carried out at 470-520 ℃ and the heat preservation and air cooling are carried out according to the radius of 2.5mm/min+270 min.
In the embodiment of the invention, the preparation method of the ultra-high strength steel adopts a smelting process of vacuum induction and vacuum consumable remelting, so that the gas content is lower, the oxides of B-type inclusions and nitrides of E-type inclusions of nonmetallic inclusions are fewer, and the strength, the plasticity and the toughness of the steel are effectively improved; and can precisely control chemical components to meet the requirement of point control. The maraging ultrahigh-strength steel produced by the method has low impurity element content, better alloying effect, high strength, good plasticity and toughness and improved crack sensitivity of the super-strength steel.
In a third aspect, the embodiment of the invention also provides application of the maraging ultrahigh-strength steel or the maraging ultrahigh-strength steel prepared by the preparation method in preparation of aircraft landing parts, bulletproof steel plates, missile shells, aerospace gear shafts, high-end dies, pressure-bearing parts and fasteners.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.2% of Ni, 9.8% of Co, 5.45% of Mo, 0.83% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002 percent, P is less than or equal to 0.005 percent), refined steel (S is less than or equal to 0.001 percent, P is less than or equal to 0.001 percent), intermediate alloy, metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) according to the weight percentage of each component, wherein the weight percentage of the intermediate alloy in the total raw materials is 0-10 percent, adding the raw materials into a vacuum induction furnace, melting the raw materials at a low speed in a melting stage, wherein the temperature after full melting is 1520 ℃, the vacuum degree in a refining stage is 5Pa, the retention time in the refining stage is 30min, and the temperature in the refining stage is 1530 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at a casting temperature of 1540 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.5Pa, the current of the vacuum consumable furnace at the beginning stage of 4.0KA, the melting speed of the vacuum consumable furnace at the melting stage of 2.5kg/min and the current of the feeding stage of 2.5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1230 ℃, the steel ingots are forged after the heat preservation time is 20 hours, the forging temperature is 1120 ℃, the forging temperature is 1000 ℃, and the final satin temperature is 850 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1100 ℃, the initial rolling temperature is 1000 ℃, and the final rolling temperature is 850 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 810 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging is carried out at 470 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of 9H11030 is obtained through air cooling.
Example 2
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.15% of Ni, 9.77% of Co, 5.40% of Mo, 0.85% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002 percent, P is less than or equal to 0.005 percent), intermediate alloy, metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) according to the weight percentage of each component, wherein the weight percentage of the intermediate alloy in the total raw materials is 10-20 percent, adding the raw materials into a vacuum induction furnace, melting the raw materials at a low speed and low temperature in a melting period, wherein the temperature after full melting is 1530 ℃, the vacuum degree in a refining period is 4.5Pa, the retention time in the refining period is 35min, and the temperature in the refining period is 1540 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at a casting temperature of 1550 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.45Pa, the current of the vacuum consumable furnace at the beginning stage of 6.0KA, the melting speed of the vacuum consumable furnace at the melting stage of 3.5kg/min and the current of the feeding stage of 4.5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then high-temperature diffusion annealing is carried out, the diffusion annealing temperature is 1235 ℃, after the heat preservation time is 25 hours, the steel ingots are forged, the forging temperature is 1125 ℃, the forging opening temperature is 1100 ℃, and the final satin temperature is 900 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1115 ℃, the initial rolling temperature is 1100 ℃, and the final rolling temperature is 900 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 815 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging is carried out at 480 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of 9H10023 is obtained through air cooling.
Example 3
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
ni 19.17%, co 9.68%, mo 5.42%, ti 0.83%, and the balance of Fe and C, mn, si, S, P.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002 percent, P is less than or equal to 0.005 percent), intermediate alloy, refined steel (S is less than or equal to 0.001 percent, P is less than or equal to 0.001 percent), metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) according to the weight percentage of each component, wherein the intermediate alloy is 20-30 percent of the total raw material by weight, adding the raw materials into a vacuum induction furnace, melting the raw materials slowly at low temperature in a melting stage, wherein the temperature after full melting is 1535 ℃, the vacuum degree in a refining stage is 4Pa, the retention time in the refining stage is 40min, and the temperature in the refining stage is 1550 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at the casting temperature of 1560 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.4Pa, the current of the vacuum consumable furnace at the beginning stage of 8.0KA, the melting speed of the vacuum consumable furnace at the melting stage of 5.5kg/min and the current of the feeding stage of 5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1240 ℃, the steel ingots are forged after the heat preservation time is 30 hours, the forging temperature is 1130 ℃, the forging temperature is 1200 ℃, and the final satin temperature is 1000 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1120 ℃, the initial rolling temperature is 1200 ℃, and the final rolling temperature is 1000 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 820 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging temperature is 490 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of 9H10103 is obtained through air cooling.
Example 4
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.21% of Ni, 9.69% of Co, 5.43% of Mo, 0.83% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002 percent, P is less than or equal to 0.005 percent), intermediate alloy, refined steel (S is less than or equal to 0.001 percent, P is less than or equal to 0.001 percent), metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) according to the weight percentage of each component, wherein 30-40 percent of the intermediate alloy in the total raw materials is added into a vacuum induction furnace, the materials are melted slowly at low temperature in a melting stage, the temperature after full melting is 1545 ℃, the vacuum degree in a refining stage is 4Pa, the holding time in the refining stage is 40min, and the temperature in the refining stage is 1560 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at a casting temperature of 1570 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.4Pa, the current of the vacuum consumable furnace at the beginning stage of 10.0KA, the melting speed of the vacuum consumable furnace at the melting stage of 6.0kg/min and the current of the feeding stage of 6.0KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1250 ℃, the steel ingots are forged after the heat preservation time is 35 hours, the forging temperature is 1140 ℃, the forging temperature is 1250 ℃, and the final satin temperature is 1050 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the heating temperature of rolling is 1130 ℃, the initial rolling temperature is 1250 ℃, and the final rolling temperature is 1050 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 830 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging is carried out at 510 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of 9H10108 is obtained through air cooling.
Example 5
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.20% of Ni, 9.76% of Co, 5.44% of Mo, 0.84% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding refined steel (S, P is less than or equal to 0.001 percent), intermediate alloy, refined steel (S is less than or equal to 0.001 percent, P is less than or equal to 0.001 percent), metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) into the raw materials according to the weight percentage of the components, wherein the intermediate alloy accounts for 40-50 percent of the total raw materials by weight, the raw materials are added into a vacuum induction furnace, the melting stage is slowly and slowly melted at 1535 ℃, the refining stage vacuum degree is 4Pa, the refining stage holding time is 40min, and the refining stage temperature is 1550 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at the casting temperature of 1560 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.4Pa, the current of the vacuum consumable furnace at the beginning stage of 8.0KA, the melting speed of the vacuum consumable furnace at the melting stage of 5.5kg/min and the current of the feeding stage of 5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1240 ℃, the steel ingots are forged after the heat preservation time is 30 hours, the forging temperature is 1130 ℃, the forging temperature is 1200 ℃, and the final satin temperature is 1000 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1120 ℃, the initial rolling temperature is 1200 ℃, and the final rolling temperature is 1000 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 820 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging is carried out at 490 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of OH10003 is obtained through air cooling.
Example 6
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.20% of Ni, 9.75% of Co, 5.44% of Mo, 0.83% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002 percent, P is less than or equal to 0.005 percent), intermediate alloy, refined steel (S is less than or equal to 0.001 percent, P is less than or equal to 0.001 percent), metallic molybdenum (purity is more than or equal to 99 percent), metallic nickel (purity is more than or equal to 99 percent) and metallic cobalt (purity is more than or equal to 99 percent) according to the weight percentage of each component, wherein 50-60 percent of the intermediate alloy in the total raw materials is added into a vacuum induction furnace, the materials are melted at a low speed, the temperature after full melting is 1550 ℃, the vacuum degree in the refining period is 4Pa, the holding time in the refining period is 40min, and the temperature in the refining period is 1570 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at the casting temperature of 1580 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.4Pa, the current of the vacuum consumable furnace at the beginning stage of 11.5KA, the melting speed of the vacuum consumable furnace at the melting stage of 6.5kg/min and the current of the feeding stage of 6.5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1250 ℃, the steel ingots are forged after the heat preservation time is 35 hours, the forging temperature is 1160 ℃, the forging opening temperature is 1250 ℃, and the final satin temperature is 1050 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1160 ℃, the initial rolling temperature is 1250 ℃, and the final rolling temperature is 1050 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 840 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out aging treatment, wherein the aging is carried out at 520 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of OH10010 is obtained through air cooling.
Example 7
The embodiment of the invention provides maraging ultrahigh-strength steel, which comprises the following components in percentage by weight:
19.20% of Ni, 9.77% of Co, 5.45% of Mo, 0.83% of Ti, and the balance of Fe, C, mn, si, S, P and other impurities.
The preparation method of the maraging ultrahigh-strength steel comprises the following steps of:
adding pure iron (S is less than or equal to 0.002%, P is less than or equal to 0.005%), metallic molybdenum (purity is more than or equal to 99%), metallic nickel (purity is more than or equal to 99%) and metallic cobalt (purity is more than or equal to 99%) into the above components in percentage by weight, adding the above raw materials into a vacuum induction furnace in batches according to the proportion, melting the raw materials at a low speed and at a low temperature in a melting stage, wherein the temperature after full melting is 1560 ℃, the vacuum degree in a refining stage is 4Pa, the holding time in the refining stage is 40min, and the temperature in the refining stage is 1570 ℃; after the refining period, when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15ppm, adding titanium sponge (the purity is more than or equal to 99 percent) according to the weight percentage of Ti;
casting to form an electrode at the casting temperature of 1580 ℃;
after polishing and flattening the electrode, smelting in a vacuum consumable furnace with the smelting vacuum degree of 0.4Pa, the current of the vacuum consumable furnace at the beginning stage of 11.5KA, the melting speed of the vacuum consumable furnace at the melting stage of 6.5kg/min and the current of the feeding stage of 6.5KA; under helium cooling, the electrode is cooled in an acceleration way, melted and coagulated simultaneously, after remelting into ingots, the surfaces of the steel ingots are polished or polished, and then are subjected to high-temperature diffusion annealing, wherein the diffusion annealing temperature is 1250 ℃, the steel ingots are forged after the heat preservation time is 35 hours, the forging temperature is 1160 ℃, the forging opening temperature is 1250 ℃, and the final satin temperature is 1050 ℃, so as to obtain blanks;
rolling the blank into a finished product, wherein the rolling heating temperature is 1160 ℃, the initial rolling temperature is 1250 ℃, and the final rolling temperature is 1050 ℃;
carrying out solid solution treatment on the finished product, carrying out solid solution at 840 ℃, calculating and preserving heat according to the radius of 2.5mm/min+60min, and carrying out air cooling;
and then carrying out ageing treatment, wherein the ageing is carried out at 520 ℃, the heat preservation is calculated according to the radius of 2.5mm/min+270min, and the maraging ultra-high strength steel with the furnace number of 1H10005 is obtained through air cooling.
Comparative example 1
18Ni300 steel grade prepared in the prior art. The mass percentages of the chemical elements are shown in the following table 1:
TABLE 1 chemical composition (wt%)
The manufacturing process of the 18Ni300 steel grade shown in table 1 is:
test example 1
The maraging ultra-high strength steels prepared in examples 1-7 were subjected to chemical composition weight percent testing and the results are shown in table 2.
TABLE 2 weight percent chemical compositions
In table 2, the balance is Fe and other unavoidable impurities.
The maraging ultra-high strength steels prepared in examples 1 to 7 were subjected to mechanical property test, and the results are shown in Table 3.
TABLE 3 mechanical property test
The mechanical properties of maraging ultra-high strength steels prepared in examples 1 to 7 and 18Ni300 steel grades prepared in comparative example 1 were compared, and the results are shown in Table 4.
Table 4 mechanical property comparison
As is clear from Table 4, the maraging ultra-high strength steel prepared by the present invention has a low impurity element content and a good steel quality.
As can be seen from tables 3 and 4, the maraging ultra-high strength steel prepared in examples 1-7 of the present invention has a tensile strength of 2240-2270 MPa, a yield strength of 2210-2230 MPa, an elongation of 8.0-8.5%, a reduction in area of 32-35%, an impact of 26-29J, a tensile strength of more than or equal to 1910MPa, a yield strength of more than or equal to 1820MPa, an elongation of more than or equal to 8.0%, a reduction in area of more than or equal to 30%, and an impact of more than or equal to 25J, all of which are greater than that of the 18Ni300 steel of comparative example 1.
The maraging ultrahigh-strength steel prepared by the method has the advantages of excellent tensile strength, yield strength, elongation, surface shrinkage and impact performance, and higher rigidity, plasticity and toughness; thereby improving crack sensitivity of the ultra-high strength steel;
from the results, the maraging ultrahigh-strength steel provided by the invention can reduce the content of impurity elements in the steel and improve the purity of the steel; the hardness of the steel is improved and the toughness is slightly improved by adjusting the chemical components; the crack sensitivity is improved by reducing residual chemical elements and optimizing the hot working process, and the effect is obviously better than that of the comparative example group.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The maraging ultra-high strength steel is characterized in that the preparation raw materials comprise the following components in percentage by weight: less than or equal to 0.005 percent of C, less than or equal to 0.05 percent of Mn, less than or equal to 0.05 percent of Si, less than or equal to 0.002 percent of S, less than or equal to 0.005 percent of P, 18.5 to 19.5 percent of Ni, 9.5 to 10.0 percent of Co, 5.0 to 6.0 percent of Mo, 0.7 to 0.90 percent of Ti, less than or equal to 0.20 percent of Al, less than or equal to 0.00005 percent of H, less than or equal to 0.0010 percent of O, less than or equal to 0.0010 percent of N, and the balance of Fe and other unavoidable impurities;
the preparation method of the maraging ultrahigh-strength steel adopts a vacuum induction furnace casting and vacuum consumable furnace remelting smelting process, and mainly comprises the following steps:
according to the mass percentage of each component in the preparation raw materials, adding other raw materials except Ti into a vacuum induction furnace, and melting at a low speed and a low temperature in a melting period, wherein the temperature after full melting is 1520-1560 ℃;
the vacuum degree in the refining period is less than or equal to 5Pa, the holding time in the refining period is more than or equal to 30min, and the temperature in the refining period is 1530-1570 ℃;
after the refining period, adding Ti with the formula amount into the raw materials when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15 ppm; casting into an electrode at the casting temperature of 1540-1580 ℃;
remelting the electrode into steel ingots in a vacuum consumable furnace, wherein the smelting vacuum degree of the vacuum consumable furnace is less than or equal to 0.5Pa; the current of the vacuum consumable furnace at the initial stage is 4.0-11.5-kA, the melting speed of the vacuum consumable furnace at the melting stage is 2.5-6.5 kg/min, and the current of the vacuum consumable furnace at the feeding stage is 2.5-6.5 kA; solidifying under helium cooling to obtain the steel ingot;
carrying out high-temperature diffusion annealing on the steel ingot, and forging to obtain a blank;
rolling the blank into a finished product;
and carrying out solution treatment and aging treatment on the finished product to obtain the maraging ultrahigh-strength steel.
2. A preparation method of maraging ultra-high strength steel adopts a vacuum induction furnace casting and vacuum consumable furnace remelting smelting process, and the main process is as follows:
according to the mass percent of each component in the preparation raw materials of claim 1, adding other raw materials except Ti into a vacuum induction furnace, melting the raw materials at a low speed and a low temperature in a melting period, wherein the temperature after full melting is 1520-1560 ℃;
the vacuum degree in the refining period is less than or equal to 5Pa, the holding time in the refining period is more than or equal to 30min, and the temperature in the refining period is 1530-1570 ℃;
after the refining period, adding Ti with the formula amount into the raw materials when the nitrogen is less than or equal to 10ppm and the oxygen is less than or equal to 15 ppm; casting into an electrode at the casting temperature of 1540-1580 ℃;
remelting the electrode into steel ingots in a vacuum consumable furnace, wherein the smelting vacuum degree of the vacuum consumable furnace is less than or equal to 0.5Pa; the current of the vacuum consumable furnace at the initial stage is 4.0-11.5-kA, the melting speed of the vacuum consumable furnace at the melting stage is 2.5-6.5 kg/min, and the current of the vacuum consumable furnace at the feeding stage is 2.5-6.5 kA; solidifying under helium cooling to obtain the steel ingot;
carrying out high-temperature diffusion annealing on the steel ingot, and forging to obtain a blank;
rolling the blank into a finished product;
and carrying out solution treatment and aging treatment on the finished product to obtain the maraging ultrahigh-strength steel.
3. The method of preparing according to claim 2, wherein the raw materials comprise: pure iron or refined steel, wherein S is less than or equal to 0.002 percent and P is less than or equal to 0.005 percent in the pure iron, and S, P is less than or equal to 0.001 percent in the refined steel;
the intermediate alloy is vacuum induction, vacuum consumable remelting and a residual stub bar after blank rolling;
the pure metal material is metal Mo, metal Ni, metal Co and metal Ti, wherein the purities of the metal Mo, the metal Ni, the metal Co and the metal Ti are all more than or equal to 99 percent.
4. The preparation method according to claim 2, wherein the diffusion annealing temperature of the steel ingot for high-temperature diffusion annealing is 1230-1250 ℃, and the heat preservation time is more than or equal to 20h;
forging the annealed steel ingot, wherein parameters for obtaining a blank comprise: the forging temperature is 1120-1160 ℃, the forging temperature is more than or equal to 1000 ℃, and the final satin temperature is more than or equal to 850 ℃.
5. The method of manufacturing according to claim 2, wherein the parameters of rolling the blank into a finished product include: the heating temperature of the rolling is 1100-1140 ℃, the initial rolling temperature is more than or equal to 1000 ℃, and the final rolling temperature is more than or equal to 850 ℃.
6. The method of manufacturing according to claim 2, wherein the solution treatment includes: the solid solution is kept at 810-840 ℃ and air-cooled according to the radius of 2.5mm/min+60 min.
7. The method of claim 2, wherein the aging comprises: and (3) preserving heat and air cooling according to the ageing temperature of 470-520 ℃ and the radius of 2.5mm/min+270 min.
8. Use of a maraging ultra-high strength steel as claimed in claim 1 or a maraging ultra-high strength steel as obtainable by a method according to any one of claims 2-7 for the manufacture of aircraft landing parts, ballistic steel sheets, missile shells, aerospace gear shafts, high-end moulds, pressure-bearing parts and fasteners.
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| CN113106356B (en) * | 2021-04-19 | 2022-04-26 | 中航上大高温合金材料股份有限公司 | High-strength martensite precipitation hardening stainless steel and preparation method thereof |
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| CN101649413A (en) * | 2008-08-15 | 2010-02-17 | 宝山钢铁股份有限公司 | Ultra-strength and high toughness maraging steel and manufacturing method thereof |
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