CN111304548A - Low-precipitation sensitivity high-performance non-magnetic stainless steel and manufacturing method thereof - Google Patents

Low-precipitation sensitivity high-performance non-magnetic stainless steel and manufacturing method thereof Download PDF

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CN111304548A
CN111304548A CN202010224635.5A CN202010224635A CN111304548A CN 111304548 A CN111304548 A CN 111304548A CN 202010224635 A CN202010224635 A CN 202010224635A CN 111304548 A CN111304548 A CN 111304548A
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屈华鹏
冯翰秋
陈海涛
郎宇平
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Central Iron and Steel Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Abstract

A non-magnetic stainless steel with low precipitation sensitivity and high performance and a manufacturing method thereof belong to the stainless steel material in the technical field of material science. The stainless steel comprises the following components in percentage by weight: cr is more than or equal to 18.50 and less than 21.50, Mo is more than or equal to 0.50 and less than or equal to 1.00, C is more than or equal to 0.030, N is more than or equal to 0.55 and less than or equal to 0.65, Ni is more than or equal to 1.00 and less than or equal to 2.50, Mn is more than 17.00 and less than or equal to 21.00, Si is more than or equal to 0.20 and less than or equal to 0.35, P is more than or equal to 0. The manufacturing method comprises the following steps: the method comprises the steps of preparing an ingot by an electric furnace, argon-oxygen decarburization external refining and electroslag remelting, heating and preserving heat of the ingot by a high-temperature heat treatment furnace, forging the ingot into an intermediate billet by a radial forging machine immediately after finishing heat preservation of the ingot and discharging, carrying out water cooling treatment on the intermediate billet, carrying out secondary forging on the intermediate billet after the water cooling treatment by the radial forging machine to obtain a finished billet, and carrying out air cooling after forging. The method has the advantages of lower harmful carbide precipitation sensitivity and lower forging deformation resistance, and simultaneously ensures good mechanical and corrosion resistance.

Description

Low-precipitation sensitivity high-performance non-magnetic stainless steel and manufacturing method thereof
Technical Field
The invention belongs to a stainless steel material in the technical field of material science, and particularly relates to a low-precipitation sensitivity high-performance non-magnetic stainless steel and a manufacturing method thereof.
Background
The non-magnetic stainless steel and the non-magnetic drill collar, rotary guide, non-magnetic stabilizer, non-magnetic drill rod and the like made of the non-magnetic stainless steel are important materials and parts which are necessary for land and ocean oil gas resources at home and abroad at present, particularly for the directional drilling and production process of unconventional oil gas resources. According to the requirements of American Petroleum institute API and related domestic material industry and technical standards, the relative magnetic permeability of the steel is lower than 1.01, namely the steel has good austenite stability and simultaneously has extremely high obdurability and corrosion resistance. The non-magnetic stainless steel part can provide a magnetic shielding environment for a Measurement While Drilling (MWD) instrument, avoid the interference of an earth magnetic field to the directional drilling process and realize the accuracy of drilling in horizontal, lateral and directional drilling directions and the like. Meanwhile, the long-term stable service life of the non-magnetic drill collar component is ensured.
Compared with the traditional Cr-Ni austenitic stainless steel, the nonmagnetic stainless steel adopts Mn and N elements to partially or completely replace expensive Ni elements as austenite stabilizing elements to ensure the stability of austenite. Because of the obvious clearance strengthening effect of the N element, the strength of the non-magnetic stainless steel matrix is greatly improved. On the other hand, the non-magnetic stainless steel adopts an advanced isothermal deformation preparation technology, so that the matrix of the non-magnetic stainless steel obtains a more obvious deformation strengthening effect, the strength of the non-magnetic stainless steel is further improved, and the room-temperature tensile strength of the non-magnetic stainless steel is more than twice of that of the traditional Cr-Ni austenitic stainless steel.
The biggest problems in the process of producing the non-magnetic stainless steel at home and abroad are the problems of high content of precipitated phases of carbonitrides, high thermal deformation resistance, poor corrosion resistance of the finished forgings of the non-magnetic stainless steel and the like caused by precipitation sensitivity in the hot working process. Compared with the prior art, the invention reasonably adjusts the contents of Cr, C, N and other elements and hot working process parameters in the non-magnetic stainless steel, so that the non-magnetic stainless steel with low precipitation sensitivity and high performance has lower precipitation sensitivity of harmful carbides and lower forging deformation resistance, and simultaneously ensures good mechanical and corrosion resistance.
Disclosure of Invention
The invention aims to provide the non-magnetic stainless steel with low precipitation sensitivity and high performance and the manufacturing method thereof, which reasonably reduces the contents of Cr element, C element and N element by researching the influence rule of the contents of Cr element, C element and N element on the precipitation behavior characteristics of carbonitride of Cr in the non-magnetic stainless steel, optimizes the smelting and hot processing technology, ensures that the non-magnetic stainless steel has wider hot processing window, good thermoplasticity and lower deformation resistance, and simultaneously ensures good mechanical and corrosion resistance.
The invention relates to a low-precipitation sensitivity high-performance non-magnetic stainless steel, which comprises the following elements in percentage by weight: cr is more than or equal to 18.50 and less than 21.50, Mo is more than or equal to 0.50 and less than or equal to 1.00, C is more than or equal to 0.030, N is more than or equal to 0.55 and less than or equal to 0.65, Ni is more than or equal to 1.00 and less than or equal to 2.50, Mn is more than 17.00 and less than or equal to 21.00, Si is more than or equal to 0.20 and less than or equal to 0.35, P is more than or equal to 0.
The invention relates to a method for manufacturing a low-precipitation sensitivity high-performance non-magnetic stainless steel, which comprises the following process steps:
(1) smelting molten steel according to the following element weight percentages: cr is more than or equal to 18.50 and less than 21.50, Mo is more than or equal to 0.50 and less than or equal to 1.00, C is more than or equal to 0.030, N is more than or equal to 0.55 and less than or equal to 0.65, Ni is more than or equal to 1.00 and less than or equal to 2.50, Mn is more than or equal to 17.00 and less than or equal to 21.00, Si is more than or equal to 0.20 and less than or equal to 0.35, P is less than or;
(2) preparing an ingot by adopting an electric furnace, argon-oxygen decarburization external refining and electroslag remelting method;
(3) heating and preserving heat of the cast ingot by a high-temperature heat treatment furnace;
(4) after the ingot casting is finished and the temperature is kept, the ingot is immediately forged into an intermediate blank by a radial forging machine;
(5) carrying out water cooling treatment on the intermediate blank;
(6) and performing secondary forging on the intermediate billet subjected to water cooling treatment by using a radial forging machine to obtain a finished billet.
(7) And air cooling after forging.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the heating and heat preservation temperature of the high-temperature heat treatment furnace in the step (3) is 1080-1120 ℃.
Further, the finish forging temperature of the radial forging machine in the step (4) is 980-1000 ℃.
Further, the surface temperature of the intermediate blank after the water-cooling treatment in the step (5) is 600 ℃ to 650 ℃.
Further, the secondary forging temperature of the radial forging machine in the step (6) is 550-600 ℃, and the minimum deformation is 20%.
The invention has the beneficial effects that: by researching the influence rule of the contents of Cr, C and N on the precipitation behavior characteristics of Cr carbonitride in the non-magnetic stainless steel, the contents of Cr, C and N are reasonably adjusted, and the smelting and hot working processes are optimized, so that the stainless steel has lower precipitation sensitivity of harmful carbide and lower forging deformation resistance, and simultaneously, good mechanical and corrosion resistance properties are ensured.
Drawings
FIG. 1 shows the Cr content and C content of Cr element in a non-magnetic stainless steel with low precipitation sensitivity and high performance23C6Influence of harmful phase precipitation characteristics.
FIG. 2 is a schematic diagram showing the influence of the content of N element and the secondary forging deformation temperature of the radial forging machine on the finish forging deformation resistance of the low precipitation sensitivity high-performance nonmagnetic stainless steel of the present invention.
FIG. 3 is a diagram showing the influence of Cr element and N element contents on the PREN value of the pitting corrosion equivalent of the low precipitation sensitivity high performance non-magnetic stainless steel of the present invention.
FIG. 4 is a schematic diagram showing the influence of pitting equivalent PREN value on the pitting potential of a low-precipitation sensitivity high-performance non-magnetic stainless steel of the present invention.
FIG. 5 is a schematic diagram showing the influence of the secondary forging deformation temperature and deformation of the radial forging machine on the room temperature yield strength of the low precipitation sensitivity high-performance nonmagnetic stainless steel of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1: the content of Cr element and C element is low to separate out the high-performance non-magnetic stainless steel of the inventionCr in steel23C6Influence of the precipitation characteristics of the harmful phase
Cr in non-magnetic stainless steel23C6The temperature range for the precipitation of the harmful phase is about 600 ℃ to 950 ℃. The secondary forging process of the non-magnetic stainless steel radial forging machine is a warm deformation strengthening process, and the deformation temperature range and Cr of the process23C6The lower temperature limit of the precipitation of harmful phases has a potential overlapping region, so the invention uses Cr23C6The lower limit of the temperature at which the harmful phase is precipitated is defined as a safety temperature below which secondary forging by a radial forging machine is carried out, and Cr is not generated in the non-magnetic stainless steel23C6A deleterious phase.
In order to investigate the content of Cr element and C element on Cr in the non-magnetic stainless steel with low precipitation sensitivity and high performance23C6The influence of the precipitation characteristics of harmful phases, the low precipitation sensitivity high-performance non-magnetic stainless steel samples H-1 to H-25 (table 1) with different Cr element and C element contents are prepared, and Cr in each sample is compared by using a metallographic statistical analysis method after the same forging deformation and different aging treatment processes23C6Difference in the precipitation characteristics of the harmful phase.
Table 1 chemical composition (wt.%) of high toughness medium nitrogen non-magnetic stainless steel samples H-1 to H-25 of the present invention
Figure BDA0002427244420000041
The metallographic observation result shows that: 1) with the increase of the content of the C element, Cr23C6The safe temperature for the precipitation of the harmful phase is gradually reduced from above 600 ℃ to about 500 ℃ (figure 1), which shows that the higher content of C element is helpful for Cr23C6The harmful phase is generated at a lower temperature. Therefore, the increase of the content of the C element is not beneficial to the temperature deformation strengthening process of the non-magnetic stainless steel, and is easy to cause larger Cr to appear in the temperature deformation process of the non-magnetic stainless steel23C6Tendency of harmful phases to precipitate. 2) The increase of the Cr element content also promotes the Cr23C6The safe temperature for the precipitation of harmful phase is gradually reduced, and the content of C element is higherIn the case of (2), the magnitude of the reduction is more pronounced (fig. 1).
Example 2: the influence of the content of N element and the secondary forging deformation temperature of the radial forging machine on the deformation resistance of the low-precipitation sensitivity high-performance non-magnetic stainless steel
Cr in non-magnetic stainless steel23C6The temperature range of harmful phase precipitation is about 600 ℃ to 950 ℃, so that the secondary forging of the radial forging machine at the temperature of less than 600 ℃ or even less than 500 ℃ can effectively avoid Cr23C6And (4) separating out a harmful phase. However, too low a forging temperature leads to a sharp increase in deformation resistance, and if forging is performed at a lower temperature for a long time, the service life of the radial forging machine is shortened.
For non-magnetic stainless steel, the main factors influencing the secondary forging deformation resistance of the radial forging machine are the content of N element and the secondary forging deformation temperature of the radial forging machine. In order to investigate the influence of the content of N element and the secondary forging deformation temperature of the radial forging machine on the deformation resistance of the low-precipitation sensitivity high-performance non-magnetic stainless steel, samples H-26 to H-29 (table 2) of the low-precipitation sensitivity high-performance non-magnetic stainless steel with different N element contents are prepared, and the samples are subjected to thermal deformation through different thermal deformation processes on a thermal simulation testing machine, so that the secondary forging deformation process of the radial forging machine of the non-magnetic stainless steel is simulated and researched. The temperatures for the thermal simulated deformation were 400 deg.C, 500 deg.C, 600 deg.C and 700 deg.C, respectively.
Table 2 chemical composition (wt.%) of high toughness medium nitrogen non-magnetic stainless steel samples H-26 to H-29 according to the invention
Figure BDA0002427244420000051
The simulation research result of the thermal simulation testing machine on the secondary forging deformation process of the non-magnetic stainless steel radial forging machine shows that: with the increase of the N content, the high-temperature deformation resistance (peak stress) of the non-magnetic stainless steel material shows a linear increasing trend (figure 2), and the N content has a particularly obvious effect on the improvement of the deformation resistance at a higher deformation temperature. Therefore, in order to ensure a good working condition of the radial forging machine, the non-magnetic stainless steel should be resistant to deformationThe force is controlled to a level below about 700MPa, and the N content is preferably not more than 0.65% in view of the total. While taking into account Cr in example 123C6The harmful phase is separated out, the temperature of the secondary forging of the radial forging machine is preferably controlled to be not higher than 600 ℃, the content of Cr element is preferably controlled to be below 21.5 percent, and the content of C element is preferably controlled to be below 0.03 percent. By adjusting the components and the process, Cr can be avoided simultaneously23C6Harmful phases are precipitated and deformation resistance is reduced.
Example 3: influence of Cr element and N element contents on pitting equivalent PREN value and pitting potential of low-precipitation sensitivity high-performance non-magnetic stainless steel
The pitting equivalent PREN value is a common method of reacting the localized corrosion resistance of stainless steel materials. For non-magnetic stainless steel, the main elements affecting the PREN value are Cr element, Mo element, and N element. The calculation relationship is as follows:
PREN＝Cr％+3.3×Mo％+16×N％
the calculation result shows that: in the non-magnetic stainless steel with low precipitation sensitivity and high performance of the present invention, when the content of Mo element is about 0.5%, the content of N element is changed from 0.5% to 0.8% as the content of Cr element is changed from 18.5% to 22.5%, and the pitting corrosion equivalent PREN value of the non-magnetic stainless steel is increased from 28 to about 37 (fig. 3).
The pitting potential is a key index for the pitting resistance of the reaction stainless steel material and is directly influenced by the PREN value of the material. In order to investigate the influence of the contents of Cr and N on the pitting potential of the low-precipitation sensitivity high-performance non-magnetic stainless steel, samples H-30 to H-40 (Table 3) of the low-precipitation sensitivity high-performance non-magnetic stainless steel with different contents of Cr and N were prepared, and pitting potential tests were performed by an electrochemical test method, and then the test results were compared.
Table 3 chemical composition (wt.%) of a high toughness medium nitrogen non-magnetic stainless steel sample of the invention H-30 to H-40
Figure BDA0002427244420000061
Figure BDA0002427244420000071
The electrochemical pitting potential test result shows that: in a sodium chloride electrolyte solution with uniformly adjusted pH value and 4% mass concentration, the pitting potential of the low-precipitation sensitivity high-performance non-magnetic stainless steel is sharply reduced from more than 800mV to less than 450mV along with the reduction of the PREN value from 37.038 to 26.939. Particularly, when the PREN value is less than 29, the degree of pitting potential decrease sharply increases. The Cr, N content of the non-magnetic stainless steel should therefore be controlled to a reasonable level to ensure a sufficient pitting equivalent PREN value. In the non-magnetic stainless steel with low precipitation sensitivity and high performance, the content of Cr element is preferably higher than 18.50 percent, the content of N element is preferably higher than 0.55 percent, and the pitting equivalent of the non-magnetic stainless steel can be ensured to be higher than 29.
Example 4: influence of secondary forging deformation temperature and deformation amount of radial forging machine on room temperature yield strength of low precipitation sensitivity high-performance nonmagnetic stainless steel
The high strength of the non-magnetic stainless steel comes from the obvious N atom gap strengthening effect and the sufficient secondary forging deformation strengthening effect of the radial forging machine. As described above, the nonmagnetic stainless steel must contain a sufficient amount of N element in order to ensure sufficient corrosion resistance. Meanwhile, in order to ensure lower deformation resistance of the radial forging machine, the secondary forging temperature of the radial forging machine must be prevented from being too low. Therefore, in order to investigate the influence of the secondary forging deformation temperature and deformation of the radial forging machine on the room-temperature yield strength of the low-precipitation sensitivity high-performance nonmagnetic stainless steel, the secondary forging of the radial forging machine is simulated and researched by forging experiments with different deformation temperatures and deformation amounts, the room-temperature tensile property of a sample in a forging state is tested, and the room-temperature yield strength results are compared. The chemical composition of the non-magnetic stainless steel sample H-41 of the present invention having low precipitation sensitivity and high performance used in this example is as follows (Table 4).
Table 4 chemical composition (wt.%, balance Fe) of a low precipitation sensitivity high performance non-magnetic stainless steel sample according to the invention H-41
Furnace number Cr C N Mo Ni Mn S P Si
H-41 20.41 0.028 0.624 0.635 1.56 19.93 0.010 0.002 0.284
The room temperature tensile property test result shows that: with the increase of the secondary forging temperature of the radial forging machine, the room-temperature yield strength of the low-precipitation sensitivity high-performance non-magnetic stainless steel is gradually reduced, and particularly, the reduction trend is more obvious under the condition of lower forging deformation (figure 5). In order to ensure that the nonmagnetic stainless steel has enough room-temperature yield strength, the secondary forging temperature of the radial forging machine is not high, and the forging deformation is not low. In order to ensure that the yield strength at room temperature is not lower than 1100MPa, the secondary forging temperature of a radial forging machine of the non-magnetic stainless steel with low precipitation sensitivity and high performance is not lower than 550 ℃, and the forging deformation is not lower than 20%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. The non-magnetic stainless steel with low precipitation sensitivity and high performance is characterized by comprising the following elements in percentage by weight: cr is more than or equal to 18.50 and less than 21.50, Mo is more than or equal to 0.50 and less than or equal to 1.00, C is more than or equal to 0.030, N is more than or equal to 0.55 and less than or equal to 0.65, Ni is more than or equal to 1.00 and less than or equal to 2.50, Mn is more than 17.00 and less than or equal to 21.00, Si is more than or equal to 0.20 and less than or equal to 0.35, P is more than or equal to 0.
2. A method for manufacturing a low precipitation sensitivity high performance non-magnetic stainless steel according to claim 1, characterized in that the process steps are as follows:
(1) smelting molten steel according to the following element weight percentages: cr is more than or equal to 18.50 and less than 21.50, Mo is more than or equal to 0.50 and less than or equal to 1.00, C is more than or equal to 0.030, N is more than or equal to 0.55 and less than or equal to 0.65, Ni is more than or equal to 1.00 and less than or equal to 2.50, Mn is more than or equal to 17.00 and less than or equal to 21.00, Si is more than or equal to 0.20 and less than or equal to 0.35, P is less than or;
(2) preparing an ingot by adopting an electric furnace, argon-oxygen decarburization external refining and electroslag remelting method;
(3) heating and preserving heat of the cast ingot by a high-temperature heat treatment furnace;
(4) after the ingot casting is finished and the temperature is kept, the ingot is immediately forged into an intermediate blank by a radial forging machine;
(5) carrying out water cooling treatment on the intermediate blank;
(6) and performing secondary forging on the intermediate billet subjected to water cooling treatment by using a radial forging machine to obtain a finished billet.
(7) And air cooling after forging.
3. The manufacturing method according to claim 2, wherein the heating and holding temperature of the high-temperature heat treatment furnace in the step (3) is 1080 ℃ to 1120 ℃.
4. The manufacturing method according to claim 2, wherein the finish forging temperature of the radial forging in the step (4) is 980 ℃ to 1000 ℃.
5. The manufacturing method according to claim 2, wherein the surface temperature of the intermediate blank after the water-cooling treatment in step (5) is 600 ℃ to 650 ℃.
6. The manufacturing method according to claim 2, wherein the temperature of the secondary forging of the radial forging machine in the step (6) is 550 ℃ to 600 ℃ and the minimum deformation amount is 20%.
CN202010224635.5A 2020-03-26 2020-03-26 Low-precipitation sensitivity high-performance non-magnetic stainless steel and manufacturing method thereof Pending CN111304548A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2042093A5 (en) * 1969-10-03 1971-02-05 Japan Steel Works Ltd
CN101368252A (en) * 2008-09-12 2009-02-18 江苏大学 Non-nickel nitrogen austenite stainless steel
CN101386962A (en) * 2008-09-11 2009-03-18 上海材料研究所 Non-magnetic high-strength stainless steel and manufacturing method thereof
CN108004487A (en) * 2016-10-28 2018-05-08 宝钢特钢有限公司 A kind of high nitrogen is without magnetic austenitic stainless steel and its manufacture method
CN110205549A (en) * 2019-06-22 2019-09-06 钢铁研究总院 A kind of high tough middle nitrogen magnetism-free stainless steel and its manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2042093A5 (en) * 1969-10-03 1971-02-05 Japan Steel Works Ltd
CN101386962A (en) * 2008-09-11 2009-03-18 上海材料研究所 Non-magnetic high-strength stainless steel and manufacturing method thereof
CN101368252A (en) * 2008-09-12 2009-02-18 江苏大学 Non-nickel nitrogen austenite stainless steel
CN108004487A (en) * 2016-10-28 2018-05-08 宝钢特钢有限公司 A kind of high nitrogen is without magnetic austenitic stainless steel and its manufacture method
CN110205549A (en) * 2019-06-22 2019-09-06 钢铁研究总院 A kind of high tough middle nitrogen magnetism-free stainless steel and its manufacturing method

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