CN109295387A - A kind of good two-phase stainless steel plate of corrosion resistance and its manufacturing method - Google Patents
A kind of good two-phase stainless steel plate of corrosion resistance and its manufacturing method Download PDFInfo
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- CN109295387A CN109295387A CN201811165248.8A CN201811165248A CN109295387A CN 109295387 A CN109295387 A CN 109295387A CN 201811165248 A CN201811165248 A CN 201811165248A CN 109295387 A CN109295387 A CN 109295387A
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
The present invention discloses a kind of good two-phase stainless steel plate of corrosion resistance and its manufacturing method.Contain C:0.001%~0.01% in steel, Si:0.2%~0.8%, Mn:0.5%~2.0%, P≤0.02%, S≤0.02%, Cr:21%~23%, Ni:4%~9%, Mo:2%~5%, N:0.13%~0.2%, Cu:2%~3%, surplus are iron and inevitable impurity, anti-spot corrosion equivalent > 35.600~650 DEG C of hot chargings keep the temperature 1~1.5h, 4~6 DEG C/min of heating rate, 1200~1300 DEG C of soaking temperature, keep the temperature 1~2h；1200~1300 DEG C of start rolling temperature, the first percentage pass reduction 20%~25%, hereafter each percentage pass reduction 15%~20%, finishing temperature >=950 DEG C, roll rear 20~40 DEG C/s of cooling rate, red temperature≤300 DEG C；1050~1200 DEG C of offline solid solutions, 3~10min/mm of soaking time.Finished steel plate 5~70mm of thickness, seawater corrosion resistance, resistance to biological adhesiveness are good.
Description
Technical field
The invention belongs to steel material preparation field, especially a kind of good two-phase stainless steel plate of sea water corrosion resistant
Ingredient design and its milling method.
Background technique
Two phase stainless steel intensity with higher, the characteristics such as good low-temperature flexibility and excellent corrosion resistance.Closely
It is receive more and more attention over year.Especially in terms of shipbuilding, such as chemical tanker, maritime platform and marine worker petroleum pipeline
Road etc., two phase stainless steel are widely used.Especially in terms of the construction of chemical tanker, due to two phase stainless steel
Resistance to corrosion is strong, follow-up maintenance maintain expense is low, be the primary selection of some special boat key position steel.
In recent years, be the ferrite of representative with 2205, austenitic stainless steel steel plate using more and more, but retrofit steel
Kind is due to joined the alloying elements such as a large amount of Cr, Ni, Mo, so that steel billet shows very poor high warm during the rolling process
Plasticity, it is difficult to guarantee the stability and higher yield rate of large-scale production steel plate.And the special ship such as chemical tanker
And the service condition of maritime platform is complicated and severe, 2205 traditional Austenite and ferriteaustenite double phases of stainless steel are difficult to meet this kind of
Environment.Cu element can effectively improve the corrosion resistance of steel under reducing atmosphere, can also effectively inhibit microorganism
Growth attachment, especially suitable for marine worker, ship domain.
Publication No. CN101812647 discloses a kind of two phase stainless steel and its manufacturing method, the two-phase of the patent disclosure
Stainless steel is molding and does not have rolling mill practice, is unable to satisfy the design requirement of current chemical tanker two phase stainless steel.
Nissin Steel Co., Ltd. discloses in the CN87105997A patent of China's application with high-intensitive and high-elongation
And low degree, respectively to the production method of double tissue stainless cr-steel bands of dissimilarity, although also there is higher Cu content, it is produced
Stainless steel be steel band, thickness specification is not able to satisfy the big thickness requirement that ship and ocean engineering need.
The patent of Publication No. CN1154419A discloses ultra hypoeutectoid, diphasic stainless steel and its manufacturing method, two-phase stainless
Cu is free of in the ingredient of steel, preparation process is not able to satisfy the demand of high Cu content two phase stainless steel.
The two phase stainless steel of publication number CN102676943A joined a large amount of Cu elements, and there is no solve production hot-rolled stainless
The problem of steel plate hot cracking tendency.CN1155908A two phase stainless steel and its system of the Pohang Iron & Steel Co., Ltd. in China's application
It makes in method, although the two phase stainless steel of described 2.0% to 5.0%W, 1.0% to 2.0%Mo and 1.0%Ce passes through reduction
Mo content improves thermoplasticity, but the Pren of the resistance to spot corrosion value of the two phase stainless steel will significantly reduce, be unfavorable for two phase stainless steel
Pitting resistance.
The steel mills such as domestic Baosteel have also carried out the development of two-phase stainless steel plate, exploitation, but not to high Cu, big thickness and
The good two phase stainless steel of corrosion resistance, which is made, specifically to be researched and analysed.
Summary of the invention
The object of the present invention is to prepare a kind of two-phase suitable for ship, the big thickness high copper content of ocean engineering field
Stainless steel, mechanical property and seawater corrosion resistance, marine climate resistant corrosive nature can achieve ship and marine worker service condition.Shape
At a set of specific two-phase stainless composition of steel and matched production technology.
It is used not based on the high performance craft that copper is added on the basis of conventional ferrite plus austenite structure two phase stainless steel
Rust steel plate key production technology, purpose, the present inventors pass through alloying element and screen and proportion, steel cleaning to realize the present invention
Several aspects such as degree control, process optimization and parameter selection have carried out the experimental study of a large amount of systems, and finally having determined can meet
The object of the invention alloying element is with when rolling mill practice.
Specific technical solution is:
A kind of good high Cu content two-phase stainless steel plate of corrosion resistance, it is characterised in that by weight percentage, packet
Include C:0.001%~0.01%, Si:0.2%~0.8%, Mn:0.5%~2.0%, P≤0.02%, S≤0.02%, Cr:
21%~23%, Ni:4%~9%, Mo:2%~5%, N:0.13%~0.2%, Cu:2%~3%, remaining is Fe and can not
The impurity avoided.Anti- spot corrosion equivalent PRE > 35, wherein anti-spot corrosion equivalent PRE=Crwt%+3.3Mowt%+30Nwt%.
The mechanism of action of steel grade chemical component are as follows:
C plays solution strengthening effect as intensified element basic in steel, in steel grade, be proof strength, hardness it is necessary
Component, but C also reduces the hot-working character of material, while presence of the C in steel can also reduce the corrosion resistant of stainless steel
Corrosion energy.So C element content in steel should be reduced as far as possible.When the mass percent of C is greater than 0.01%, stainless steel sea water resistance
Corrosivity decline, so controlling the content of C 0.001%~0.01% in the present invention.
The intensity of steel can be improved in Si, can effectively stable ferritic phase, reduction O content therefore contain Si in the present invention
Amount control is 0.2%~0.8%.
Mn element is to expand austenite phase p-block element p, improves stabilization of austenite, but the content of Mn also must be controlled strictly
System, when Mn element mass percentage is greater than 10%, the hot rolling surface of steel plate is second-rate, and the segregation of Mn element can make again
The low-temperature flexibility of slab core is poor, so the upper limit of Mn element wants strict control.In addition, Mn element is not only austenite phase field
Stable element, while the hot-working character of steel can also be improved.Therefore, in the present invention by the control of the content of Mn 0.5%~
2.0%.
P, S element is no advantage to the mechanical property and corrosion resistance of two phase stainless steel, should control below 0.02%.
Cr element is the main addition element of two phase stainless steel, can effectively improve the corrosion resistance of steel, through grinding
When studying carefully the mass fraction for showing Cr less than 21% or less, steel do not show good corrosion resistance.In addition, when Cr contains
Measure it is excessively high will cause plate surface quality decline, uniform fold cannot be formed in the Cr oxide skin(coating) shown, and less economical.Cause
This present invention controls Cr 21%~23%.
Effect of the Ni element in stainless steel is to improve hot-working character, improves toughness.Meanwhile two-phase can be improved not in Ni
The stability of austenite phase in rust steel, if wanting to have the function that stable austenite phase, Ni element has to be larger than 4%.If wanting double
Cu element is added in phase stainless steel, since Cu element can deteriorate the thermoplasticity of steel, it is necessary to which the Ni element that sufficient amount is added improves
Hot-workability, so, the above analysis, the present invention controls Ni 4%~9%.
The corrosion resistance of stainless steel can be improved in Mo element, and the micro element, which is added, can reach corrosion resistance.In the present invention
It is 2%~5% by the control of Mo content.
When N element content is not less than 0.13%, the intensity and corrosion resistance of two phase stainless steel can be dramatically increased, stablizes Ovshinsky
Body phase.But when N content is excessive, the thermoplasticity of steel declines, and is unfavorable for the Plastic Forming such as forging rolling, therefore N element is not
0.2% should be more than.Therefore, N content is limited in 0.13%~0.2% by the present invention.
Cu element can effectively improve the corrosion resistance of steel under reducing atmosphere, can also effectively inhibit microorganism
Growth attachment, especially suitable for marine worker, ship domain, so ingredient design Cu content is not less than 2%.But Cu element plus
Enter so that the thermoplasticity of steel sharply declines, so the present invention should be controlled by the control of Cu content no more than 3%.
The manufacturing method of the two phase stainless steel uses high-cleanness, high and alloying smelting+two stages heating+big pressure of high temperature
Lower rolling+solid solution treatment process twice, finished product thickness range are 5~70mm, yield strength >=500MPa, tensile strength >=
750MPa, -20 DEG C of Charpy-V impact power >=150J.Seawater corrosion resistance, resistance to biological attachment.
The feature of two phase stainless steel manufacturing method of the invention includes the following steps: electric furnace smelting-external refining-continuous casting-
Rolling-solution treatment.
(1) molten steel smelting and external refining: is passed through into electric furnace smelting plus the decarburization of aod (AOD) furnace, LF furnace secondary fine
Refining, further decreases P, S and non-metallic inclusion content.Obtain mass percentage composition are as follows: C≤0.01%, Si:0.2%~
0.8%, Mn:0.5%~2.0%, P≤0.02%, S≤0.02%, Cr:21%~23%, Ni:4%~9%, Mo:2%~
5%, N:0.13%~0.2%, Cu:2%~3%, remaining is Fe and inevitable impurity.
(2) rolling mill practice: by slab in 600~650 DEG C of loading heating furnaces of furnace temperature, when 600~650 DEG C of low-temperature zones are kept the temperature
Between be 1~1.5 hour, slab heating rate control in temperature-rise period avoids steel billet from being heated too fast generation in 4~6 DEG C/min
Crackle.1200~1300 DEG C of soaking temperature keep the temperature 1~2 hour, and heating furnace atmosphere guarantees the condition in low oxygen content, prevent
The slab of high Cu content is heated at high temperature for a long time under Oxygen Condition, and surface layer liquid Cu is caused to be enriched with, and causes under rolling thermoplasticity
Drop.
Start rolling temperature is controlled at 1200~1300 DEG C, by the control of the first percentage pass reduction 20%~25%, improves slab
As-cast structure, average percentage pass reduction control hereafter is 15%~20%, and final guarantee finishing temperature is at 950 DEG C or more, eventually
Online watering is directly carried out after rolling and accelerates cooling, and cooling velocity is 20~40 DEG C/s, and red temperature is at 300 DEG C or less；
(3) solution treatment: solid solution carries out solution treatment using step-by-step movement solid solution furnace, and solid solubility temperature is controlled 1050~1200
Between DEG C, soaking time is 3~10min/mm, and cooling velocity is 20~40 DEG C/s, is cooled to room temperature.
The utility model has the advantages that
The present invention compared with the existing technology, has the beneficial effect that:
(1) 2%~3% Cu element is added, the effective impact flexibility for improving two phase stainless steel improves the corrosion resistant of steel plate
Erosion ability, and Cu element can also inhibit certain marine organisms to adhere to, and further improve the resistance to marine corrosion of ship, marine worker equipment
Performance.
(2) can production specification be 5~70mm thickness two-phase stainless steel plate, chemical tanker, marine worker steel, composite plate can be met
Demand.
(3) use present component system two phase stainless steel steel plate, good mechanical properties, yield strength >=500MPa,
Tensile strength >=750MPa, -20 DEG C of Charpy-V impact power >=150J.
Detailed description of the invention
Fig. 1 is the two phase stainless steel metallographic structure of embodiment 1, the Phase Proportion of ferrite and austenite is 50%~
50%, austenite structure is tiny and is uniformly distributed.
Specific embodiment
For following embodiment for illustrating the content of present invention, these embodiments are only the general description of the content of present invention,
The content of present invention is not limited.
Table 1 is the chemical component of embodiment steel.Table 2 is embodiment steel rolling method.Table 3 is the solid solution of steel of the embodiment of the present invention
Method；Table 4 is embodiment steel conventional mechanical property；Table 5 is steel of embodiment of the present invention spot corrosion performance；Table 6 is that the present invention is implemented
Example steel corrosion among crystalline grains.
1 steel chemical composition of the embodiment of the present invention (wt, %) of table
| Embodiment | C | Si | Mn | P | S | Cr | Ni | Mo | N | Cu | PRE |
| 1 | 0.005 | 0.4 | 0.72 | 0.002 | 0.002 | 22.3 | 8.5 | 2.5 | 0.18 | 2.5 | 35.95 |
| 2 | 0.007 | 0.21 | 1.91 | 0.001 | 0.001 | 21.1 | 4.2 | 4.66 | 0.13 | 2 | 40.38 |
| 3 | 0.009 | 0.36 | 1.28 | 0.002 | 0.0015 | 21.5 | 5.1 | 3.61 | 0.17 | 2.9 | 38.51 |
| 4 | 0.01 | 0.68 | 0.54 | 0.002 | 0.0017 | 22.5 | 7.8 | 3 | 0.14 | 3 | 36.6 |
| 5 | 0.002 | 0.71 | 0.84 | 0.002 | 0.0009 | 21.8 | 6.5 | 2.71 | 0.2 | 2.2 | 36.74 |
| 6 | 0.001 | 0.52 | 1.49 | 0.001 | 0.0011 | 23.0 | 8.9 | 2.23 | 0.16 | 2.4 | 35.16 |
2 steel rolling method of the embodiment of the present invention of table
3 steel solid dissolving method of the embodiment of the present invention of table
| Embodiment | Solid solubility temperature/DEG C | Soaking time/(minmm-1) | Cooling velocity/(DEG C s-1) |
| 1 | 1050 | 3 | 23 |
| 2 | 1180 | 9 | 26 |
| 3 | 1200 | 6 | 31 |
| 4 | 1150 | 5 | 21 |
| 5 | 1080 | 4 | 39 |
| 6 | 1120 | 8 | 34 |
4 steel conventional mechanical property of the embodiment of the present invention of table
5 steel spot corrosion performance of the embodiment of the present invention of table
| Embodiment | Area/mm2 | Weight/g before testing | Weight/g after test | Weightlessness/g | Corrosion rate/(gm-2·h-1) |
| 1 | 1607.69 | 24.4128 | 24.4125 | 0.0003 | 0.0078 |
| 2 | 1617.10 | 24.0724 | 24.0722 | 0.0002 | 0.0052 |
| 3 | 1608.12 | 24.4212 | 24.421 | 0.0002 | 0.0052 |
| 4 | 1597.49 | 24.2622 | 24.2619 | 0.0003 | 0.0078 |
| 5 | 2824.31 | 47.0041 | 47.004 | 0.0001 | 0.0015 |
| 6 | 2838.07 | 47.2316 | 47.2315 | 0.0001 | 0.0015 |
Note: spot corrosion performance is measured according to the ASTM G48 method A ferric trichloride method of inspection.
6 steel corrosion among crystalline grains of the embodiment of the present invention of table
By table 1~6 as it can be seen that the good two-phase stainless steel plate of corrosion resistance produced using technical solution of the present invention, power
Function admirable is learned, the yield strength of embodiment reaches 522MPa or more in table, and -20 DEG C of Charpy-V impact power monodromes are in 169J or more；And
And the steel has good corrosion resistance, can be widely applied to ship and ocean engineering field.
Claims (3)
1. a kind of good two-phase stainless steel plate of corrosion resistance, which is characterized in that chemical component is by mass percentage in steel are as follows:
C:0.001%~0.01%, Si:0.2%~0.8%, Mn:0.5%~2.0%, P≤0.02%, S≤0.02%, Cr:21%
~23%, Ni:4%~9%, Mo:2%~5%, N:0.13%~0.2%, Cu:2%~3%, surplus is for iron and unavoidably
Impurity, anti-spot corrosion equivalent PRE > 35, wherein PRE%=Crwt%+3.3Mowt%+30Nwt%.
2. a kind of good two-phase stainless steel plate of corrosion resistance as described in claim 1, which is characterized in that finished steel plate
With a thickness of 5~70mm.
3. a kind of manufacturing method of the good two-phase stainless steel plate of corrosion resistance as claimed in claim 1 or 2, the life of steel plate
Production. art are as follows: electric furnace smelting-external refining-continuous casting-rolling-solution treatment, which is characterized in that
Rolling mill practice: by slab in 600~650 DEG C of loading heating furnaces of furnace temperature, 600~650 DEG C of low-temperature zone soaking times be 1~
1.5 hours, heating rate control was in 4~6 DEG C/min in temperature-rise period for slab, and soaking temperature is 1200~1300 DEG C, heat preservation 1
~2 hours；1200~1300 DEG C of start rolling temperature, by the control of the first percentage pass reduction 20%~25%, improve slab as cast condition group
It knits, average percentage pass reduction hereafter is controlled 15%~20%, and finishing temperature is at 950 DEG C or more；Directly watered online
Accelerate cooling, cooling velocity is 20~40 DEG C/s, and red temperature is at 300 DEG C or less；
Solution treatment: solid solubility temperature be 1050~1200 DEG C, soaking time be 3~10min/mm, cooling velocity be 20~40 DEG C/
S is cooled to room temperature.
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Cited By (5)
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| CN111088459A (en) * | 2019-12-31 | 2020-05-01 | 兴化市锐达建材机械有限公司 | High-strength corrosion-resistant stainless steel for bridge piles |
| CN113549825A (en) * | 2021-06-29 | 2021-10-26 | 鞍钢股份有限公司 | High-corrosion-resistance super stainless steel for ocean engineering equipment and manufacturing method thereof |
| EP3978641A4 (en) * | 2019-05-29 | 2022-10-26 | JFE Steel Corporation | Duplex stainless steel and method for manufacturing same, and duplex stainless steel pipe |
| CN115584443A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Copper-containing antibacterial duplex stainless steel continuous tube and processing method thereof |
| CN116288064A (en) * | 2022-12-14 | 2023-06-23 | 鞍钢股份有限公司 | Ultrahigh-strength corrosion-resistant low Wen Haigong steel plate and manufacturing method thereof |
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| CN115584443A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Copper-containing antibacterial duplex stainless steel continuous tube and processing method thereof |
| CN116288064A (en) * | 2022-12-14 | 2023-06-23 | 鞍钢股份有限公司 | Ultrahigh-strength corrosion-resistant low Wen Haigong steel plate and manufacturing method thereof |
| CN116288064B (en) * | 2022-12-14 | 2024-05-14 | 鞍钢股份有限公司 | Ultra-high-strength corrosion-resistant low Wen Haigong steel plate and manufacturing method thereof |
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