CN102560285A - Soft austenitic stainless steel and preparation method thereof - Google Patents
Soft austenitic stainless steel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a soft austenitic stainless steel which comprises the following components by weight: less than or equal to 0.025% of C, less than or equal to 0.020% of N, more than or equal to 6C of Ti, 10.00-12.00% of Ni, 18.00-19.00% of Cr, less than or equal to 2% of Mn, less than or equal to 0.40% of Si, less than or equal to 0.015% of S, less than or equal to 0.045% of P, and the balance of Fe and inevitable impurities. The high-temperature ferrite delta content of the austenitic stainless steel is less than 5%. The invention also relates to a preparation method of the soft austenitic stainless steel. The preparation method comprises the following steps of: skimming slags after completing the reduction at a refining station; after skimming slags, adding lime and fluorite in each ton of liquid steel, and performing slagging at least twice, with the N content being controlled within the range of 0.015-0.025%; after two slaggings, adding TiFe powder into each ton of liquid steel till tapping ladle; after tapping, adding low-carbon synthetic slag so as to perform a slag exchanging operation and further absorb TiN impurities; when the liquid steel reaches an LF (ladle furnace) refining furnace for refining, adding a certain quantity of TiFe wires, thereby causing Ti to be more than or equal to 6C; and casting after stirring, wherein the nitrogen content of an end product after being cast is less than or equal to 0.020%. The soft austenitic stainless steel provided by the invention is applied to the field with higher demand on forming property and corrosion resistance.
Description
Technical field
The present invention relates to a kind of stainless steel, particularly a kind of soft attitude austenitic stainless steel and preparation method thereof, this method can be controlled nitrogen content effectively.This stainless steel has good processability, also has excellent corrosion resisting performance, except substituting existing materials used, also can be used for the forming materials performance, especially the multi-pass moulding field of having relatively high expectations.
Background technology
18-8 series austenitic stainless steel like SUS304, SUS304L, all has excellent corrosion resisting performance, mechanical property, processability and welding property and is widely used in every field such as chemical industry, the energy, engineering machinery, kitchen tools, goods under high low temperature.Because it is the meta austenite structure; In the process of machining deformation, can produce martensite, thereby can improve intensity through cold hardening, this also is one of advantage of such austenitic stainless steel; But the hardness that can cause material when improving intensity through this method becomes big; Plasticity reduces, even produces fragility, is unfavorable for the deep processing distortion of material.A feasible method that improves this problem is the content that increases austenite former, like Ni, N, C.Except increasing Ni, though austenite structure has been stablized in the increase of other element, owing to N, C are all strengthening element, a spot of adding will produce the work hardening that significantly causes owing to cold deformation, thereby also is unfavorable for the deep processing distortion of material.Copper is the important element that significantly improves all kinds of austenitic stainless steel cold formabilities; It joins the intensity and the cold hardening tendency that can significantly reduce austenitic stainless steel in the austenitic stainless steel; Improve the plasticity of steel, one of purpose that adds 1.4-2.0% copper like patent US444588A is exactly to improve its cold-forming property, but the hot workability that adds affiliation reduction austenitic stainless steel of copper; Can separate out the ε intermetallic compound of rich copper when at high temperature using simultaneously, influence its corrosion resistance nature.
Another feasible pattern that solves such problem is to obtain stable austenite structure, and makes steel softer simultaneously, is difficult for producing work hardening.Patent US4784828A discloses a kind of low-carbon and nitrogen, the good austenitic stainless steel of cutting ability, and its disclosed patent composition is following: C+N≤0.065%, Cr:16-30%; Ni:5-26%, S:0.10-0.45%, Mn:0.75-2.0%; Si≤1%, P≤0.20%, Mo≤1.0%; Cu≤1.00, Yu Weitie and unavoidable impurities.But aspects such as its deep processing performance and corrosion resistance nature still need further to improve.
Also need a kind of austenitic stainless steel at present with good deep processing performance and corrosion resistance nature of excellence.
Summary of the invention
The object of the present invention is to provide a kind of soft attitude austenite stainless steel plate material, this austenitic stainless steel also has excellent corrosion resistance nature except having good deep processing performance.Hope that especially this stainless steel materials can be applicable to any field that the 304L austenitic stainless steel is used, in addition also be specially adapted to the field that processability and corrosion resistance nature are had relatively high expectations.
To achieve these goals, the invention provides a kind of austenite stainless steel plate material, its mass percent consists of: C≤0.025%; N≤0.020%, Ti>=6C, Ni:10.00-12.00%; Cr:18.00-19.00%, Mn≤2%, Si≤0.40%; S≤0.015%, P≤0.045%, surplus is Fe and unavoidable impurities.
Said austenitic stainless steel, at the high temperature ferritic δ of as cast condition content less than 5 quality %.
Another object of the present invention provides a kind of nitrogen content control method of above-mentioned steel, and this method comprises the steps:
Two-step approach is smelted, and promptly EAF+AOD+LF technology is at first passed through EAF melting waste steel and alloy raw material; Carry out the decarburization denitrogenation at AOD refining station then; And carry out the alloying constituent fine setting, feed silk at LF at last, and make temperature satisfy the casting process requirement; Continuous casting becomes slab then, and concrete characteristics are presented as:
1) skim after the reduction of refining station finishes, the back molten steel per ton of skimming adds lime and fluorite carries out the secondary slag making, and N content is controlled at 0.015-0.025%;
2) after the secondary slag making, in molten steel, add TiFe powder (for example, molten steel 3-10Kg per ton);
3) tapping back adding low-carbon (LC) synthetic slag changes slag operation, further absorbs TiN and is mingled with;
4) when molten steel arrives the refining of LF refining furnace, can choose wantonly and add a certain amount of TiFe silk, guarantee to satisfy Ti >=6C, and cast after stirring that finished product nitrogen content may command is less than 0.020% after the casting.
The present invention is through on common 304L austenitic stainless steel basis, and optimized composition is: C≤0.025%, N≤0.020%; Ti>=6C, Ni:10.00-12.00%, Cr:18.00-19.00%; Mn≤2%, Si≤0.40%, S≤0.015%; P≤0.045% through adjustment Ni, Cr equivalent forming element and make high temperature ferritic δ content in the as cast condition austenitic stainless steel less than 5%, makes austenitic stainless steel of the present invention except having good deep processing performance; Also have excellent corrosion resistance nature, can be applicable to any field that the 304L austenitic stainless steel is used, but also be specially adapted to field that processability and corrosion resistance nature are had relatively high expectations.The nitrogen content control method that the present invention is special is skimmed after the reduction of refining station finishes, and the back molten steel of skimming adds lime and fluorite carries out the secondary slag making, and N content is controlled at 0.015-0.025%; Molten steel per ton adds 70% above purity TiFe powder 3-10Kg to the ladle of tapping after the secondary slag making; The tapping back adds the low-carbon (LC) synthetic slag and changes slag operation, further absorbs TiN and is mingled with; When molten steel arrives the refining of LF refining furnace, can add a certain amount of TiFe silk, guarantee to satisfy Ti >=6C, and cast after stirring that casting back finished product nitrogen content can be controlled in below 0.020%.
Embodiment
Below the present invention is carried out comparatively detailed explanation.
Among the present invention, unless otherwise, content all is mass percentage content.
In order to realize the object of the invention; Soft attitude austenite stainless steel plate material is provided; This austenitic stainless steel also has excellent corrosion resistance nature except having good deep processing performance, can be applicable to any field that the 304L austenitic stainless steel is used; But also be specially adapted to field that processability and corrosion resistance nature are had relatively high expectations, each constituent content control is as follows in the austenitic stainless steel of the present invention:
Carbon is strong formation and stable austenite and enlarge the element of austenitic area in austenitic stainless steel, so carbon plays effect of crucial importance to forming austenite structure, but carbon content can cause carbide Cr when too high
23C
6Separate out, reduce the intergranular corrosion resistance performance and the pitting resistance of austenitic stainless steel, can cause the work hardening of material in addition; Material is anti-corrosion to be considered with reduction work hardening angle from improving; Its content is low more good more, but carbon content was controlled low obviously increase smelting procedure cost, therefore can usually solidify the carbon content in the steel through adding trace amount of titanium unit; The poor chromium phenomenon of crystal boundary that prevents to form the chromium carbon cpd in the steel and cause; Thereby the corrosion resisting property that causes descends, and the reduction of particularly intergranular corrosion performance is therefore in the present invention with carbon content≤0.025%; Preferably, carbon content≤0.020%, more preferably carbon content is 0.011-0.020%.
Nitrogen is the element of strong formation and stable austenite and expansion austenitic area; But in austenitic stainless steel, nitrogen is tangible work hardening element, and the cold hardening effect of its generation is very obvious; This cold hardening is unfavorable for the deep processing of material, especially multi-pass deep processing distortion.In addition owing to added micro-titanium elements in the alloying constituent of the present invention; If thereby the too high meeting of nitrogen content causes in the casting cycle and to produce TiN and be mingled with and cause the continuously cast bloom surface to form a large amount of defectives, perhaps even stop up the mouth of a river and cause being difficult to casting, therefore from reducing the materials processed sclerosis and improving the surface quality of continuously cast slab angle and consider; Its content is low more good more; So nitrogen in steel content of the present invention≤0.02%, preferably, N:0.009-0.02%.Ti is as the strong stabilizing element that forms carbon, nitrogen compound in the stainless steel; Be mainly used in and prevent that chromium in the steel from combining with carbon to form the chromium carbon cpd and the poor chromium of intergranular that causes; Thereby cause solidity to corrosion to descend; But the nitrogen that adds in affiliation and the stainless steel of titanium forms the TiN compound, thereby influences the surface quality and the inner quality of steel; In the process of smelting, add titanium, the TiN of its formation can float in the process that stirs, thereby reduces the nitrogen content in the molten steel to a certain extent, and the present invention is controlled to be Ti >=6C from solidifying the angle of carbon with finished product.
The control of other element mainly is to design with reference to 304 alloying constituent system, wherein Cr, Ni content confirm it mainly is the requirement of on 304 stainless bases, satisfying its Ni, Cr equivalence ratio, and S, P are impurity element, require low as far as possible.Mn is the reductor product, also is inevitable.
Preferably, Cr:18.00-19.00 among the present invention, more preferably, Cr:18.00-18.50%;
Ni:10.00-12.00%, preferably, Ni:10.00-11.20%;
Mn≤2%, preferably, Mn≤1.5%, more preferably, Mn:1.0-1.5%;
Si≤0.40%, preferably, Si:0.30-0.40%;
S≤0.015%, preferably, S≤0.005%;
P≤0.045%, preferably, P≤0.030%.
Because the ferrite content in the austenitic stainless steel is high more, explains that it is more unstable, easy more generation martensitic transformation in the process of cold deformation, thus influence its cold-forming property, multi-pass cold deformation especially.Therefore through balance nickel chromium equivalent forming element; Austenitic stainless steel as cast condition high temperature ferritic δ content is controlled to be less than 5%; Mainly be in order to guarantee the stability of austenite structure in the material, it is too much because the work hardening that martensite causes that it can not produced in the process of cold deformation.
The denitrogenation of tradition austenitic stainless steel mainly is the omnidistance Argon through argon oxygen degasification furnace AOD; Utilize argon gas bubbles refining theory to remove a part of nitrogen content; Realize the reduction of nitrogen content in the molten steel, tap after AOD skims, then casting to the LF refining; And the nitrogen pick-up phenomenon of the limited and AOD that the present invention considers AOD denitrogenation ability in the LF process; Therefore after the reduction of AOD station finishes, skim, the back molten steel of skimming adds lime and fluorite carries out the secondary slag making, and N content is controlled at 0.015-0.025%; Molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping after the secondary slag making; The tapping back adds the low-carbon (LC) synthetic slag and changes slag operation, further absorbs TiN and is mingled with; Be with slag to tap then to LF; When molten steel arrives the refining of LF refining furnace, can add a certain amount of TiFe silk, guarantee to satisfy Ti >=6C, and cast after stirring that casting back finished product nitrogen content can be controlled in below 0.020%;
Carrying out skimming for twice after the AOD reduction finishes, mainly is the inclusion of removing in the molten steel for better, and pure molten steel is for follow-up reduction nitrogen content is laid a good foundation;
Molten steel per ton adds 70% above purity TiFe powder 3-10Kg to the ladle of tapping after the secondary slag making; And the tapping back adds the low-carbon (LC) synthetic slag and changes slag operation; Mainly be to contain titanium alloy through adding to make the nitrogen content in itself and the molten steel form the TIN inclusion; The part that neutralizes in advance nitrogen content, and these nitride inclusions can be absorbed by covering slag through come-up, the low-carbon (LC) synthetic slag that the tapping back adds also is to be mingled with in order better to absorb TiN; Avoid TiN to be mingled with and reside in the molten steel, reduce the nitrogen content in the molten steel;
Band slag tapping mainly is that the molten steel in the ladle is exposed in the atmosphere, and covering slag can play the effect of secluding air, reduces the nitrogen pick-up phenomenon in the molten steel.
At molten steel when the refining of LF refining furnace, can add a certain amount of (like 70% above purity, TiFe silk 40-250Kg), its effect mainly is for the carbon content in the solidified alloy better, avoids the formation of carbon chromium cpd and influences its corrosive nature.
Particularly, the present invention is controlled to be carbon content less than 0.025% through on common 304L austenitic stainless steel basis; Nitrogen content is controlled at below 0.020%; Thereby reduce because the cold hardening phenomenon that strengthening element causes, through adjustment Ni, Cr equivalent forming element and make high temperature ferritic δ content in the as cast condition austenitic stainless steel, thereby reduce because the work hardening that the martensite that forms in the cold hardening process causes less than 5%; Ti content is controlled to be Ti >=6C; Mainly be for guarantee its superior corrosion resistance can, and adopted special nitrogen content control method, i.e. skim after refining station reduction finishes; Carry out the secondary slag making after skimming, N content is controlled at 0.015-0.025%; Molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping after the secondary slag making; The tapping back adds the low-carbon (LC) synthetic slag and changes slag operation, further absorbs TiN and is mingled with; When the refining of LF refining furnace, can add that a certain amount of (like 70% above purity, TiFe silk 40-250Kg) guarantees to satisfy Ti >=6C, and casts after stirring, and the finished product nitrogen content can be controlled in below 0.020% after the casting at molten steel; Through the optimization of mentioned component and the employing of control nitrogen process program, obtained a kind of soft attitude austenitic stainless steel.
The austenite stainless steel plate material that the present invention obtained, material is softer, and plasticity and toughness are better, and processability is excellent, also has good solidity to corrosion.Than conventional products 304L sheet material, the austenite stainless steel plate material that the present invention is prepared, the finished product have better plasticity and toughness, and material has excellent corrosion resisting performance.
Embodiment 1-4
According to austenite stainless composition of steel of the present invention, see table 1, adopt electric furnace+AOD+LF melting, after finishing, the reduction of refining station skims, carry out the secondary slag making after skimming, N content is controlled at 0.015-0.025%; Molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping after the secondary slag making; The tapping back adds the low-carbon (LC) synthetic slag and changes slag operation; When molten steel arrives the refining of LF refining furnace, add the TiFe silk 40-250Kg of 70% purity, Ti content is controlled at 0.10-0.25%; And being cast into the thick continuously cast bloom of 200mm after stirring, casting back finished product nitrogen content is controlled at below 0.020%; Continuously cast bloom obtains the 3-60mm heavy-gauge sheeting through heating, rolling back pickling;
In order to contrast; Present general 304L (Comparative Examples 1) has also been carried out the EAF+AOD+LF smelting; Through finding such steel behind the hot rolling acid-cleaning because the work hardening phenomenon that martensite deformation and strengthening element C, N cause is very obvious; Apparently higher than composition of the present invention, smelted a stove and the very approaching austenitic stainless steel of composition of the present invention like its Md30 simultaneously, but owing to do not adopt control nitrogen method described in the invention in the smelting link; Find that the finished product nitrogen content obviously increases, there is the nitride inclusion defective in surface of steel plate.
Md30 is the stabilization of austenite metric, is an important indicator that influences the austenitic stainless steel cold-forming property, and wherein Md30 is more little, shows that austenite is stable more mutually.Low Md30 value explanation austenite structure is more stable in deformation process, promptly when the cold working of material or moulding, especially in the cold working and moulding process of multiple operation, has avoided to a certain extent because the processability deterioration that the sclerosis of last working procedure processing causes.Wherein Md30 adopts following calculation formula: Md30=497-462 (C%+N%)-9.2Si%-8.1Mn%-13.7Cr%-20Ni%.
Test Example 1: mechanical property
According to the mechanical property of GB/T 228-2002 method mensuration embodiment of the invention steel, like ys Rp0.2, tensile strength Rm and unit elongation A50, its result sees table 2.
Table 1 embodiment composition and Comparative Examples composition (mass percent %, surplus is iron and inevitable impurity element)
| Element | C | Mn | Si | S | P | Cr | Ni | N | Ti | δ |
| Embodiment 1 | 0.020 | 1.50 | 0.40 | 0.002 | 0.020 | 18.10 | 10.05 | 0.015 | 0.19 | 4.96 |
| Embodiment 2 | 0.015 | 1.15 | 0.30 | 0.001 | 0.025 | 18.05 | 10.50 | 0.009 | 0.15 | 4.41 |
| Embodiment 3 | 0.011 | 1.10 | 0.32 | 0.003 | 0.028 | 18.20 | 11.15 | 0.018 | 0.14 | 4.07 |
| Embodiment 4 | 0.017 | 1.20 | 0.35 | 0.003 | 0.030 | 18.15 | 11.10 | 0.020 | 0.19 | 3.85 |
| Comparative Examples 1 | 0.025 | 1.45 | 0.50 | 0.002 | 0.029 | 18.10 | 8.20 | 0.050 | - | 8.86 |
| Comparative Examples 2 | 0.021 | 1.20 | 0.50 | 0.002 | 0.030 | 18.10 | 10.60 | 0.029 | 0.21 | 4.91 |
Test Example 2: hardness
According to the Rockwell hardness HRB of GB/T 230.1-2004 method mensuration embodiment of the invention steel, its result sees table 2.
The contrast of table 2 embodiment and Comparative Examples mechanical property
Visible from table 2, austenitic stainless steel Md30 of the present invention is lower, and low Md30 value shows that it has good deep processing performance.And from table 1, can find out; Austenitic stainless steel of the present invention not only carbon content is lower; And contain a certain amount of titanium; This has improved in the austenitic stainless steel commonly owing to carbide is separated out the intergranular corrosion cracking problem that causes with the poor chromium layer of intergranular with regard to obvious, so this stainless steel both had good deep processing performance, also had excellent corrosion resistance nature; Can be applicable to any field that the 304L austenitic stainless steel is used, in addition also be specially adapted to the field that processability and corrosion resistance nature are had relatively high expectations.
More than through some embodiment characteristics of the present invention have been carried out comparatively detailed explanation, but be not limited only to these embodiment, under the condition that does not break away from the present invention's design, more other equivalent embodiment can also be arranged.
Claims (17)
1. austenite stainless steel plate material, its mass percent consists of: C≤0.025%, N≤0.020%, Ti>=6C; Ni:10.00-12.00%, Cr:18.00-19.00%, Mn≤2%, Si≤0.40%; S≤0.015%, P≤0.045%, surplus is Fe and unavoidable impurities.
2. austenite stainless steel plate material as claimed in claim 1 is characterized in that, said austenitic stainless steel, at the high temperature ferritic δ of as cast condition content less than 5 quality %.
3. according to claim 1 or claim 2 austenite stainless steel plate material is characterized in that C≤0.020 quality %.
4. like the arbitrary described austenite stainless steel plate material of claim 1-3, it is characterized in that C:0.011-0.020 quality %.
5. like the arbitrary described austenite stainless steel plate material of claim 1-4, it is characterized in that N:0.009-0.02 quality %.
6. like the arbitrary described austenite stainless steel plate material of claim 1-5, it is characterized in that Ni:10.00-11.20 quality %.
7. like the arbitrary described austenite stainless steel plate material of claim 1-6, it is characterized in that Cr:18.00-18.50 quality %.
8. like the arbitrary described austenite stainless steel plate material of claim 1-7, it is characterized in that Mn≤1.5 quality %.
9. like the arbitrary described austenite stainless steel plate material of claim 1-8, it is characterized in that Mn:1.0-1.5 quality %.
10. like the arbitrary described austenite stainless steel plate material of claim 1-9, it is characterized in that Si:0.30-0.40 quality %.
11., it is characterized in that S≤0.005 quality % like the arbitrary described austenite stainless steel plate material of claim 1-10.
12., it is characterized in that P≤0.030 quality % like the arbitrary described austenite stainless steel plate material of claim 1-11.
13. the method for manufacture like the arbitrary described austenite stainless steel plate material of claim 1-12 comprises the steps:
At first through EAF melting waste steel and alloy raw material, carry out the decarburization denitrogenation at AOD refining station then, and carry out the alloying constituent fine setting, feed silk at LF at last, and make temperature satisfy the casting process requirement, continuous casting becomes slab then, wherein
1) skim after the reduction of refining station finishes, the back of skimming adds lime and fluorite carries out secondary slag making at least, and N content is controlled at 0.015-0.025 quality %;
2) at least after the secondary slag making, in molten steel, add the TiFe powder;
3) tapping back adding low-carbon (LC) synthetic slag changes slag operation, further absorbs TiN and is mingled with;
4) when molten steel arrives the refining of LF refining furnace, the optional TiFe silk that adds makes Ti>=6C, and casts finished product nitrogen content≤0.020% after the casting after stirring.
14. method as claimed in claim 13 is characterized in that, the back of skimming adds lime and fluorite carries out the secondary slag making, and N content is controlled at 0.015-0.025 quality %.
15., it is characterized in that the purity of added TiFe powder is more than 70% like claim 13 or 14 described methods.
16., it is characterized in that added TiFe powder amount is molten steel 3-10Kg per ton like the arbitrary described method of claim 13-15.
17., it is characterized in that the amount of the optional TiFe powder that adds is molten steel 40-250Kg per ton like the arbitrary described method of claim 13-16.
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| CN107419169A (en) * | 2011-04-18 | 2017-12-01 | 奥托库姆普联合股份公司 | Method for manufacturing and using ferrite austenitic stainless steel |
| CN104250673A (en) * | 2013-06-25 | 2014-12-31 | 江苏万恒铸业有限公司 | Smelting process for reducing ferrite content of nuclear grade stainless steel castings |
| CN104250673B (en) * | 2013-06-25 | 2016-06-29 | 江苏万恒铸业有限公司 | A kind of smelting technology reducing nuclear grade stainless steel foundry goods ferrite content |
| CN103667589A (en) * | 2013-12-04 | 2014-03-26 | 蚌埠华泰特种钢有限公司 | Two-step method for producing austenitic stainless steel by using stainless steel scrap |
| CN112899575A (en) * | 2021-01-20 | 2021-06-04 | 钢铁研究总院 | Austenitic stainless steel wire material manufactured based on cold metal transition arc additive manufacturing and process |
| CN113136533A (en) * | 2021-04-15 | 2021-07-20 | 鞍钢股份有限公司 | Austenitic stainless steel for low temperature and manufacturing method thereof |
| CN113136522A (en) * | 2021-04-26 | 2021-07-20 | 河南中原特钢装备制造有限公司 | Process for smelting titanium-containing austenitic stainless steel by argon oxygen furnace |
| CN115852237A (en) * | 2021-09-24 | 2023-03-28 | 宝武特种冶金有限公司 | Austenitic stainless steel bar and preparation method thereof |
| CN114318144A (en) * | 2021-12-24 | 2022-04-12 | 浦项(张家港)不锈钢股份有限公司 | Austenitic stainless steel for spiral welded pipe, manufacturing process and application |
| CN115747662A (en) * | 2022-11-30 | 2023-03-07 | 山西太钢不锈钢股份有限公司 | Method for refining stainless steel for high-pressure common rail of engine |
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