CN102560285B - 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 state austenitic stainless steel and preparation method thereof, the method can be controlled nitrogen content effectively.This stainless steel has good processability, also has good corrosion resistance nature, except substituting existing use material, also can be used for forming materials performance, especially the higher field of multi-pass forming requirements.
Background technology
18-8 series austenitic stainless steel as SUS304, SUS304L, all has good corrosion resistance nature, mechanical property, processability and welding property and is widely used in the every field such as chemical industry, the energy, engineering machinery, kitchen tools, goods under high low temperature.Because it is metastable austenite tissue, in the process of machining deformation, can produce martensite, thereby can improve intensity by cold hardening, this is also one of advantage of such austenitic stainless steel, but by the method, put forward the high-intensity hardness of material that simultaneously can cause and become large, Plasticity Decreasing, 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, as Ni, N, C.Except increasing Ni, although austenite structure has been stablized in the increase of other element, because N, C are all strengthening element, a small amount of adding will produce the work hardening significantly causing due to cold deformation, thereby is also 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 intensity and the cold hardening tendency that can significantly reduce austenitic stainless steel in austenitic stainless steel, improve the plasticity of steel, one of object that adds 1.4-2.0% copper as patent US444588A is exactly to improve its cold-forming property, but the hot workability that adds membership reduction austenitic stainless steel of copper, the ε intermetallic compound that can separate out rich copper while at high temperature using, affects its corrosion resistance nature simultaneously.
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, its disclosed patent composition is as follows: 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 inevitably impurity.But the aspects such as its deep processing performance and corrosion resistance nature still require further improvement.
Also need at present a kind of austenitic stainless steel with good deep processing performance and excellent corrosion resistance nature.
Summary of the invention
The object of the present invention is to provide a kind of soft state austenite stainless steel plate material, this austenitic stainless steel, except having good deep processing performance, also has excellent corrosion resistance nature.Wish that especially this stainless steel materials can be applicable to any field of 304L austenitic stainless steel application, be in addition also 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 inevitable impurity.
Described austenitic stainless steel, is less than 5 quality % at the high temperature ferrite δ of as cast condition content.
Another object of the present invention is to provide a kind of nitrogen content control method of above-mentioned steel, and the method comprises the steps:
Two-step approach is smelted, be EAF+AOD+LF technique, first by EAF melting waste steel and alloy raw material, then at AOD refining station, carry out decarburization denitrogenation, and carry out alloying constituent fine setting, finally at LF, feed silk, and make temperature meet casting process requirement, then continuous casting becomes slab, and concrete feature is presented as:
1) reduction of refining station is skimmed after finishing, and after skimming, molten steel per ton adds lime and fluorite to carry out secondary slag making, and N content is controlled at 0.015-0.025%;
2), after secondary slag making, in molten steel, add TiFe powder (for example, molten steel 3-10Kg per ton);
3) after tapping, add low-carbon (LC) synthetic slag to change slag operation, further absorb TiN and be mingled with;
4) when molten steel arrives the refining of LF refining furnace, can optionally add a certain amount of TiFe silk, guarantee to meet Ti >=6C, and cast after stirring, after casting, finished product nitrogen content can be controlled and be less than 0.020%.
The present invention is by common 304L austenitic stainless steel basis, be optimized to and be divided into: 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%, by adjusting Ni, Cr equivalent forming element and make the high temperature ferrite δ content in as-cast austenitic stainless steel be less than 5%, make austenitic stainless steel of the present invention except having good deep processing performance, also there is excellent corrosion resistance nature, can be applicable to any field of 304L austenitic stainless steel application, 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, skims after the reduction of refining station finishes, and after skimming, molten steel adds lime and fluorite to carry out secondary slag making, and N content is controlled at 0.015-0.025%; After secondary slag making, molten steel per ton adds 70% above purity TiFe powder 3-10Kg to the ladle of tapping; After tapping, add low-carbon (LC) synthetic slag to change slag operation, further absorb TiN and be mingled with; When molten steel arrives the refining of LF refining furnace, can add a certain amount of TiFe silk, guarantee to meet Ti >=6C, and cast after stirring, after casting, finished product nitrogen content can be controlled in below 0.020%.
Embodiment
Below the present invention is described in detail.
In the present invention, unless otherwise, content is all mass percentage content.
In order to realize object of the present invention, soft state austenite stainless steel plate material is provided, this austenitic stainless steel is except having good deep processing performance, also there is excellent corrosion resistance nature, can be applicable to any field of 304L austenitic stainless steel application, but also be specially adapted to field that processability and corrosion resistance nature are had relatively high expectations, in austenitic stainless steel of the present invention, each constituent content is controlled as follows:
Carbon is strong formation and stable austenite and expand the element of austenitic area in austenitic stainless steel, so carbon plays effect of crucial importance to forming austenite structure, but carbon content is when too high, can cause carbide Cr
23c
6separate out, reduce intergranular corrosion resistance performance and the pitting resistance of austenitic stainless steel, can cause the work hardening of material in addition, from improving, material is anti-corrosion to be considered with reduction work hardening angle, its content is more low better, but the too low meeting of carbon content control obviously increases smelting procedure cost, therefore can usually solidify the carbon content in steel by adding trace amount of titanium unit, the poor chromium phenomenon of crystal boundary that prevents from forming chromium carbide in steel and cause, thereby the corrosion resisting property causing declines, the particularly reduction of corrosion among crystalline grains, therefore in the present invention by carbon content≤0.025%; Preferably, carbon content≤0.020%, more preferably carbon content is 0.011-0.020%.
Nitrogen is strong formation stable austenite and the element that expands austenitic area, but in austenitic stainless steel, nitrogen is obvious 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 having added micro-titanium elements in alloying constituent of the present invention, if thereby the too high meeting of nitrogen content causes and produces TiN in casting cycle and be mingled with and cause continuously cast bloom surface to form a large amount of defects, or even stop up the mouth of a river and cause being difficult to casting, therefore from reducing materials processing sclerosis and improving surface quality of continuously cast slab angle and consider, its content is more low better, so nitrogen in steel content≤0.02% of the present invention, preferably, N:0.009-0.02%.Ti is as the strong stabilizing element that forms carbon, nitrogen compound in stainless steel, be mainly used in preventing in steel that chromium is combined the poor chromium of intergranular that forms chromium carbide and cause with carbon, thereby cause solidity to corrosion to decline, but the nitrogen adding in membership and stainless steel of titanium forms TiN compound, thereby affects 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 stirring, thereby reduces to a certain extent the nitrogen content in molten steel, and the present invention, from solidifying the angle of carbon, controls finished product for Ti >=6C.
The control of other element is mainly that the alloying constituent system of reference 304 designs, and wherein determining of Cr, Ni content is mainly on 304 stainless bases, to meet the requirement of its Ni, Cr equivalence ratio, and S, P are impurity element, require as far as possible low.Mn is reductor product, is also inevitable.
Preferably, Cr:18.00-19.00 in 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 austenitic stainless steel is higher, illustrate that it is more unstable, in the process of cold deformation, more easily produce martensitic transformation, thereby affect its cold-forming property, especially multi-pass cold deformation.Therefore by balance nickel chromium equivalent forming element, austenitic stainless steel as cast condition high temperature ferrite δ content is controlled as being less than 5%, be mainly in order to guarantee the stability of austenite structure in material, make it in the process of cold deformation, can not produce the too much work hardening causing due to martensite.
The denitrogenation of tradition austenitic stainless steel is mainly by the omnidistance Argon of 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 molten steel, after skimming, AOD taps to LF refining, then casting, and the limited and AOD that the present invention considers AOD denitrification ability is to the nitrogen pick-up phenomenon in LF process, therefore after finishing, the reduction of AOD station skims, after skimming, molten steel adds lime and fluorite to carry out secondary slag making, and N content is controlled at 0.015-0.025%; After secondary slag making, molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping; After tapping, add low-carbon (LC) synthetic slag to change slag operation, further absorb TiN and be mingled with; Then be with slag to tap to LF; When molten steel arrives the refining of LF refining furnace, can add a certain amount of TiFe silk, guarantee to meet Ti >=6C, and cast after stirring, after casting, finished product nitrogen content can be controlled in below 0.020%;
After AOD reduction finishes, carrying out skimming for twice, is mainly the inclusion of removing in molten steel for better, and pure molten steel, for follow-up reduction nitrogen content is laid a good foundation;
After secondary slag making, molten steel per ton adds 70% above purity TiFe powder 3-10Kg to the ladle of tapping, and add low-carbon (LC) synthetic slag to change slag operation after tapping, mainly to make the nitrogen content in itself and molten steel form TIN inclusion by adding containing titanium alloy, neutralize in advance part nitrogen content, and these nitride inclusions can absorb by the protected slag that floats, the low-carbon (LC) synthetic slag adding after tapping is to be also mingled with in order better to absorb TiN, avoid TiN to be mingled with and reside in molten steel, reduce the nitrogen content in molten steel;
With slag tapping, be to be mainly exposed in atmosphere for fear of the molten steel in ladle, covering slag can play the effect of isolated air, reduces the nitrogen pick-up phenomenon in molten steel.
At molten steel when the refining of LF refining furnace, can add a certain amount of (as 70% above purity, TiFe silk 40-250Kg), its effect is mainly for the carbon content in solidified alloy better, avoids the formation of carbon chromium cpd and affects its corrosive nature.
Particularly, the present invention is by common 304L austenitic stainless steel basis, by carbon content control for being less than 0.025%, Control of Nitrogen Content is below 0.020%, thereby reduce the cold hardening phenomenon causing due to strengthening element, by adjusting Ni, Cr equivalent forming element and make the high temperature ferrite δ content in as-cast austenitic stainless steel be less than 5%, thereby reduce the work hardening causing due to the martensite forming in cold hardening process, Ti content is controlled as Ti >=6C, it is mainly the corrosion resistance nature in order to guarantee that it is good, and adopted special nitrogen content control method, be to skim after the reduction of refining station finishes, after skimming, carry out secondary slag making, N content is controlled at 0.015-0.025%, after secondary slag making, molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping, after tapping, add low-carbon (LC) synthetic slag to change slag operation, further absorb TiN and be mingled with, at molten steel, when the refining of LF refining furnace, can add that a certain amount of (as 70% above purity, TiFe silk 40-250Kg), guarantees to meet Ti >=6C, and casts after stirring, and the rear finished product nitrogen content of casting can be controlled in below 0.020%, by the optimization of mentioned component and the employing of control nitrogen process program, obtained a kind of soft state austenitic stainless steel.
The austenite stainless steel plate material that the present invention obtains, 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 good corrosion resistance nature.
Embodiment 1-4
According to austenite stainless composition of steel of the present invention, in Table 1, adopt electric furnace+AOD+LF melting, after finishing, the reduction of refining station skims, after skimming, carry out secondary slag making, N content is controlled at 0.015-0.025%; After secondary slag making, molten steel per ton adds 70% purity TiFe powder 3-10Kg to the ladle of tapping; After tapping, add low-carbon (LC) synthetic slag to change 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 to 0.10-0.25%, and being cast into the thick continuously cast bloom of 200mm after stirring, after casting, finished product Control of Nitrogen Content is below 0.020%; Continuously cast bloom pickling after heating, rolling obtains 3-60mm heavy-gauge sheeting;
In order to contrast, current general 304L (comparative example 1) has also been carried out to EAF+AOD+LF smelting, after hot rolling acid-cleaning, find that such steel is because the work hardening phenomenon that martensite deformation and strengthening element C, N cause is very obvious, if its Md30 is apparently higher than composition of the present invention, a stove and the very approaching austenitic stainless steel of composition of the present invention have been smelted simultaneously, but owing to not adopting control nitrogen method described in the invention in smelting link, finding that finished product nitrogen content obviously increases, there is nitride inclusion defect in surface of steel plate.
Md30 is stabilization of austenite metric, is an important indicator that affects austenitic stainless steel cold-forming property, and wherein Md30 is less, shows that austenite is more stable mutually.Low Md30 value explanation austenite structure is more stable in deformation process,, 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 the processability causing due to upper operation work hardening to worsen.Wherein Md30 adopts following calculation formula: Md30=497-462 (C%+N%)-9.2Si%-8.1Mn%-13.7Cr%-20Ni%.
Test example 1: mechanical property
The mechanical property of measuring embodiment of the present invention steel according to GB/T 228-2002 method, as yield strength Rp0.2, tensile strength Rm and unit elongation A50, it the results are shown in Table 2.
Table 1 embodiment composition and comparative example 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 example 1 | 0.025 | 1.45 | 0.50 | 0.002 | 0.029 | 18.10 | 8.20 | 0.050 | - | 8.86 |
| Comparative example 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
The Rockwell hardness HRB that measures embodiment of the present invention steel according to GB/T 230.1-2004 method, it the results are shown in Table 2.
The contrast of table 2 embodiment and comparative example mechanical property
As seen 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 as can be seen from Table 1, austenitic stainless steel of the present invention not only carbon content is lower, and contain a certain amount of titanium, this has improved the common intergranular corrosion cracking problem causing due to Carbide Precipitation and intergranular poor chromium layer in austenitic stainless steel with regard to obvious, therefore this stainless steel had both had good deep processing performance, also there is excellent corrosion resistance nature, can be applicable to any field of 304L austenitic stainless steel application, be in addition also specially adapted to the field that processability and corrosion resistance nature are had relatively high expectations.
By some embodiment, feature of the present invention is described in further detail above, but is not limited only to these embodiment, not departing under the condition of the present invention's design, can also have more other equivalent embodiment.
Claims (16)
1. an 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 inevitable impurity; Described austenitic stainless steel, is less than 5 quality % at the high temperature ferrite δ of as cast condition content;
Described austenite stainless steel plate material is manufactured by the method that comprises following steps:
First by EAF melting waste steel and alloy raw material, then at AOD refining station, carry out decarburization denitrogenation, and carry out alloying constituent fine setting, finally at LF, feed silk, and make temperature meet casting process requirement, then continuous casting becomes slab, wherein
1) reduction of refining station is skimmed after finishing, and adds lime and fluorite to carry out at least secondary slag making after skimming, and N content is controlled to 0.015-0.025 quality %;
2), at least after secondary slag making, in molten steel, add TiFe powder;
3) after tapping, add low-carbon (LC) synthetic slag to change slag operation, further absorb TiN and be mingled with.
2. austenite stainless steel plate material as claimed in claim 1, is characterized in that, C≤0.020 quality %.
3. austenite stainless steel plate material as claimed in claim 1, is characterized in that, C:0.011-0.020 quality %.
4. austenite stainless steel plate material as claimed in claim 1, is characterized in that, N:0.009-0.02 quality %.
5. austenite stainless steel plate material as claimed in claim 1, is characterized in that, Ni:10.00-11.20 quality %.
6. austenite stainless steel plate material as claimed in claim 1, is characterized in that, Cr:18.00-18.50 quality %.
7. austenite stainless steel plate material as claimed in claim 1, is characterized in that, Mn≤1.5 quality %.
8. austenite stainless steel plate material as claimed in claim 1, is characterized in that, Mn:1.0-1.5 quality %.
9. austenite stainless steel plate material as claimed in claim 1, is characterized in that, Si:0.30-0.40 quality %.
10. austenite stainless steel plate material as claimed in claim 1, is characterized in that, S≤0.005 quality %.
11. austenite stainless steel plate material as claimed in claim 1, is characterized in that, P≤0.030 quality %.
12. austenite stainless steel plate materials as claimed in claim 1, is characterized in that, add lime and fluorite to carry out secondary slag making after skimming, and N content is controlled to 0.015-0.025 quality %.
13. austenite stainless steel plate materials as claimed in claim 1, is characterized in that, the purity of added TiFe powder is more than 70%.
14. austenite stainless steel plate materials as claimed in claim 13, is characterized in that, added TiFe powder amount is molten steel 3-10Kg per ton.
15. austenite stainless steel plate materials as claimed in claim 1, is characterized in that, also comprise 4) when molten steel arrives the refining of LF refining furnace, add TiFe silk, make Ti >=6C, and cast after stirring, the finished product nitrogen content≤0.020 quality % after casting.
16. austenite stainless steel plate materials as claimed in claim 15, is characterized in that, the amount of the TiFe silk of interpolation is molten steel 40-250Kg per ton.
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| 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 |
| CN113136533B (en) * | 2021-04-15 | 2022-08-16 | 鞍钢股份有限公司 | Austenitic stainless steel for low temperature and manufacturing method thereof |
| CN113136522B (en) * | 2021-04-26 | 2022-05-03 | 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 |
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