CN102618804B - Austenitic heat-resistant steel and production method thereof - Google Patents
Austenitic heat-resistant steel and production method thereof Download PDFInfo
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Abstract
The invention relates to austenitic heat-resistant steel, which comprises, in weight percentage, 0.10-0.20% of C, 5.00-6.00% of Si, 0.50-2.00% of Mn, 24.0-26.0% of Cr, not less than 0.045% of P, not less than 0.035% of S, 19.0-22.00% of Ni, 0.50-1.00% of Mo, 0.050-0.10% of N, not less than 0.005% of O, and the balance of Fe and unavoidable impurities. A production method of the austenitic heat-resistant steel includes: casting at a superheat degree (delta T) of 20-40 DEG C, rolling, allowing for deformation under rolling at 900-1250 DEG C with total deformation of 65-90%, and cooling strip steel to 400-500 DEG C at a cooling speed of 30-60 DEG C/s, wherein the molten steel casting temperature T is equal to Tl and the delta T, TL refers to liquidus temperature, the delta T refers to superheat degree of the steel plate, casting blank in a furnace stays for not less than 1.2-1.5m/mm according to the thickness of the blank, and discharge temperature of the blank is 1230-1265 DEG C.
Description
Technical field
The present invention relates to high temperature steel, particularly relate to high alloy austenitic heat-resistance steel and manufacture method thereof.
Background technology
310S high temperature steel belongs to traditional heat-resistant high alloy steel, the chromium that its main component is 25% and 20% nickel, and alloy average content reaches 45%.310S heatproof zone steel is widely used in the high-temperature heat-resistance occasions such as steel stove, process furnace, annealing furnace, and its heat resisting temperature can reach 1000 ℃ of left and right.But, be subject to impact and the restriction in cold cycling cycle the work-ing life at this temperature always.The chemical composition (% by weight) of 310S high temperature steel is: C:1.5, Si:0.08, Mn:2.00, P:0.035, S:0.030, Cr:24-26, Ni:19-22.Strip steel hot rolling process flow process and the austenitic stainless steel of this high temperature steel are basic identical, and technical process is as follows: the continuous annealing of smelting → sheet billet continuous casting → heating of plate blank → hot strip rolling → strip coiling → band steel, pickling → inspection → batching, pack.Slab heating temperature is about 1250 ℃, and strip finishing temperature is greatly about more than 900 ℃.For even strip property, remove iron scale, need carry out high temperature annealing at continuous annealing, pickling unit, need spray iron sand strike belt steel surface in order to remove belt steel surface iron scale, use afterwards the strong corrosive mediums such as sulfuric acid, hydrochloric acid, hydrofluoric acid to remove remaining black oxidation iron sheet, make belt steel surface present argenteous finished product state.
Summary of the invention
The object of the present invention is to provide a kind of high alloy austenitic heat-resistance steel, there is good hot strength and high-temperature oxidation resistance.
To achieve these goals, the chemical composition of high alloy austenitic heat-resistance steel of the present invention is (quality %): C:0.10-0.20%, Si:5.00-6.00%, Mn:0.50-2.00%, Cr:24.0-26.0%, P≤0.045, S≤0.035%, Ni:19.0-22.00%, Mo:0.50-1.00%, [N]: 0.050-0.10%, [O]≤0.005%, all the other are iron and inevitable impurity.
Another object of the present invention is to provide the manufacture method of above-mentioned high alloy austenitic heat-resistance steel, and the method comprises the steps:
Cast:
Superheating temperature (Δ T) is 20-40 ℃, and molten steel casting temperature T=TL+ Δ T, in formula: TL-liquidus temperature, Δ T-molten steel overheat;
In cast, the temperature of cooling water of crystallizer remains on 35-45 ℃; The speed control of cast slab is at 0.5-1.1m/min;
Rolling:
According to slab thickness, the slab time inside furnace of cast is not less than 1.2 minutes/mm, and slab tapping temperature is 1230-1265 ℃;
At 900-1250 ℃, by slab rolling distortion, total deformation is 65-90%; Then with the speed of cooling of 30-60 ℃/s, the band steel of finish rolling is cooled to 400-500 ℃.
The present invention designs by reasonable component, add in right amount high silicon content, make Si reach 5-6%, and a small amount of molybdenum and nitrogen, iron scale adhesivity under the high temperature of steel is improved, difficult drop-off, makes the matrix under iron scale avoid further oxidative attack, thereby has improved the work-ing life of high temperature steel.The hot strength of high alloy austenitic heat-resistance steel of the present invention and high temperature life are significantly improved than 310S hot rolling heatproof zone steel.
Accompanying drawing explanation
Fig. 1 is hot strength (yield strength and tensile strength) the variation with temperature curve of 310S steel.
Fig. 2 is hot strength (yield strength and tensile strength) the variation with temperature curve of the embodiment of the present invention 2 steel.
Fig. 3 is the embodiment of the present invention 2 steel and 310S steel at the high-temperature oxidation resistance correlation curve of 1000 ℃, and wherein X-coordinate is time (t), and unit is hour; Ordinate zou is gain in weight, and unit is mg/cm
2.
Embodiment
Below in conjunction with embodiment, the features and advantages of the invention are described in detail.
In the present invention, unless otherwise, content all refers to weight percent content.
In order to realize the object that high alloy austenitic heat-resistance steel is provided of the present invention, each control of element is as follows:
Carbon is the important element in austenitic stainless steel, and carbon can expand austenitic area, and the intensity of raising exists in steel or with solid solution form, or exists with the form of Carbide Precipitation.As required, by suitable metallurgical mode, make the effect of carbon to the performance future development that is conducive to improve steel.In the present invention, control C:0.10-0.20%, improved the Testing Tensile Strength at Elevated Temperature of steel, preferably, C:0.140-0.160%.
Silicon is indispensable element in stainless steel smelting.Lower at silicone content, take reductor as Main Function in the situation that, can make the oxygen level in steel reduce, improve the purity of steel.In high temperature steel, due to the raising of silicone content, make enrichment in the surface scale of silicone content steel, form silicon-rich oxide film (SiO
2) improve the tack of oxide skin and matrix steel, make oxide skin be difficult for separating with matrix steel, improve the anti-deciduous of oxide skin, thereby improved resistance toheat and the work-ing life of steel.In the present invention, control Si:5.00-6.00%.
Manganese is weak austenite former, and it is a kind of reductor in high temperature steel, along with the increase of manganese content in steel, can significantly improve the solubleness of nitrogen in steel.Manganese, nitrogen can be used for replacing nickel expensive in steel compound adding.Manganese can also improve the strength property of steel.In the present invention, control Mn:0.50-2.00%, manganese has the characteristic that reduces active in austenite of nitrogen and don't cause the displacement solute of precipitation, the solid solution nitrogen in can stabilized steel, the effect that therefore can give full play to nitrogen and improve the tensile strength of steel.Preferably, Mn:0.80-1.60%.
Oxidation-resistance and the solidity to corrosion of chromium to steel has important effect, and chromium is stronger than the affinity of other element with oxygen, and the surface that chromium and oxygen are combined in steel forms fine and close oxide film, makes oxygen be difficult in steel, permeating again, thus the further oxidation of the steel preventing.Along with the increase of chromium content, not only the solidity to corrosion in Oxidant strengthens, and the raising of stainless other etch resistant properties is had to remarkable effect.Carbon in chromium and high temperature steel forms carbide at a certain temperature, but when one timing of carbon amount, with the increase of chromium content in steel, antioxidant property is improved.In the present invention, control Cr:24.0-26.0%.
Phosphoric is the impurity element in steel, in 310S steel phosphoric on be limited to 0.035%, still, the alloy content of high temperature steel is high at present, and the phosphorus content of steel is along with returning to the use of steel, and constantly accumulation improves, the dephosphorization cost of high-chromium alloy high temperature steel is very high, and has larger danger.In the Composition Design of steel, by improving silicone content, it is minimum that reduction sulphur content is down to the detrimental action of phosphorus.In the present invention, control P≤0.045%, be preferably P≤0.035%, more preferably 0.010-0.030%.
Sulphur is the impurity element of steel, different from phosphorus, in steel the removal of sulphur comparatively easy, sulphur and oxygen level in steel are closely related.In smelting, strengthen the deoxidation of steel, reduce the oxygen level of steel, and improve the control of the metallurgical slag of steel, can well reduce sulphur content, improve processing characteristics and the use properties of high temperature steel.In the present invention, control S≤0.035%, in the situation that processing conditions allows, higher sulphur content can reduce smelting cost, preferably, S≤0.030%, more preferably, S≤0.020%, reduction sulphur content can be improved the high-temp plastic of steel, improves the high temperature process performance of steel.
Controlling oxygen level is mainly to consider that oxygen content in steel and inclusion content have relation, controls total oxygen content and can reduce as far as possible inclusion content, improves formability.In the present invention, control [O] control and be less than 0.005%.
Nickel is the important alloying element that is only second to chromium in high temperature steel.In order to improve hot strength and the austenite structure of steel, the enough nickel of essential interpolation.Nickel can promote the stability of high temperature steel oxide film, improves the thermodynamic stability of steel.Therefore, the coexisting of chromium and nickel in high temperature steel, can significantly strengthen the resistance toheat of steel.In the present invention, control Ni:19.0-22.00%.
Molybdenum is the important element in high temperature steel, and when containing the chromium element of q.s in steel, the interpolation of molybdenum can increase the hot strength of steel, the high-temperature behavior of stabilized steel.In the present invention, control Mo:0.50-1.00%.
The application of nitrogen element in high temperature steel has good benefit.Nitrogen is austenite former, can improve the hot strength of high temperature steel, in the Composition Design in this steel, improves the content of nitrogen element, makes hot strength and stability more stable compared with 310S.In the present invention, control total nitrogen content [N]: 0.050-0.10%.
High temperature steel composition interalloy content of the present invention reaches more than 50%, and therefore, for this high alloy system, the preferred manufacturing process of steel of the present invention is as follows:
1) in smelting steel, the control of molten steel chromium component is put in place, preferential carbon content control is 0.140-0.160%, and manganese is controlled at 0.80-1.60%, and nickel content is controlled at lower limit; Sulphur content is preferably controlled as≤0.0020%, and other element is pressed normal level control.
2) because the alloy content of steel is high, silicone content reaches 5-6%, the cross dimensions span of control of continuous casting steel billet: thick × wide=(150～300) × (750～2100) mm; In continuous casting steel billet process, liquid steel temperature is difficult for too high, and superheating temperature (Δ T) is controlled as 20-40 ℃; Too low molten steel overheat (Δ T) is unfavorable for the fusing of covering slag and the floating of steel inclusion.
Water=TL+ of molten steel casting temperature: T Δ T
In formula: TL---liquidus temperature
Δ T---molten steel overheat
The temperature of cooling water of crystallizer remains on 35-45 ℃; The speed control of cast slab, at 0.5-1.1m/min, with slower speed Pour Steel, can make continuous casting plate surface solidification layer thickness in crystallizer increase, and prevents that strand from going out bleed-out after crystallization and the crackle of steel slab surface produces.
3) process furnace heating process:
Slab time inside furnace and to take out steel temperature as follows:
Time inside furnace is 1.2-1.5 minute/mm according to slab thickness, and the control of slab tapping temperature is 1230-1265 ℃, guarantees that board briquette is even, has good deformability.
4) between the best high temperature rolling of this high temperature steel trade mark distorted area, be 900-1250 ℃.Slab rolling must be deformed into target thickness in this temperature range, complete the control of product specification.In band steel finishing stands, rolling reduction requires to reach 65-90%, and the velocity of discharge with steel finishing train requires to reach 10-20 meter per second.Under moderate finite deformation amount and fair speed condition, less in the temperature reduction of finishing train with steel, guarantee the finishing temperature higher with steel, prevent separating out of carbide.
5) within the scope of 900-1100 ℃, complete after the final distortion of belt steel rolling, must fast belt steel temperature be down to 400-500 ℃ by water-cooled.Band steel speed of cooling is controlled at 30-60 ℃/s, prevents too much separating out of carbide, and through water-cooled fast, band steel conventional mechanical property can reach standard-required, meets processing and the working conditions of standard-required.
Cooling fast by the time that rolling completes, can omit the solution annealing process in the conventional high temperature steel technological process of production, reduce by a process procedure, can reduce production costs.
The technical process of high temperature steel of the present invention is: smelt---sheet billet continuous casting---heating of plate blank---hot strip rolling---cooling (band steel speed of cooling 30-60 ℃/s)---strip coiling---strip pickling---inspection----batch, pack fast.
Conventional high temperature steel technical process is: smelt---sheet billet continuous casting---heating of plate blank---hot strip rolling---strip coiling---continuous annealing of band steel, pickling---inspection----batch, pack.
Above-mentioned technical process of the present invention is obviously different from conventional heatproof zone steel production technique, has reduced band steel finished product annealing process link.
High quality steel of the present invention has following advantages: the high temperature steel trade mark of the present invention makes opposing high temperature oxidation resistance, the thermostrength of steel be improved (seeing Fig. 2) by adding silicon, molybdenum, nitrogen.Because band steel is by shrend chilling, the Carbide Precipitation of steel is inhibited, guarantee the conventional mechanical property of steel, meet the requirement of band steel processing conditions.Therefore cancel conventional heatproof zone Heat Treatment Of Steel operation, reduced production cost.In the situation that adding silicon, nitrogen and a small amount of molybdenum, the high-temperature oxidation resistance of steel is improved preferably (seeing Fig. 3).The control of sheet billet continuous casting technique, can avoid the generation of steel slab surface defect.
Embodiment
Below by embodiment and comparative example, the present invention is further detailed.
Conventional high temperature steel and high temperature steel composition of the present invention are in table 1.As can be seen from Table 1, high temperature steel trade mark noble metal content of the present invention is fewer than close standard brand, and the high-temperature behavior of steel is improved and conventional mechanical property meets standard-required.
The chemical composition of table 1 embodiment of the present invention steel, % by weight
| Sequence number | C | Si | Mn | P | S | Cr | Ni | Mo | | O | |
| 1 | 0.10 | 6.0 | 2.0 | 0.035 | 0.01 | 24.0 | 19.0 | 0.50 | 0.10 | 0.0050 | |
| 2 | 0.12 | 5.8 | 1.7 | 0.030 | 0.02 | 24.5 | 19.8 | 0.60 | 0.08 | 0.0048 | |
| 3 | 0.15 | 5.5 | 1.3 | 0.025 | 0.015 | 25.0 | 20.4 | 0.80 | 0.07 | 0.0046 | |
| 4 | 0.17 | 5.2 | 0.9 | 0.020 | 0.03 | 25.5 | 21.0 | 0.90 | 0.06 | 0.0042 | |
| 5 | 0.20 | 5.0 | 0.5 | 0.010 | 0.030 | 26.0 | 22.0 | 1.00 | 0.05 | 0.0040 | |
| 6 | 0.18 | 5.1 | 0.7 | 0.045 | 0.002 | 25.7 | 21.6 | 0.95 | 0.05 | 0.0040 | |
| 309S | 0.08 | 1.00 | 2.00 | 0.035 | 0.030 | 22-24 | 12-15 |
The processing condition of table 2 embodiment of the present invention steel
Test example 1: mechanical property
According to mechanical properties such as the yield strength of GB/T228 method mensuration embodiment of the present invention steel, tensile strength, unit elongation, measure the hardness of embodiment of the present invention steel according to GB/T230.1 method, it the results are shown in Table 3.
The mechanical property of table 3 embodiment of the present invention steel
| Sequence number | Yield strength, MPa | Tensile strength, MPa | Unit elongation A5, % | Hardness, HB |
| 1 | 600 | 750 | 55 | 180 |
| 2 | 635 | 755 | 53 | 177 |
| 3 | 624 | 760 | 52 | 182 |
| 4 | 641 | 773 | 56 | 169 |
| 5 | 650 | 780 | 50 | 185 |
Test example 2: the standard mechanical property of conventional thermal treatment process high temperature steel
According to mechanical properties such as the yield strength of GB/T228 method mensuration embodiment of the present invention steel, tensile strength, unit elongation, measure the hardness of embodiment of the present invention steel according to GB/T230.1 method, it the results are shown in Table 4.
The conventional thermal treatment process high temperature steel of table 4 standard mechanical property
| The trade mark | Yield strength, MPa | Tensile strength, MPa | Unit elongation A5, % | Hardness, HB |
| 310S | ≥205 | ≥515 | ≥40 | ≤217 |
| 310H | ≥205 | ≥515 | ≥40 | ≤217 |
| 309S | ≥205 | ≥515 | ≥40 | ≤217 |
| 309H | ≥205 | ≥515 | ≥40 | ≤217 |
Test example 3: hot strength
Fig. 1 is the hot strength variation with temperature curve of 310S steel, and touchstone is GB/T4338.
Fig. 2 is the hot strength variation with temperature curve of the embodiment of the present invention 2 steel.Other embodiment steel have also obtained similar result.
From Fig. 1 and Fig. 2, can find out hardness of steel of the present invention at 1000 ℃ higher than 310S, have good room temperature strength and hot strength.
The high temperature oxidation of steel of the present invention is less than 310S steel as can be seen from Figure 3, is better than 310S steel at same high temperature condition resistance to high temperature oxidation, can improve the high temperature life of steel.
As can be seen from the above results, the hot strength of high alloy austenitic heat-resistance steel of the present invention and high temperature life are improved.
Produce at present heatproof zone steel both at home and abroad and all adopt the standard analysis trade mark, have improved high temperature steel to add more noble metal alloy element, as W, Ni, Mo etc., and make manufacture method complicated.Metallurgical cost and tooling cost are improved.And adopt high temperature steel composition of the present invention only take ordinary silicon, nitrogen alloying as main, and be accompanied by less molybdenum alloy element, the hot strength of high temperature steel and high temperature life are improved.In addition, due to by the control of process for cooling, save heat treatment step, reduced production cost, met service requirements.
Claims (11)
1. austenitic heat-resistance steel, its mass percent chemical composition is: C:0.10-0.20%, Si:5.00-6.00%, Mn:0.50-2.00%, Cr:24.0-26.0%, P≤0.045%, S≤0.035%, Ni:19.0-22.00%, Mo:0.50-1.00%, [N]: 0.050-0.10%, [O]≤0.005%, all the other are iron and inevitable impurity;
Described steel is by the method manufacture that comprises following steps:
Cast:
Superheating temperature Δ T is 20-40 ℃, and molten steel casting temperature T=TL+ Δ T, in formula: TL-liquidus temperature, Δ T-molten steel overheat;
In cast, the temperature of cooling water of crystallizer remains on 35-45 ℃; The speed control of cast slab is at 0.5-1.1m/min;
Rolling:
According to slab thickness, the slab time inside furnace of cast is not less than 1.2 minutes/mm, and slab tapping temperature is 1230-1265 ℃;
At 900-1250 ℃ of rolling deformation, total deformation is 65-90%; Then with the speed of cooling of 30-60 ℃/s, band steel is cooled to 400-500 ℃.
2. austenitic heat-resistance steel as claimed in claim 1, is characterized in that, C:0.140-0.160%.
3. austenitic heat-resistance steel as claimed in claim 1 or 2, is characterized in that, Mn:0.80-1.60%.
4. austenitic heat-resistance steel as claimed in claim 1 or 2, is characterized in that, P≤0.035%.
5. austenitic heat-resistance steel as claimed in claim 1 or 2, is characterized in that, P:0.010-0.030%.
6. austenitic heat-resistance steel as claimed in claim 1 or 2, is characterized in that, S≤0.030%.
7. austenitic heat-resistance steel as claimed in claim 1, is characterized in that, the slab time inside furnace of cast is 1.2-1.5 minute/mm.
8. austenitic heat-resistance steel as claimed in claim 1, is characterized in that, finishing temperature is 900-1100 ℃.
9. austenitic heat-resistance steel as claimed in claim 1, is characterized in that, the band steel of rolling is cooling fast by water-cooled.
10. austenitic heat-resistance steel as claimed in claim 1, is characterized in that, the cross dimensions of continuous casting steel billet is controlled at (150～300) × (750～2100) mm.
11. austenitic heat-resistance steels as claimed in claim 1, is characterized in that, the velocity of discharge with steel finishing train is 10-20 meter per second.
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| JP6856083B2 (en) * | 2018-03-02 | 2021-04-07 | Ｊｆｅスチール株式会社 | High Mn steel and its manufacturing method |
| CN110850915A (en) * | 2018-08-21 | 2020-02-28 | 上海梅山钢铁股份有限公司 | Self-learning-based steelmaking molten steel process temperature control system and control method |
| CN115948688A (en) * | 2023-01-29 | 2023-04-11 | 共享铸钢有限公司 | Component control method of austenitic heat-resistant steel casting |
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| CN101708537A (en) * | 2009-11-28 | 2010-05-19 | 山西太钢不锈钢股份有限公司 | Austenitic heat-resistant stainless steel continuous casting method |
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| JP4233628B2 (en) * | 1998-03-31 | 2009-03-04 | 新日鐵住金ステンレス株式会社 | Austenitic stainless steel for hydrogen generator with excellent scale peeling resistance |
| JP4454777B2 (en) * | 2000-03-29 | 2010-04-21 | 日新製鋼株式会社 | Hydrophilic austenitic stainless steel |
| SE0101602A0 (en) * | 2001-05-07 | 2002-11-08 | Alfa Laval Corp Ab | Material for coating and product coated with the material |
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| CN101708537A (en) * | 2009-11-28 | 2010-05-19 | 山西太钢不锈钢股份有限公司 | Austenitic heat-resistant stainless steel continuous casting method |
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