CN102260826A - High temperature resistant martensitic stainless steel and production method thereof - Google Patents
High temperature resistant martensitic stainless steel and production method thereof Download PDFInfo
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Abstract
The invention discloses a high temperature resistant martensitic stainless steel, comprising the following chemical components: 0.11-0.15 wt% of C, 0.50-0.80 wt% of Mn, no larger than 0.10 wt% of Si, 9.80-11.50 wt% of Cr, 0.60-0.80 wt% of Ni, 1.00-1.30 wt% of Mo, 0.13-0.23 wt% of V, no larger than 0.10 wt% of Al, 0.09-0.15 wt% of Nb, 0.25-0.40 wt% of W, 0.050-0.080 wt% of N, no larger than 0.010 wt% of P, no larger than 0.005 wt% of S, and the balance consisting of Fe and inevitable impurities. Accordingly, the invention further discloses a method for smelting with vacuum induction and electro slag remelting to produce the martensitic stainless steel. The produced martensitic stainless steel has low content of impurity elements, good quality of steel, excellent high temperature resistance, good combination of strength and toughness, and high yield.
Description
Technical field
The present invention relates to field of metallurgy, relate in particular to a kind of martensite steel grade and manufacture method thereof.
Background technology
Martensite Stainless Steel is the stainless steel that a class can be adjusted its performance by thermal treatment, and what amount ratio was bigger at present is Cr13 type Martensite Stainless Steel.This class stainless steel generally is used to make component such as blade, fastening piece, pump shaft, valve, bolt, but this class Martensite Stainless Steel can only use in the lower Working environment of temperature, and the general work temperature is below 300 ℃; In addition, this class Martensite Stainless Steel, not high to the content requirement of impurity element such as S, P and Si, Mn element in the chemical ingredients, similar stainless requirement with other is the same substantially.But there is too much impurity element in the steel, will increases the probability that occurs inclusion in the steel, reduce the internal soundness of steel, finally reduce the use properties of material.
Along with constant development of economy, the demand of making high-effect power station also constantly increases.High-effect power station is exactly by working temperature that improves material medium and a kind of novel power station that pressure improves efficiency of plant, and therefore this power station is also more and more higher in the requirement of the metallic substance in power station to being on active service.Martensite Stainless Steel with the Cr13 type is made the component such as blade that the power station is used, and can not satisfy the demand in present high-effect power station.Therefore, develop some high quality, resistant to elevated temperatures Martensite Stainless Steel for adapting to the demand in the high-effect power station of present construction, pressing for.This high temperature resistant Martensite Stainless Steel should satisfy in the Working environment more than 450 ℃ and uses.
Shown in the table 1 is a kind of high temperature resistant Martensite Stainless Steel, and its chemical element quality per distribution ratio is as shown in table 1:
Table 1 (wt%)
| Grade of steel | C | Mn | Si | Ni | Cr | Mo | V | Al | Nb | B | W | Co | N | S | P |
| 1Cr11Co3W3 NiMoVNbNB | 0.08 0.13 | 0.35 0.65 | ≤ 0.10 | 0.30 0.70 | 10.00 12.00 | 0.10 0.40 | 0.15 0.25 | ≤ 0.015 | 0.05 0.12 | 0.01 0.04 | 2.40 3.00 | 2.50 3.50 | 0.010 0.035 | ≤ 0.010 | ≤ 0.015 |
The martensite heat-resistance stainless steel of the trade mark shown in the table 1, manufacturing process is: vacuum induction cast Φ 520mm electrode bar → vacuum consumable remelting Φ 610mm ingot → forge cogging → precise forging machine soon to become a useful person.There is following problem in this steel grade when producing:
(1) owing to adopted the two vacuum technologies of vacuum induction+vacuum consumable to smelt its smelting cost height;
(2) adopt the vacuum consumable remelting processing to smelt, do not have the bits protection, surface of steel ingot is good not as the electroslag remelting steel ingot surface quality, forges excellent surface quality for improving, and the consumable ingot surface needs car light, causes metal loss big, has reduced lumber recovery;
(3) this steel requires control N element and Mn element, and these two kinds of elements are smelted under vacuum and are easy to volatilization, particularly N element, and recovery rate is very unstable under vacuum, and this content to these two kinds of elements of accurate control brings certain difficulty.And these two kinds of elements, the particularly height of N constituent content are bigger to the performance and the ferrite content influence of steel grade.
Except that the high temperature resistant Martensite Stainless Steel steel grade shown in the above-mentioned table 1, publication number is JP 5311347, a kind of heat-resisting Martensite Stainless Steel is disclosed in the Japanese documentation that open day is on November 22nd, 1993, do not contain strong carbide forming element W, Mo, V in this steel grade, it is by element and C element formation carbide such as Nb, N, reaches the stable on heating purpose of strengthening matrix and improving steel.Publication number is CN1891846, open day is on January 10th, 2007, name is called in the Chinese patent literature of " Martensite Stainless Steel " and discloses a kind of heat-resisting Martensite Stainless Steel, this steel grade is by element and C element formation carbide such as V, Nb, N, reach the resistance toheat of strengthening matrix and improving steel, but do not contain Ni element and carbon content height in this steel grade, so its toughness and corrosion resisting property are on the low side.
Summary of the invention
The purpose of this invention is to provide a kind of high temperature resistant Martensite Stainless Steel and manufacture method thereof, impurity content in this steel grade is low, and can be under the temperature environment more than 450 ℃ steady operation, can be used for the career field of having relatively high expectations to metallic substance in high-effect power station etc., make component such as blade, fastening piece, pump shaft, valve, bolt.
According to above-mentioned purpose of the present invention, a kind of high temperature resistant Martensite Stainless Steel is proposed, the quality percentage composition of its chemical element is: C 0.11～0.15%; Mn 0.50～0.80%; Si≤0.10%; Cr 9.80～11.50%; Ni 0.60～0.80%; Mo 1.00～1.30%; V 0.13～0.23%; Al≤0.010%; Nb 0.09～0.15%; W 0.25～0.40%; N 0.050～0.080%; P≤0.010%; S≤0.005%; Surplus is Fe and other unavoidable impurities.
The principle of design of steel grade of the present invention is as follows:
The C element is an austenite former, and for guaranteeing to produce martensitic transformation, the C constituent content is generally decided on the Cr constituent content in the steel.Usually C content increases, and the Cr constituent content can correspondingly increase.In Martensite Stainless Steel, along with the increase of C constituent content, the intensity and the hardness of steel improve thereupon, and solidity to corrosion descends and flexible descends but also be accompanied by simultaneously.Therefore in order to guarantee the intensity of steel grade, steel grade of the present invention is controlled a certain amount of C element, also helps reducing ferritic content in the steel.
The Cr element is a ferrite former.In Martensite Stainless Steel, Cr constituent content height, ferritic content increases in the steel, and ferrite content increases, and will reduce the homogeneity of steel performance.But Cr constituent content height can improve the corrosion resisting property of steel.Therefore, the Cr constituent content is controlled between 9.80～11.5% among comprehensive consideration the present invention.
In Martensite Stainless Steel, C and N are effective elements.The effect of N and C element is similar, and the N element also can enlarge the austenite phase region.In the steel grade of the present invention, the N constituent content is higher than existing 1Cr11Co3W3NiMoVNbNB steel, and design helps reducing ferrite content in the steel like this, improves the intensity of steel grade, improves the vertical, horizontal performance difference, improves forgeability.
The Mo element is a ferrite former.The Mo element can increase temper resistance and secondary hardening effect in Martensite Stainless Steel, increase the intensity of steel simultaneously, and toughness does not reduce.This helps improving the high temperature resistant use properties of steel concerning the steel that contains the Mo element.In the steel grade of the present invention, the Mo constituent content is higher than existing 1Cr11Co3W3NiMoVNbNB steel, and She Ji purpose is to improve the high temperature resistant use properties of steel grade like this.
W is a ferrite former, and it also is the strong carbide forming element simultaneously.The W element can increase the high temperature resistant property that temper resistance improves steel in Martensite Stainless Steel.But W content height makes easily that ferrite content increases in the steel, and distribution of carbides is inhomogeneous, and these all will influence the homogeneity of steel performance.Therefore among the present invention the W constituent content is controlled between 0.25～0.40%.
The Si element is controlled at≤when 1.00% scope is interior, does not influence the tissue of Martensite Stainless Steel is obvious.Al element and Si element all exist as deoxidant element in Martensite Stainless Steel.The Si element and the Al element that contain appropriate amount, purpose are to guarantee that the deoxidation effect of steel is good.But in order to obtain high-quality Martensite Stainless Steel, be mingled with in the minimizing steel, the content of strict control Si, Al, P and S element among the present invention to improve the purity of steel, improves every performance of steel.
Correspondingly, the present invention has also passed through the manufacture method of described high temperature resistant Martensite Stainless Steel, and it comprises the steps:
(1) technology of employing vacuum induction furnace smelting casting+electroslag furnace remelting is smelted into steel ingot with raw material, and control each chemical element quality percentage composition and be: C 0.11～0.15%; Mn 0.50～0.80%; Si≤0.10%; Cr 9.80～11.50%; Ni 0.60～0.80%; Mo 1.00～1.30%; V 0.13～0.23%; Al≤0.010%; Nb 0.09～0.15%; W 0.25～0.40%; N 0.050～0.080%; P≤0.010%; S≤0.005%; Surplus is Fe and other unavoidable impurities; Wherein when carrying out esr, be coated with aluminium powder, adopt rare gas element to do protection gas on the electrode bar surface with electroslag furnace.
Being coated with aluminium powder in this step on the electrode bar surface and adopting rare gas element to do protection gas is in order to prevent to take place in the esr process scaling loss of Nb element.
(2) steel ingot annealing: will anneal 680～720 ℃ of annealing temperatures, soaking time 20～30h, air cooling then behind steel ingot cover cold (steel ingot is covered in the cooling cowl, play slow refrigerative effect) 50～65h.
(3) forge: steel ingot is forged cogging soon become steel billet, then steel billet is carried out finish forge, to forge temperature be 1100～1160 ℃ to wherein fast opening of forging, and finishing temperature is 900～1000 ℃, and it is 1050～1140 ℃ that the opening of finish forge forged temperature, and finishing temperature is 900～950 ℃.This finishing temperature has guaranteed that the steel shaping does not exceed the optimal heat plastic zone, thereby has avoided forging crack.
(4) annealing billet: anneal through behind the steel billet air cooling 8～14h of finish forge above-mentioned, annealing temperature is 680～720 ℃, soaking time 45～60h, air cooling then.Because Martensite Stainless Steel is relatively more responsive to crackle, therefore must adopt suitably reasonably annealing process.The purpose of carrying out the air cooling of for some time before annealing is that the internal and external temperature unanimity of assurance steel guarantees that also austenite is transformed into martensite fully simultaneously.Anneal if forge the back, also residual in the steel have a not austenite of transformation, and the austenite and the martensite coefficient of expansion are different will to produce internal stress, and when this internal stress was higher than the yield strength of steel, crackle will appear in steel inside at once.
Preferably, in order to prevent that steel ingot from producing crack due to thermal stress in fast forging process, the weave construction that guarantees steel simultaneously is even, when steel ingot is forged soon in the step of manufacturing of described high temperature resistant Martensite Stainless Steel (3), earlier steel ingot is heated to 600～750 ℃, insulation 1～2h, the heat-up rate with 45～50 ℃/h is warmed up to 1170～1190 ℃ then, insulation 3～5h forges soon again.
Preferably, for the mechanical property that guarantees that surface quality of steel and steel are final, in the manufacture method step (3) of described high temperature resistant Martensite Stainless Steel during finish forge, earlier steel billet is heated to 600～750 ℃, insulation 0.5～1h, heat-up rate with 70～80 ℃/h is warmed up to 1150～1170 ℃ then, and insulation 2～3h carries out finish forge again.
The present invention makes it compared with prior art to have the following advantages owing to adopted above technical scheme:
1. steel grade of the present invention is compared with existing steel grade 1Cr11Co3W3NiMoVNbNB, does not contain the Co element, has reduced the content of W element, thereby greatly reduces raw-material cost; Though do not contain the Co element and reduced the content of W element, steel grade of the present invention designs by reasonable component, has guaranteed the resistance to elevated temperatures of steel equally; In addition, by improving the content of N element, this steel grade does not cause the reduction of plasticity when improving intensity.
2. steel grade of the present invention adopts vacuum induction+electroslag remelting process to smelt, and adopts the two vacuum technologies of vacuum induction+vacuum consumable to smelt than existing steel grade, and the electroslag smelting expense is relatively low.In addition, vacuum induction+electroslag remelting process can guarantee that the content of N element is controlled in the described scope of the technical program, and difficulty reaches this index to adopt the two vacuum technologies of vacuum induction+vacuum consumable to smelt then.Because smelt under the vacuum, the recovery rate of N element is very low, and unstable, finally can influence the performance of material.
3. adopt vacuum induction+electroslag remelting process of the present invention to smelt, the Ingot Surface Quality that obtains is good, and simultaneously than existing production technology, this method can reduce production costs and production cycle, and reduces the loss of steel, improves the lumber recovery of steel.
Description of drawings
Fig. 1 is the process curve of steel ingot heating in the high temperature resistant Martensite Stainless Steel manufacture method of the present invention.
Fig. 2 is the process curve of steel billet heating in the high temperature resistant Martensite Stainless Steel manufacture method of the present invention.
Embodiment
Embodiment 1-5
Produce high temperature resistant Martensite Stainless Steel according to the following step:
(1) chromium metal that selected purity is good, chromium nitride, metal niobium or ferro-niobium, furnace charges such as metal molybdenum or molybdenum-iron, tungsten or ferrotungsten and alum iron, select for use the low starting material of impurity content to insert in the vacuum induction furnace simultaneously, the content of impurity element is controlled to minimum the smelting as far as possible, smelt the electrode bar N elemental composition of casting and enter the control specification, in cast forward direction stove, arrive 333mbar towards Ar for guaranteeing vacuum induction, and then add nitrided ferro-chromium, improve the recovery rate of N element.When carrying out esr, for preventing the scaling loss of Nb element, evenly be coated with aluminium powder on electrode bar, electrode bar Nb element quality percentage composition is by the super Nb element upper limit (the super upper limit 0.01～0.03%) control, and it is as shown in table 2 finally to control each chemical element quality percentage composition.The slag system that adopts in this step is CaF
2: Al
2O
3: MgO=65: 30: 5, the slag system quality was 130KG.The average molten speed of esr is pressed 6.6kg/min control.
Each chemical element quality per distribution ratio among the table 2. embodiment 1-5
(surplus is Fe and other unavoidable impurities)
| |
|
|
Embodiment 4 | Embodiment 5 | |
| C | 0.14 | 0.13 | 0.12 | 0.11 | 0.13 |
| Mn | 0.50 | 0.56 | 0.65 | 0.60 | 0.70 |
| Si | 0.09 | 0.06 | 0.05 | 0.04 | 0.07 |
| Ni | 0.69 | 0.65 | 0.75 | 0.78 | 0.72 |
| Cr | 10.00 | 10.23 | 10.50 | 11.2 | 10.45 |
| Mo | 1.15 | 1.25 | 1.08 | 1.20 | 1.27 |
| V | 0.14 | 0.16 | 0.15 | 0.17 | 0.20 |
| Nb | 0.14 | 0.12 | 0.13 | 0.11 | 0.10 |
| W | 0.34 | 0.29 | 0.36 | 0.38 | 0.37 |
| N | 0.061 | 0.055 | 0.070 | 0.076 | 0.065 |
| Al | 0.004 | 0.008 | 0.006 | 0.005 | 0.004 |
| S | 0.002 | 0.003 | 0.004 | 0.002 | 0.0015 |
| P | 0.007 | 0.006 | 0.005 | 0.004 | 0.005 |
(2) steel ingot annealing: behind the cold 50～65h of steel ingot cover, anneal 680～720 ℃ of annealing temperatures, soaking time 20～30h, air cooling then.Concrete processing parameter among the embodiment 1-5 sees Table 5.
(3) forge: steel ingot is forged cogging soon become steel billet, as shown in Figure 1, earlier steel ingot is heated to 600～750 ℃ (preheating temperatures) during fast the forging, insulation 1～2h, heat-up rate with 45～50 ℃/h is warmed up to 1170～1190 ℃ then, insulation 3～5h, the fast start rolling temperature of forging of control is 1100～1160 ℃ then, finishing temperature is 900～1000 ℃ and forges soon.To carry out finish forge through the steel billet of too fast forging then, as shown in Figure 2 during finish forge, earlier steel billet is heated to 600～750 ℃, insulation 0.5～1h, heat-up rate with 70～80 ℃/h is warmed up to 1150～1170 ℃ then, insulation 2～3h, the start rolling temperature of controlling finish forge then is 1050～1140 ℃, finishing temperature is 900～950 ℃ and carries out finish forge.Concrete processing parameter among the embodiment 1-5 sees Table 3 and table 4.
(4) annealing billet: anneal through behind the steel billet air cooling 8～14h of finish forge above-mentioned, annealing temperature is 680～720 ℃, soaking time 45～60h, air cooling then.Concrete processing parameter among the embodiment 1-5 sees Table 5.
The fast processing parameter of forging of steel ingot among the watch 3. embodiment 1-5
| Embodiment | The steel ingot preheating temperature (℃) | Steel ingot preheating temperature soaking time (h) | The steel ingot heat-up rate (℃/h) | Steel ingot intensification final temperature (℃) | Steel ingot soaking time (h) | Steel ingot open forge temperature (℃) | The steel ingot final forging temperature (℃) |
| 1 | 650 | 1 | 45 | 1175 | 3.0 | 1120 | 940 |
| 2 | 700 | 1.2 | 50 | 1185 | 3.8 | 1100 | 950 |
| 3 | 600 | 1.5 | 45 | 1190 | 3.5 | 1150 | 970 |
| 4 | 730 | 1.7 | 50 | 1180 | 4.0 | 1140 | 960 |
| 5 | 750 | 2.0 | 45 | 1170 | 4.5 | 1130 | 920 |
The processing parameter of steel billet finish forge among the table 4. embodiment 1-5
| Embodiment | The steel billet preheating temperature (℃) | Steel billet preheating temperature soaking time (h) | The steel billet heat-up rate (℃/h) | Steel billet intensification final temperature (℃) | The steel billet heat insulating time (h) | Steel billet open forge temperature (℃) | The steel billet final forging temperature (℃) |
| 1 | 660 | 0.9 | 75 | 1150 | 2.5 | 1110 | 910 |
| 2 | 700 | 0.7 | 80 | 1170 | 2.8 | 1080 | 950 |
| 3 | 620 | 1.0 | 70 | 1160 | 2.4 | 1120 | 930 |
| 4 | 680 | 0.8 | 80 | 1155 | 3.0 | 1100 | 940 |
| 5 | 750 | 0.6 | 75 | 1165 | 2.0 | 1130 | 920 |
The processing parameter of steel ingot annealing and annealing billet among the table 5. embodiment 1-5
| Embodiment | Cooling time (h) before the steel ingot annealing | The steel ingot annealing temperature (℃) | Steel ingot annealing soaking time (h) | The annealing billet preincubation time (h) | The annealing billet temperature (℃) | Annealing billet soaking time (h) |
| 1 | 56 | 690 | 30 | 8 | 710 | 48 |
| 2 | 60 | 700 | 28 | 10 | 700 | 55 |
| 3 | 58 | 720 | 20 | 11 | 710 | 50 |
| 4 | 65 | 710 | 25 | 12 | 690 | 60 |
| 5 | 62 | 710 | 23 | 14 | 700 | 58 |
With manufactured finished steel among the embodiment 1-5 through 1100 ℃ of quenchings, oil cooling, after the processing of 700 ℃ of tempering (45 minutes), the mechanical property that records steel among each embodiment is as shown in table 6:
Table 6. mechanical property
As seen from the above table, steel grade intensity R of the present invention
mCan reach 1000Mpa, yield strength R
P 0.2Can reach 890Mpa, elongation A can reach 21%, and relative reduction in area Z can reach 66%, δ-ferrite content＜1%, and ballistic work Akv can reach 86J, and hardness can reach 313HB.This shows that steel grade of the present invention is the high-quality steel that a kind of hardness, toughness and intensity all can reach better index; And this steel grade under 660 ℃ high-temperature work environment, phenomenon of rupture do not occur more than the work 100h under the 245MPa stress, illustrate that this steel has the good temperature resistance energy.In addition, because this steel grade has adopted manufacture method of the present invention, it is than existing production method, and is as shown in table 7, has reduced to become to produce cost, has improved the lumber recovery of product, has the implementation result of marked improvement.
Table 7
| Smelting technology | The steel ingot state | The raw material input amount | Quantum of output | Lumber recovery | |
| Steel grade of the present invention | Vacuum induction+esr | Figuring of surface | 6 stoves/30 ton | 23.962 ton | 79.87％ |
| Existing steel grade | Vacuum induction+consumable remelting | Surface car light | 6 stoves/30 ton | 18.63 ton | 62.10％ |
Be noted that above enumerate only for specific embodiments of the invention, obviously the invention is not restricted to above embodiment, many similar variations are arranged thereupon.If those skilled in the art all should belong to protection scope of the present invention from all distortion that content disclosed by the invention directly derives or associates.
Claims (4)
1. a high temperature resistant Martensite Stainless Steel is characterized in that, the quality percentage composition of its chemical element is:
C 0.11～0.15％
Mn 0.50～0.80％
Si ≤0.10％
Cr 9.80～11.50％
Ni 0.60～0.80％
Mo 1.00～1.30％
V 0.13～0.23％
Al ≤0.010％
Nb 0.09～0.15％
W 0.25～0.40％
N 0.050～0.080％
P ≤0.010％
S ≤0.005％
Surplus is Fe and other unavoidable impurities.
2. the manufacture method of a high temperature resistant Martensite Stainless Steel is characterized in that, comprises the steps:
(1) technology of employing vacuum induction furnace smelting casting+electroslag furnace remelting is smelted into steel ingot with raw material, and control each chemical element quality percentage composition and be: C 0.11～0.15%; Mn 0.50～0.80%; Si≤0.10%; Cr 9.80～11.50%; Ni 0.60～0.80%; Mo 1.00～1.30%; V 0.13～0.23%; Al≤0.010%; Nb 0.09～0.15%; W 0.25～0.40%; N 0.050～0.080%; P≤0.010%; S≤0.005%; Surplus is Fe and other unavoidable impurities; Wherein when carrying out esr, be coated with aluminium powder, adopt rare gas element to do protection gas on the electrode bar surface with electroslag furnace;
(2) steel ingot annealing: will anneal 680～720 ℃ of annealing temperatures, insulation 20～30h, air cooling then behind the cold 50～65h of steel ingot cover;
(3) forge: steel ingot is forged cogging soon become steel billet, then steel billet is carried out finish forge, the wherein fast start rolling temperature of forging is 1100～1160 ℃, and finishing temperature is 900～1000 ℃, and the start rolling temperature of finish forge is 1050～1140 ℃, and finishing temperature is 900～950 ℃;
(4) annealing billet: anneal through behind the steel billet air cooling 8～14h of finish forge above-mentioned, annealing temperature is 680～720 ℃, insulation 45～60h, air cooling then.
3. the manufacture method of high temperature resistant Martensite Stainless Steel as claimed in claim 2, it is characterized in that, when steel ingot is forged soon in the step (3), earlier steel ingot is heated to 600～750 ℃, insulation 1～2h, heat-up rate with 45～50 ℃/h is warmed up to 1170～1190 ℃ then, and insulation 3～5h forges soon again.
4. the manufacture method of high temperature resistant Martensite Stainless Steel as claimed in claim 3, it is characterized in that, in the step (3) during finish forge, earlier steel billet is heated to 600～750 ℃, insulation 0.5～1h, heat-up rate with 70～80 ℃/h is warmed up to 1150～1170 ℃ then, and insulation 2～3h carries out finish forge again.
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| CN110358983A (en) * | 2019-07-04 | 2019-10-22 | 中国科学院金属研究所 | A kind of precipitation hardening of martensitic stainless steel and preparation method thereof |
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| CN110835674A (en) * | 2019-10-14 | 2020-02-25 | 攀钢集团江油长城特殊钢有限公司 | Forging method of tungsten-containing high-chromium martensitic stainless steel |
| US11220733B1 (en) | 2020-08-31 | 2022-01-11 | University Of Science And Technology Beijing | Low carbon martensitic high temperature strength steel and preparation method thereof |
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| CN112501490A (en) * | 2020-11-13 | 2021-03-16 | 中国原子能科学研究院 | Method for manufacturing low-silicon high-nitrogen ferrite/martensite steel billet |
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