CN101532110B - Method for removing Delta ferrite from high strength and toughness martensitic stainless steel - Google Patents
Method for removing Delta ferrite from high strength and toughness martensitic stainless steel Download PDFInfo
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- CN101532110B CN101532110B CN2008100132310A CN200810013231A CN101532110B CN 101532110 B CN101532110 B CN 101532110B CN 2008100132310 A CN2008100132310 A CN 2008100132310A CN 200810013231 A CN200810013231 A CN 200810013231A CN 101532110 B CN101532110 B CN 101532110B
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011651 chromium Substances 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 15
- 238000005275 alloying Methods 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004576 sand Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The invention relates to the field of metallic material, specially a method for removing Delta ferrite from high strength and toughness martensitic stainless steel, and particularly relates to a composition design and phase control method for materials used for casting martensitic stainless steel. By controlling the ratio of nickel equivalent to chromium equivalent in martensitic stainless steelsof 0Cr13Ni4 to 6Mo as well as cooling velocity in casting high temperature stage, the invention removes the Delta ferrite completely. The method comprises the following steps of 1) calculating nickelequivalent and chromium equivalent according to that nickel equivalent (Ni eq)=Ni+30(C+N)+0.5Mn and chromium equivalent (Cr eq)=Cr+Mo+1.5Si when carrying out alloying composition design to high strength and toughness martensitic stainless steels of 0Cr13Ni4 to 6Mo; 2) controlling the ratio of nickel equivalent to chromium equivalent being more than or equal to 0.42; and 3) controlling the averagecooling velocity of the casting being smaller than 500 DEG C/h between solidus curve and 1300 DEG C. By controlling the alloying composition design and casting cooling velocity, the invention removesthe Delta ferrite phase which severely worsens the performances of the high strength and toughness martensitic stainless steels of 0Cr13Ni4 to 6Mo, and remarkably improves the strength as well as plasticity and toughness of the casting.
Description
Technical field
The present invention relates to metal material field, be specially a kind of method of eliminating delta ferrite in the high strength and toughness martensitic stainless steel, especially relate to the composition design and the phase control method of class casting martensite stainless steel material.
Background technology
0Cr13Ni4～6Mo type Martensite Stainless Steel has good castibility, large section homogeneity and weldability, and the circle is described as " the successful steel grade that casting person dreams of " in casting.Because have excellent normal temperature and cryogenic mechanics performance, fatigue property, welding technological properties and anti-cavitation corrosion polishing machine under water, casting high strength and toughness martensitic stainless steel (0Cr13Ni4～6Mo type) is widely used on the parts such as power station flow passage components, water pump, compressor impeller, atomic power station foundry goods and pressurized vessel.In China along with of the large-scale and huge unit development of water wheels unit to high-power, high water head, performance requriements to 0Cr13Ni4～6Mo section bar material is also more and more higher, when improving requirement of strength, also plasticity and toughness are also had higher requirement, therefore rationally the microtexture of control 0Cr13Ni4～6Mo type Martensite Stainless Steel more and more obtains the attention of each manufacturer.
If can not reasonably control the speed of cooling of the content and the castingprocesses of various alloying elements, be prone to the delta ferrite phase that not exclusively remains to room temperature owing to Peritectic Reaction in the type steel grade, see accompanying drawing 1.While is higher owing to delta ferrite generates temperature mutually, and the conventional heat treating method after casting is finished can't be eliminated it, can only retain to service state.Delta ferrite belongs to softening phase, often is distributed in original austenite crystal prevention, being stretched, often becoming the position that crackle at first germinates when impact and cavitation corrosion, sees accompanying drawing 2.Because its crack arrest characteristic is poor, after crackle produces, can expand along delta ferrite again, intensity, plasticity, toughness and the anti-cavitation corrosion performance of material are seriously descended, reduce the use properties and the work-ing life of material, directly influence reliability and security in big-and-middle-sized rotary wheel of water turbine manufacturing and the operational process.Along with of the raising of large-sized water turbine unit design and use condition to material requirements, eliminate the delta ferrite phase in 0Cr13Ni4～6Mo type Martensite Stainless Steel, improve the material over-all properties and seem particularly important.
Summary of the invention
The object of the present invention is to provide the method that easily has the problem of delta ferrite in a kind of 0Cr13Ni4 of overcoming～6Mo type Martensite Stainless Steel, solved the problem that is difficult to control and eliminate delta ferrite in the actual production process; Adopt the method for alloy designs and the dual control of casting cooling rate, do not increase any production process and cost.
The technical solution used in the present invention is:
A kind of method of eliminating delta ferrite in the high strength and toughness martensitic stainless steel is eliminated delta ferrite fully by nickel equivalent in control 0Cr13Ni4～6Mo type Martensite Stainless Steel and the chromium equivalent speed of cooling realization of foundry goods hot stage when.
1) the austenizer content in the alloying element is represented with nickel equivalent that ferritisey content is represented with chromium equivalent, nickel equivalent (Ni
Eq) and chromium equivalent (Cr
Eq) method of calculation as follows:
Ni
eq＝Ni+30(C+N)+0.5Mn；
Cr
eq＝Cr+Mo+1.5Si；
More than each element all calculate by the quality percentage composition.
2) control Ni
Eq/ Cr
Eq〉=0.42 (being generally 0.42～0.65);
3) when cast, by adjusting teeming temperature, mold material, rising head size and lagging material etc., average cooling rate≤500 of control foundry goods between material solidus curve and 1300 ℃ ℃/h (lower limit of speed of cooling can be unrestricted).
The chemical ingredients of 0Cr13Ni4～6Mo type Martensite Stainless Steel is (a quality percentage composition): C≤0.06, and Si≤1.00, Mn≤1.00, Cr 11.5～14.0, and Ni 3.5～6.0, and Mo 0.40～1.00, N≤0.02, S≤0.03, P≤0.04, Fe surplus.
It is as follows that the present invention eliminates in the high strength and toughness martensitic stainless steel mechanism of delta ferrite:
In the type stainless steel, nickel, carbon, nitrogen and manganese belong to ferritisey, promote ferritic formation and stable, enlarge high temperature delta ferrite phase region; Chromium, molybdenum and silicon belong to austenizer, promote austenitic formation and stable, enlarge the austenite phase region.The present invention promotes the different of ferrite and austenitizing ability according to each element, and different weighting factors is set, and is nickel equivalent and chromium equivalent with its difference equivalence.Come Comprehensive Control ferritisey content and austenizer content by control nickel equivalent/chromium equivalent, make the type material in the equilibrium state phasor, can eliminate delta ferrite fully.Simultaneously, because the hot stage delta ferrite is influenced by speed of cooling to the Peritectic Reaction L+ of austenitic transformation δ → γ bigger, too fast cooling rate will make Peritectic Reaction incomplete, so must limit in the speed of cooling between solidus temperature and 1300 ℃ material, this reaction can be carried out under the approximate equilibrium state.
The present invention has following beneficial effect:
1. the present invention is under the prerequisite that does not increase production process and cost, composition proportion by control material and castingprocesses cooling rate realize controlling accurately, easily with eliminate 0Cr13Ni4～6Mo type Martensite Stainless Steel in harmful delta ferrite mutually, improved comprehensive mechanical performance.
2. application of the present invention can solve the problem of the long-term puzzlement domestic water merchant of power plant to 0Cr13Ni4～6Mo type Martensite Stainless Steel organizational controls difficulty, lay the first stone for realizing that the large-sized water turbine unit domesticizes, and then solve the situation of Chinese large-sized water turbine assembly dependence on import.
3. application of the present invention can promote the over-all properties of material, satisfy of the harsh requirement of large-sized water turbine unit to material mechanical performance, according to national hydroelectric development planning, calculate by 4,500 ten thousand yuan of costs of every 700MW level water wheels unit, the year two thousand twenty can have tens yuan benefit in the past.
Description of drawings
Fig. 1 contains the ZG06Cr13Ni4Mo metallographic structure of delta ferrite, and brilliant white wherein is organized as delta ferrite.
Crackle was along containing delta ferrite germinating and expansion when Fig. 2 impacted.
The metallograph of Fig. 3 embodiments of the invention one.
The metallograph of Fig. 4 embodiments of the invention two.
The metallograph of Fig. 5 embodiments of the invention three.
The metallograph of Fig. 6 embodiments of the invention four.
Embodiment
Embodiment one
Design the chemical ingredients (quality percentage composition) of ZG04Cr13Ni4Mo according to the present invention: C 0.028%, Si 0.44%, Mn 0.77%, Cr 12.07%, Ni 4.14%, Mo 0.52%, N 0.008%, S 0.005%, P 0.017%, Fe surplus.Adopt phenolic sand molding, 1550 ℃ of teeming temperatures, test block size 70 * 150 * 200mm, attached casting is on massive casting.
Calculate Ni
Eq=Ni+30 (C+N)+0.5Mn=5.605%;
Cr
eq＝Cr+Mo+1.5Si＝13.25％；
Ni
eq/Cr
eq＝0.423＞0.42；
Because of its attached casting on the bigger massive casting of thermal capacitance, so its speed of cooling is far below unidimensional independent foundry goods.Through measuring, test block foundry goods average cooling rate between solidus curve to 1300 ℃ is 300 ℃/h.
The typical gold phase constitution does not contain delta ferrite as shown in Figure 3.
Embodiment two
Design the chemical ingredients (quality percentage composition) of ZG06Cr13Ni4Mo according to the present invention: C 0.038%, Si 0.30%, Mn 0.52%, Cr 12.54%, Ni 3.85%, Mo 0.44%, N 0.015%, S 0.005%, P 0.025%, Fe surplus.Adopt phenolic sand molding, 1570 ℃ of teeming temperatures, test block size 200 * 200 * 200mm, the test block top is provided with insulated feeder.
Calculate Ni
Eq=Ni+30 (C+N)+0.5Mn=5.70%;
Cr
eq＝Cr+Mo+1.5Si＝13.43％；
Ni
eq/Cr
eq＝0.424＞0.42；
By improving teeming temperature, the insulated feeder that φ 140 * 100mm is set is controlled the speed of cooling of foundry goods at hot stage, and through measuring, foundry goods speed of cooling between solidus curve to 1300 ℃ is 450 ℃/h.
The typical gold phase constitution does not contain delta ferrite as shown in Figure 4.
Embodiment three
Design the chemical ingredients (quality percentage composition) of ZG04Cr13Ni5Mo according to the present invention: C 0.02%, Si 0.44%, Mn 0.45%, Cr 11.80%, Ni 4.66%, Mo 0.43%, N 0.015%, S 0.007%, P 0.024%, Fe surplus.Adopt phenolic sand molding, chromite sand is applied on the surface, 1550 ℃ of teeming temperatures, and test block size 100 * 100 * 150mm, attached casting is on massive casting.
Calculate Ni
Eq=Ni+30 (C+N)+0.5Mn=5.935%;
Cr
eq＝Cr+Mo+1.5Si＝12.89％；
Ni
eq/Cr
eq＝0.460＞0.42；
Because of its attached casting on the bigger massive casting of thermal capacitance, though adopt chromite sand to do facing sand, its speed of cooling is far below unidimensional independent foundry goods.Through measuring, foundry goods speed of cooling between solidus curve to 1300 ℃ is 200 ℃/h.
The typical gold phase constitution does not contain delta ferrite as shown in Figure 5.
Embodiment four
Design according to the present invention in the chemical ingredients of ZG06Cr13Ni5Mo and contain (quality percentage composition): C0.034%, Si 0.48%, Mn 0.79%, Cr 12.52%, Ni 4.50%, Mo 0.56%, N 0.01%, S 0.009%, P 0.019%, Fe surplus.Adopt phenolic sand molding, 1550 ℃ of teeming temperatures, test block size 70 * 150 * 200mm, attached casting is on massive casting.
Calculate Ni
Eq=Ni+30 (C+N)+0.5Mn=6.215%;
Cr
eq＝Cr+Mo+1.5Si＝13.80％；
Ni
eq/Cr
eq＝0.450＞0.42；
Because of its attached casting on the bigger massive casting of thermal capacitance, so its speed of cooling is far below unidimensional independent foundry goods.Through measuring, speed of cooling is 300 ℃/h between the foundry goods solidus curve to 1300 ℃.
The typical gold phase constitution does not contain delta ferrite as shown in Figure 6.
Claims (1)
1. a method of eliminating delta ferrite in the high strength and toughness martensitic stainless steel is characterized in that: eliminate delta ferrite fully by nickel equivalent in control OCr13Ni4～6Mo type Martensite Stainless Steel and the chromium equivalent speed of cooling realization of foundry goods hot stage when;
Nickel equivalent Ni
Eq=Ni+30 (C+N)+0.5Mn, chromium equivalent Cr
Eq=Cr+Mo+1.5Si, each element calculates by the quality percentage composition;
Control nickel equivalent/chromium equivalent 〉=0.42;
Average cooling rate≤500 of control foundry goods between solidus curve to 1300 ℃ ℃/h.
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| CN101532110B true CN101532110B (en) | 2010-06-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103032330B (en) * | 2013-01-16 | 2016-01-20 | 东莞市金瑞五金制品有限公司 | A kind of compressor and application thereof |
| CN107245563A (en) * | 2017-07-10 | 2017-10-13 | 青岛大学 | It is a kind of to improve indissoluble delta ferrite solid solution speed in martensite type refractory steel ingot casting while the technology of fining austenite grains |
| CN109082608A (en) * | 2018-10-26 | 2018-12-25 | 成都先进金属材料产业技术研究院有限公司 | The method for controlling delta ferrite level in low straight-chromiun stainless steel |
| CN114959508B (en) * | 2022-07-28 | 2022-10-21 | 北京科技大学 | Stainless steel and preparation method thereof |
| CN115121918B (en) * | 2022-08-24 | 2022-12-13 | 中国科学院金属研究所 | Welding method for reducing content of delta-ferrite harmful phase in weld joint of martensite refractory steel with 12% of Cr in nuclear reactor core |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4047941A (en) * | 1974-09-23 | 1977-09-13 | Allegheny Ludlum Industries, Inc. | Duplex ferrit IC-martensitic stainless steel |
| EP0481377A2 (en) * | 1990-10-16 | 1992-04-22 | Nisshin Steel Co., Ltd. | Process for producing high-strength stainless steel strip |
| CN101070579A (en) * | 2002-07-15 | 2007-11-14 | 住友金属工业株式会社 | Martensitic stainless steel seamless pipe and a manufacturing method thereof |
-
2008
- 2008-09-17 CN CN2008100132310A patent/CN101532110B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4047941A (en) * | 1974-09-23 | 1977-09-13 | Allegheny Ludlum Industries, Inc. | Duplex ferrit IC-martensitic stainless steel |
| EP0481377A2 (en) * | 1990-10-16 | 1992-04-22 | Nisshin Steel Co., Ltd. | Process for producing high-strength stainless steel strip |
| CN101070579A (en) * | 2002-07-15 | 2007-11-14 | 住友金属工业株式会社 | Martensitic stainless steel seamless pipe and a manufacturing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JP昭63-149320A 1988.06.22 |
| 王淑霞.氮对0Cr13Ni4Mo马氏体不锈钢机械性能的影响.特殊钢22 5.2001,22(5),23-25. |
| 王淑霞.氮对0Cr13Ni4Mo马氏体不锈钢机械性能的影响.特殊钢22 5.2001,22(5),23-25. * |
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Effective date of registration: 20220822 Address after: 256218 west side of middle section of Xiwang Avenue, Xiwang Industrial Park, Zouping City, Binzhou City, Shandong Province Patentee after: Zhongke Xiwang Special Steel Co.,Ltd. Address before: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |