CN105779901A - High-strength stainless steel for deep sea cryogenic engineering and manufacturing method of steel - Google Patents
High-strength stainless steel for deep sea cryogenic engineering and manufacturing method of steel Download PDFInfo
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- CN105779901A CN105779901A CN201610141371.0A CN201610141371A CN105779901A CN 105779901 A CN105779901 A CN 105779901A CN 201610141371 A CN201610141371 A CN 201610141371A CN 105779901 A CN105779901 A CN 105779901A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses high-strength stainless steel for deep sea cryogenic engineering and a manufacturing method of the steel, and belongs to the technical field of stainless steel. Chemical components of the stainless steel comprise, by weight percent, smaller than 0.05% of C, 12.2% to 13% of Cr, 8.0% to 8.5% of Ni, 2.1% to 2.5% of Mo, smaller than 0.3% of Al, smaller than 0.0015% of N, smaller than 0.1% of Si, smaller than 0.01% of Mn, smaller than 0.005% of P, smaller than 0.001% of S and the balance Fe and inevitable impurities. The manufacturing method comprises the steps that a vacuum induction furnace and consumable electrode vacuum furnace dual smelting technology is adopted, and after smelting, a steel ingot is subject to annealing, cogging, forging or rolling to form the steel. The steel and the method have the beneficial effects that after heat treatment is carried out, and the steel has the excellent strength and toughness matching performance and excellent salt-fog resistance performance, and is suitable for structural parts, fasteners and the like of deep sea drilling exploitation or fishing equipment.
Description
Technical field
The invention belongs to rustless steel technical field, in particular, provide a kind of deep sea low temperature engineering high-strength stainless steel and manufacture method thereof, it is adaptable to the structural member of deep-sea drilling or marine salvage equipment and securing member etc..
Background technology
Deep-sea is richly stored with petroleum resources, mineral resources and living resources, is the grand strategy target of various countries' contention commanding heights of economy.A lot of countries are all controlling and occupy the measure of these resources to list national development plan in, to robbing the right of possession corporeal right of " blue public soil ".
Due to abyssal environment complexity harsh (low temperature, high-temperature hot liquid zone, high pressure, extreme microorganism corrosion etc.), thus the comprehensive mechanical property and decay resistance to military service material proposes requirements at the higher level.At present compared to developed countries, China's marine resources development technology, scientific research are in for a long time and relatively fall behind level, international deep-sea resources fight has lost first chance, maximum of which technical bottleneck is the research and development problem of deep sea equipment supplementary material, for deep-sea oil gas drilling, the current domestic helicoid hydraulic motor life-span is only 80 hours, and the drill collar life-span is only 200-500h, and bumper jar jarring number of times is only 100 times.Meanwhile, deep-sea fishing tool such as milling class fishing tool, more it is only 6h its average life, selected material all exposes serious problems in intensity, low-temperature flexibility, corrosion resistance etc., and this significantly constrains country's development and utilization at deep-sea resources.Thus it is a kind of suitable in the load material used under deep sea low temperature operating mode to be badly in need of development, to promote country's synthesized competitiveness in deep-sea resources exploitation.
Summary of the invention
The purpose of the present invention is by alloying component, smelting mode and supporting Design of Heat Treatment Process, produce a kind of novel high-strength stainless steel material suitable in deep sea low temperature engineering, to solve the selection bottleneck problem of current domestic deep-sea drilling or marine salvage equipment structural member and securing member.
The chemical composition of steel of the present invention is by weight percentage: C:< 0.05%, Cr:12.2～13%, Ni:8.0～8.5%, Mo:2.1～2.5%, Al:< 0.3%, N:< 0.0015%, Si:< 0.1%, Mn:< 0.01%, P:< 0.005%, S:< 0.001% surplus are Fe and inevitable impurity.
Based on above-mentioned alloying component proportioning, after heat treatment, invention steel has possessed the obdurability coupling of excellence and excellent salt spray corrosion resistance: reach 1200MPa in room temperature tensile intensity, yield strength reaches 1100MPa, elongation percentage is more than 19%, the contraction percentage of area is more than under the premise of 70%, and the room temperature summer of invention steel reaches more than 250J than V-type ballistic work, and-100 DEG C of ballistic works remain at more than 210J.Meanwhile, the detection method according to " GBT10125-2012 artificial atmosphere corrosion testing-salt spray test ", the salt spray resistance annual corrosion rate of invention steel also controls at below 0.1mm/a, has reached III grade of (anti-corrosion) standard of metal material corrosion resistance.
The effect of each element of the present invention and proportioning are according to as follows:
Carbon: carbon is as gap solid solution atom, though the matrix strength of steel can be improved, but can damage plasticity and toughness and the weldability of steel while intensity raises.Additionally, the existence of carbon can cause that matrix precipitates out Cr in ag(e)ing process in steel23C6Deng carbide, significantly reduce the sea water corrosion resistant of steel.Considering, the carbon of steel of the present invention controls within 0.05%.
Nitrogen: nitrogen is similar with the effect of carbon, on the one hand as gap solid solution atom, can damage plasticity and toughness and the weldability of steel while improving intensity.On the other hand, owing to containing the nitride forming elements such as aluminum in steel of the present invention, its meeting and nitrogen high temp form AlN field trash, significantly reduce the plasticity and toughness of steel, particularly low-temperature impact toughness.Additionally, AlN also can form spot corrosion source, reduce the pitting resistance of steel.Thus the requirement of nitrogen of steel of the present invention controls within 0.0015%.
Chromium: chromium is that steel of the present invention possesses corrosion proof most important alloying element, along with the rising of chromium content in steel, environmental corrosion resisting performance and antioxygenic property significantly improve, and there are some researches show that the chromium content lower limit causing corrosion resistance to suddenly change is about 12%.Additionally, the existence of chromium element can also improve resistance to tempering in steel, to keep dislocation strengthening and solution strengthening effect.Thus the chromium content range of steel of the present invention is 12.2～13%.
Nickel: nickel, as one of most important alloying element of steel of the present invention, mainly has two aspect effects: first nickel is as austenite former, it is possible to expand austenite phase field, reduces delta ferrite level in steel.Secondly when Ageing Treatment, nickel also can form γ '-Ni with aluminum in the base3The intermetallic hardening constituents such as Al and β-NiAl, significantly improve the intensity of steel.But too high nickel content can make the M of steelsPoint temperature significantly reduces, and causes residual austenite content in matrix to increase and reduces the intensity of steel.Considering, the nickel content range of steel of the present invention is 8.0～8.5%.
Molybdenum: molybdenum is remarkably improved the quenching degree of steel as ferrite former, in martensitic chromium nickel and stainless steel, molybdenum, except the corrosion resistance improving steel, can also form the Mo with hexagonal crystallographic texture in ag(e)ing process2C carbide, thus improving steel belt roof bolt stability and post-curing effect.But too high molybdenum content can promote the formation of delta ferrite, and steel band is come adverse effect.Considering, the molybdenum content of steel of the present invention is 2.1～2.5%.
Aluminum: aluminum is most important hardening constituent element in steel of the present invention, Ni tiny by forming disperse in ag(e)ing process on the one hand3The Precipitation phases such as Al and NiAl, play significant precipitation hardening effect.But then, too much Ni3Al and NiAl particle can cause that the impact flexibility of steel and corrosion resisting property significantly reduce.Considering, the aluminum content of steel of the present invention controls within 0.3%.
Silicon and manganese: silicon and manganese act primarily as deoxidation in steel, owing to simple metal material selected by steel of the present invention and adopts vacuum induction+vacuum consumable duplex smelting ultra-pure technique, thus be not required to add too much silicon and manganese deoxidation.Additionally, relatively low silicon and the Fe content corrosion resisting property to steel, particularly resistance to spot corrosion are highly beneficial with crevice corrosion behavior.To sum up considering, the silicon of steel of the present invention and manganese control respectively within 0.1% and 0.01%.
P and s: impurity element in steel, significantly reduce plasticity and toughness and welding performance, selecting simple metal material to smelt while adopting vacuum induction+vacuum consumable duplex smelting ultra-pure technique due to steel of the present invention, p and s content can control respectively within 0.005% and 0.001%.
The manufacture method of deep sea low temperature engineering high-strength stainless steel involved in the present invention is as follows:
(1) adopting vaccum sensitive stove+consumable electrode vacuum furnace two-link smelting process, raw material is simple metal material；The stress relief annealing that after smelting, steel ingot through 660～680 DEG C, need to be incubated 16～20 hours simultaneously；
(2) forging, rolling mill practice
Forge Heating temperature 1150～1200 DEG C, opens forging temperature 1050～1080 DEG C, final forging temperature 800～850 DEG C, and total forging ratio of becoming a useful person requires more than 10；
Rolling heating-up temperature 1050～1100 DEG C, start rolling temperature 1000～1020 DEG C, finishing temperature 850～900 DEG C.
(3) Technology for Heating Processing
Bar after thermoforming needs quenched+deep cooling+Ageing Treatment, and concrete technology is as follows:
Hardening heat is 920～950 DEG C, temperature retention time 1～2 hour, and air cooling or oil cooling are to room temperature；Cryogenic temperature is 0 DEG C, temperature retention time 1～2 hour, and air cooling is to room temperature；Aging temp is 450～520 DEG C, and temperature retention time is 4～6 hours, and air cooling is to room temperature.
It is an advantage of the current invention that:
Being coordinated with manufacturing process by the alloy system design innovated, steel of the present invention has been taken into account extremely excellent low-temperature flexibility while keeping higher room temperature strength and has been coordinated with corrosion resistance.Reaching 1200MPa in room temperature tensile intensity, yield strength reaches 1100MPa, and elongation percentage is more than 19%, and the contraction percentage of area is more than under the premise of 70%, and the room temperature summer of invention steel reaches more than 250J than V-type ballistic work, and-100 DEG C of ballistic works remain at more than 210J.Meanwhile, the detection method according to " GBT10125-2012 artificial atmosphere corrosion testing-salt spray test ", the salt spray resistance annual corrosion rate of invention steel also controls at below 0.1mm/a, has reached III grade of (anti-corrosion) standard of metal material corrosion resistance.May be directly applied to the structural member of deep-sea drilling or marine salvage equipment and securing member etc., it is possible to be applied to the association areas such as cryogenic engineering, there is wide market prospect.
Accompanying drawing explanation
The EBSD microstructure phenogram of Fig. 1 embodiment 3.
The transmission electron microscope bright field image of Fig. 2 embodiment 1, it is shown that martensite lath structure and morphology figure.
The transmission electron microscope bright field image of Fig. 3 embodiment 1, it is shown that adverse transformation austenite pattern and scattergram.
The transmission electron microscope bright field image of Fig. 4 embodiment 3, it is shown that nanoscale precipitated phase shape appearance figure.
Detailed description of the invention
The embodiment of the present invention is the prototype steel of three stove different aluminum content, and its chemical composition is as shown in table 1.Embodiment all adopts vaccum sensitive stove+consumable electrode vacuum furnace two-link smelting process, and after smelting, steel ingot is annealed, be rolled into Φ 30 bar after cogging.Table 2 gives three kinds of embodiments mechanics after 925 DEG C/1h oil cooling+0 DEG C/1h air cooling+450～520 DEG C/4h air cooling heat treatment and salt spray corrosion resistance.Visible, along with the gradually rising of aluminum content in embodiment composition, under same heat treating regime, the tension of steel and yield strength gradually rise, but salt spray corrosion resistance is gradually lowered.Thus consider, while meeting intensity rank requirement, the corrosion resisting property in order to ensure steel should reduce aluminum content in steel as far as possible.Additionally, inventor also measured weres embodiment 3, after 480 DEG C of Ageing Treatment, its result is as shown in table 3 than V-type ballistic work the series of temperatures summer of (in embodiment, intensity rank is the highest) sample.Associative list 2 is visible with table 3, and steel of the present invention shows that the intensity of excellence, plasticity and toughness coordinate with corrosion resistance.Reaching 1200MPa in room temperature tensile intensity, yield strength reaches 1100MPa, and elongation percentage is more than 19%, and the contraction percentage of area is more than under the premise of 70%, and the room temperature summer of invention steel reaches more than 250J than V-type ballistic work, and-100 DEG C of ballistic works remain at more than 210J.Meanwhile, the detection method according to " GBT10125-2012 artificial atmosphere corrosion testing-salt spray test ", the salt spray resistance annual corrosion rate of invention steel also controls at below 0.1mm/a, has reached III grade of (anti-corrosion) standard of metal material corrosion resistance.
Adopting EBSD technology that the embodiment 3 microstructure after 480 DEG C of Ageing Treatment is characterized, its result is as shown in Figure 1.The matrix of visible invention steel is the tempered martensite typically with lath pattern.Fig. 2 and Fig. 3 sets forth embodiment 1 after 480 DEG C of Ageing Treatment, the transmission electron microscope bright field image pattern of the tempered martensite of intrinsic silicon and adverse transformation austenite.Visible after aging strengthening model the dislocation density of martensite substantially reduce, but still substantially remain battened construction, adverse transformation austenite is many simultaneously is distributed between martensite lath with sheet-like morphology.Fig. 4 is for adopting high-resolution-ration transmission electric-lens, and the embodiment 3 of observation is after 520 DEG C of Ageing Treatment, and the nanoscale Precipitation phase morphology (extraction replica carbon film sample) within invention steel, after EDS energy spectrum analysis, video disc shape or corynebacterium precipitated phase are Ni3The second phase particles such as Al or NiAl.
Table 1 embodiment of the present invention chemical composition (wt.%)
Table 2 embodiment mechanical property after different Ageing Treatment and corrosion resisting property
The table 3 embodiment 3 series of temperatures summer after 480 DEG C of Ageing Treatment is than V-type ballistic work
Claims (2)
1. a deep sea low temperature engineering high-strength stainless steel, it is characterized in that, chemical composition is by weight percentage: C:< 0.05%, Cr:12.2～13%, Ni:8.0～8.5%, Mo:2.1～2.5%, Al:< 0.3%, N:< 0.0015%, Si:< 0.1%, Mn:< 0.01%, P:< 0.005%, S:< 0.001% surplus are Fe and inevitable impurity；Based on above-mentioned alloying component proportioning, after heat treatment, 1200MPa is reached in room temperature tensile intensity, yield strength reaches 1100MPa, and elongation percentage is more than 19%, and the contraction percentage of area is more than under the premise of 70%, the room temperature summer reaches more than 250J than V-type ballistic work, and-100 DEG C of ballistic works remain at more than 210J；Salt spray resistance annual corrosion rate also controls at below 0.1mm/a.
2. the manufacture method of the deep sea low temperature engineering high-strength stainless steel described in a claim 1, it is characterised in that:
(1) adopting vaccum sensitive stove+consumable electrode vacuum furnace two-link smelting process, raw material is simple metal material；The stress relief annealing that after smelting, steel ingot through 660～680 DEG C, need to be incubated 16～20 hours simultaneously；
(2) forging, rolling mill practice
Forge Heating temperature 1150～1200 DEG C, opens forging temperature 1050～1080 DEG C, final forging temperature 800～850 DEG C, and total forging ratio of becoming a useful person requires more than 10；
Rolling heating-up temperature 1050～1100 DEG C, start rolling temperature 1000～1020 DEG C, finishing temperature 850～900 DEG C.
(3) Technology for Heating Processing
Bar after thermoforming needs quenched+deep cooling+Ageing Treatment, and concrete technology is as follows:
Hardening heat is 920～950 DEG C, temperature retention time 1～2 hour, and air cooling or oil cooling are to room temperature；Cryogenic temperature is 0 DEG C, temperature retention time 1～2 hour, and air cooling is to room temperature；Aging temp is 450～520 DEG C, and temperature retention time is 4～6 hours, and air cooling is to room temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113186462A (en) * | 2021-04-20 | 2021-07-30 | 钢铁研究总院 | High-strength Cr-Ni-Co-Mo stainless steel for ultralow temperature and toughening heat treatment method |
Citations (3)
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| CN1154419A (en) * | 1996-10-14 | 1997-07-16 | 冶金工业部钢铁研究总院 | ultra hypoeutectoid, diphasic stainless steel, and prodn. method thereof |
| CN101050509A (en) * | 2007-05-17 | 2007-10-10 | 钢铁研究总院 | Martensite ageing stainless steel with high strength and high toughness |
| CN104862598A (en) * | 2015-06-03 | 2015-08-26 | 钢铁研究总院 | 00Cr13Mo corrosion-resistant ferrite stainless steel |
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2016
- 2016-03-11 CN CN201610141371.0A patent/CN105779901B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154419A (en) * | 1996-10-14 | 1997-07-16 | 冶金工业部钢铁研究总院 | ultra hypoeutectoid, diphasic stainless steel, and prodn. method thereof |
| CN101050509A (en) * | 2007-05-17 | 2007-10-10 | 钢铁研究总院 | Martensite ageing stainless steel with high strength and high toughness |
| CN104862598A (en) * | 2015-06-03 | 2015-08-26 | 钢铁研究总院 | 00Cr13Mo corrosion-resistant ferrite stainless steel |
Non-Patent Citations (1)
| Title |
|---|
| 程志伟 等: "热处理工艺对PH13-8Mo钢的组织和性能的影响", 《材料热处理学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113186462A (en) * | 2021-04-20 | 2021-07-30 | 钢铁研究总院 | High-strength Cr-Ni-Co-Mo stainless steel for ultralow temperature and toughening heat treatment method |
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