CN106381453B - A kind of cast steel components and its production technology for nuclear power unit - Google Patents
A kind of cast steel components and its production technology for nuclear power unit Download PDFInfo
- Publication number
- CN106381453B CN106381453B CN201610840947.2A CN201610840947A CN106381453B CN 106381453 B CN106381453 B CN 106381453B CN 201610840947 A CN201610840947 A CN 201610840947A CN 106381453 B CN106381453 B CN 106381453B
- Authority
- CN
- China
- Prior art keywords
- cast steel
- molten steel
- steel components
- casting
- steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001208 Crucible steel Inorganic materials 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000005516 engineering process Methods 0.000 title claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 87
- 239000010959 steel Substances 0.000 claims description 87
- 238000005266 casting Methods 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 238000004458 analytical method Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000004576 sand Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 238000007670 refining Methods 0.000 claims description 14
- 239000000523 sample Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 4
- 244000035744 Hura crepitans Species 0.000 claims description 4
- 108010038629 Molybdoferredoxin Proteins 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000003780 insertion Methods 0.000 claims description 4
- 230000037431 insertion Effects 0.000 claims description 4
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000007528 sand casting Methods 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000000306 component Substances 0.000 description 64
- 239000000463 material Substances 0.000 description 7
- 238000009659 non-destructive testing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910001563 bainite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- 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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- 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
-
- 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
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- 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
-
- 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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses a kind of nuclear power zero-fault high-quality cast steel components, which is characterized in that the weight percent of the cast steel components chemical composition are as follows: C:0.18~0.20%, Si≤0.60%, Mn:0.60~0.80%, P≤0.02%, S≤0.015%, Cr:1.35~1.50%, Ni≤0.50%, Mo:0.90~1.10%, V:0.20~0.30%, Sn≤0.025%, Zr:0.08~0.12%, remaining is Fe and inevitable trace impurity.It also discloses a kind of for producing the technique of above-mentioned cast steel components, so that the cast steel components is reached zero-fault high-quality, there is preferable wearability, corrosion resistance and stronger toughness under high temperature environment, suitable for nuclear power unit.
Description
Technical field
The present invention relates to a kind of cast steel components and its production technology, specifically seed nucleus zero-fault high-quality
Cast steel components and its production technology.
Background technique
Core cast steel components are to be applied to nuclear armament key position, since other technical techniques can not make or make
Make the core components that cost is excessively high, makes as desired by casting.Nuclear armament is high-end equipment, due to running environment side
Face, the needs of secure context and durable aspect lead to have higher requirement to some performances and quality of cast steel components.In addition to
Meet outside conventional mechanical property requirements, due to, often up to 500 DEG C or more high temperature, it requires and also want at high temperature under its operation
There is good performance.
The cast steel components (such as: cylinder, semi-ring casting) are the important component of nuclear power unit, the direct shadow of its quality
Ring the running of nuclear power unit.Since the figure of cast steel components is relatively large, structure is complicated, and casting thermal center is big and disperses, and causes
Casting Technology Design is difficult；In addition, the use environment due to nuclear power unit is special, it is higher to the material requirements of cast steel components.
Currently, domestic have some limitations the production of cast steel components, the tensile strength and yield strength of product are lower,
Corrosion resistance, wearability are also poor, and the relatively low technology for not being able to satisfy external advanced core casting of yield strength under the high temperature conditions
It is required that.Casting quality quality is not high to cause its service life short, and be easy to cause security risk.
Summary of the invention
The present invention provides a seed nucleus cast steel components and its production technology, and its object is to solve cast steel components power
Learn the problem that performance is poor, product quality is not high, production difficulty is big.
A kind of cast steel components for nuclear power unit, it is characterised in that: the weight hundred of the cast steel components chemical composition
Divide ratio are as follows: C:0.18~0.20%, Si≤0.60%, Mn:0.60~0.80%, P≤0.02%, S≤0.015%, Cr:1.35~
1.50%, Ni≤0.50%, Mo:0.90~1.10%, V:0.20~0.30%, Sn≤0.025%, Zr:0.08~0.12%, remaining is
Fe and inevitable trace impurity.
Further, the cast steel components are cylinder or semi-ring casting.
A kind of production technology producing cast steel components described in claim 1, its step are as follows:
(1) the low-carbon punching briquetting of steel cuttings, rustless stain is formed into the molten steel of molten condition by electric furnace heating and melting；
(2) molten steel is sent into oxygen top-blown converter, Si, Mn, P, S, C, Ni and Cr in oxidation removal molten steel obtain low miscellaneous
Matter molten steel；
(3) by low impurity steel water with carrying out Refining in AOD refining furnace；
(4) ferrosilicon, electrolytic manganese are added in the molten steel after refining, low-carbon ferrochromium and metal zirconium carry out melting；
(5) foundry returns for the same trade mark being added after cleaning carries out melting, after molten steel melting, takes molten steel sample
Learn analysis of components；
(6) for analysis gained chemical analysis, addition is baked to 240~260 DEG C of alloy material, carries out ingredient to molten steel
It is finely adjusted, mass percent ratio requirement can be met；
(7) after furnace temperature being risen to 1640~1650 DEG C, two step deoxidations are carried out；4~5 points of electromagnetic agitation are carried out to electric furnace
Whether Zhong Hou, insertion apparatus for determination of oxygen probe measure oxygen content PPM value in molten steel and come out of the stove after the assay was approved in specified value；
(8) with ladle dryer baking ladle to 900 DEG C~1000 DEG C, backpack body is aglow；
(9) nickel plate, molybdenum-iron, cathode copper and vanadium iron are broken into fritter, drying is placed on ladle bottom, then deoxidier is set
In Ladle Bottom, with pouring in packet, method carries out compound modification treatment to molten steel and final deoxidizing is handled；
(10) Argon processing, Argon pressure >=0.15MPa, argon blowing time >=15 minute are carried out to molten steel, and uses determine again
Oxygen instrument is measured steel water oxygen level；
(11) it is sent into vacuum tank after heating molten steel and carries out vacuum outgas deoxidation；
(12) sand casting cast steel components are used, carry out flow coat and drying before sand mold casting.It is poured using open symmetric form
Injection system is poured, and pouring temperature is 1555~1565 DEG C；
(13) casting is unpacked after solidifying heat preservation 72~84 hours in sandbox after being poured, and air-cooled cast steel components to 200~
250 DEG C hereinafter, gas flame cuttiug dead head, cleaning undesirable root, overlap, burr etc.；
(14) cast steel components are quenched at 950~1050 DEG C, 80 DEG C of heating rate~100 DEG C/H, soaking time 3
~8 hours.Hardening, hardening enter 45~70S of water time immediately after coming out of the stove, and are again heated to 200~250 DEG C of tempering, heat preservation, cold with furnace
But air-cooled to carrying out after 150 DEG C.
Further, Chemical bath deposition described in step (5) is carried out with portable spectrometer to molten steel sample in stokehold
Chemical analysis is quickly analyzed.
Further, two step deoxidations described in step (7) are, fine aluminium deoxidation is first added and carries out first step deoxidation, then plus
The double deoxidizer for entering siliceous, calcium, barium and aluminium carries out second step deoxidation.
Further, ladle medium position temperature is measured with infrared temperature-measuring gun in step (8), backpack body is aglow.
Further, deoxidier described in step (9) is calcium, silicon, manganese double deoxidizer.
Further, coating flow coat sand mold is carried out to sand mold with flow coater in step (12).With industrial hot wind before mould assembling
Machine toasts sand mold.
Further, the water time is entered described in step (14) to be exposed to casting in casting to play casting to open heat-treatment furnace
Part is completely into until in water.Wherein the water in pond used in hardening is necessary for recirculated water, guarantees that water temperature is no more than 38 DEG C always.
The present invention controls the dosage of Cr 1.35~1.5%, mentions intensity, hardness, harden ability and the wearability of steel significantly
Height, while the inoxidizability and corrosion resistance of steel can be improved again.The elements such as Mo, Ni, V, Sn, Zr are added in Steel material to be used for
Cast steel components are manufactured, the mechanical property of cast steel components is greatly improved, higher tensile strength is made it have and surrender is strong
Degree, biggish ballistic work and hardness, make cast steel components show good working performance and service life in nuclear power unit,
The cost of maintenance is greatly reduced, meanwhile, so that cast steel components is had biggish elongation percentage and the contraction percentage of area, guarantees cast steel zero
Component using safe.Wherein Mo promotes the formation of ferrite and bainite, improves the obdurability of casting；It improves simultaneously micro-
Solid solubility of the alloying element V in austenite, delays the Precipitation of microalloy carbonitride, and more V will be enable to protect
Be left under lower temperature and be precipitated from ferrite, generate bigger precipitation enhancement, the thermal stability of the carbonitride containing Mo compared with
It is good, guarantee high-temperature behavior；And V can thinning microstructure crystal grain, improve intensity and toughness, the carbide that V and carbon are formed, in high temperature and pressure
Under hydrogen attack resistance can be improved；Ni forms tiny carbide and nitride in steel, prevents tissue during reheating
Coarse grains prevent the roughening of welding heat affected zone crystal grain in the welding process；Zr as metallurgical industry " vitamin " not only
Have stronger deoxidation, denitrogenate, desulfuration, and can significantly promote the hardness and strength of steel, at the same part Zr with Sn,
The intensity of material, the thermal conductivity of corrosion resistance and Corrosion Resistant Film can be improved under Cr, Ni interaction, reduce surface state to the quick of corrosion
Perception.
In order to produce above-mentioned cast steel components, the present invention also provides a kind of improved production technologies, using the production
Technique can produce the large volume cast steel components of high-quality, for having stronger toughness in nuclear power unit and longer making
Use the service life.With the production technology compared with traditional cast steel components production technology, have the advantage that (1) using steel cuttings,
The low-carbon punching briquetting and certain proportion of rustless stain with the trade mark foundry returns as raw material, under the premise of guaranteeing product quality
Production cost is greatly reduced, waste resource, energy conservation and environmental protection is rationally utilized.(2) oxygen top blown is first passed through before liquid steel refining to turn
Furnace carries out oxidation impurity elimination, prevents the impurity contents such as Si, Mn, P, S, C, Ni and Cr in molten steel excessively high, facilitates below to molten steel
The fine tuning of ingredient.(3) molten steel is refined using AOD refining furnace, reduces the impurity such as P, S in rigid water, to promote molten steel
Degree of purity.(4) analysis of stokehold fast component and Determination of octafluoropropane content are carried out, it is up to standard in the molten steel come out of the stove, to guarantee the property of product
Energy.(5) Argon is carried out to ladle bottom, impurity and argon gas rolling taken out of, to keep molten steel purer.(6) four times are carried out to take off
Oxygen processing, makes the abundant deoxidation of molten steel, to promote properties of product.(7) it is sent into vacuum tank and is de-gassed after the processing of molten steel Argon
Deoxidation, not only further deoxidation promotes properties of product, but also can further purify molten steel, reduces to greatest extent nonmetallic miscellaneous
Matter.(8) manganese iron is replaced to be added in molten steel using electrolytic manganese, to improve the purity of manganese, to promote the mechanical property of cast steel components
Can, improve product quality.(9) ladle needs to first pass through high-temperature baking, keeps backpack body aglow, to guarantee liquid steel temperature abundant enough
Without making the too fast decline of liquid steel temperature due to cold ladle, guarantee that molten steel has suitable pouring temperature.(10) it is poured
Before, coating flow coat is carried out to sand mold with flow coater, sand mold exquisiteness surface is obtained, guarantees cast product surface quality, improve work
Efficiency.Sand mold is toasted with industrial air heater, avoids product air holes defect caused by the sand mold moisture absorption, reduces cold mould to steel flow
The influence of dynamic property, thus greatly reduces defect rate；(11) it uses full open model symmetric form running gate system and carries out zero, cast steel
The casting of part, it is steady to fill type, small to type chamber scouring force, reduces because of volume gas, product casting flaw caused by slag turbulent flow.
In conclusion the dosage of strict control Cr of the present invention, is added to the elements such as Ni, Mo, Sn, Zr, V in Steel material,
Make the cast steel components that there is preferable wearability, corrosion resistance, heat resistance and stronger toughness, reaches external elder generation
Into the technical indicator of core casting.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further elaborated.
Embodiment one
A kind of the step of cast steel components for nuclear power unit, production technology, is as follows:
(1) the low-carbon punching briquetting of steel cuttings, rustless stain is formed into the molten steel of molten condition by electric furnace heating and melting.
(2) molten steel is sent into oxygen top-blown converter, Si, Mn, P, S, C, Ni and Cr in oxidation removal molten steel obtain low miscellaneous
Matter molten steel.
(3) by low impurity steel water with carrying out Refining in AOD refining furnace.
(4) ferrosilicon, electrolytic manganese are added in the molten steel after refining, low-carbon ferrochromium and metal zirconium carry out melting.
(5) foundry returns for the same trade mark being added after cleaning carries out melting, after molten steel melting, takes molten steel sample
Analysis of components is learned, is to carry out chemical analysis to molten steel sample with portable spectrometer in stokehold quickly to analyze.
(6) for analysis gained chemical analysis, addition is baked to 220 DEG C of alloy material, carries out ingredient progress to molten steel
Fine tuning, can meet mass percent ratio requirement.
(7) after furnace temperature being risen to 1635 DEG C, two step deoxidations are carried out, fine aluminium deoxidation is first added and carries out first step deoxidation,
The double deoxidizer that siliceous, calcium, barium and aluminium is then added carries out second step deoxidation；It is carried out electromagnetic agitation 4~5 minutes to electric furnace
Afterwards, insertion apparatus for determination of oxygen probe, measures oxygen content PPM value position 4.8PPM in molten steel, meets≤the requirement of 5PPM, comes out of the stove.
(8) ladle is toasted with ladle dryer, infrared temperature-measuring gun measures ladle middle portion temperature up to 938 DEG C, and visual backpack body is aglow.
(9) by material fragmentations such as nickel plate, molybdenum-iron, cathode copper and vanadium iron at fritter, drying is placed on ladle bottom, then will
Calcium, silicon, manganese double deoxidizer are placed in Ladle Bottom, and with pouring in packet, method carries out compound modification treatment to molten steel and final deoxidizing is handled.
(10) Argon processing carried out to molten steel, Argon pressure 0.18MPa, argon blowing time 16 minutes, and use apparatus for determination of oxygen again
Steel water oxygen level is measured and meets≤the requirement of 5PPM for 4.5PPM.
(11) it will be sent into vacuum tank through Argon treated molten steel heating and carry out vacuum outgas deoxidation, vacuum outgas deoxidation
Time is 30 minutes, vacuum degree 0.5Mbar.
(12) sand casting cast steel components are used, carry out flow coat, air-heater air cooking sand mold before mould assembling before sand mold casting
4H.It is poured using open symmetric form running gate system, pouring temperature is 1556 DEG C.
(13) casting is unpacking after solidify heat preservation in sandbox 72 hours after being poured, air-cooled cast steel components to 230 DEG C or so,
Gas flame cuttiug dead head, cleaning undesirable root, overlap, burr etc..
(14) cast steel components are quenched at 1000 DEG C, 80 DEG C -100 DEG C/H of heating rate, and soaking time is 6 hours.
Hardening, hardening enter water time 60S immediately after coming out of the stove, and are again heated to 200 DEG C of tempering, heat preservation, carry out after cooling to 150 DEG C with the furnace empty
It is cold.Enter the water time and be exposed to casting in casting to open heat-treatment furnace to play casting completely into until in water.Wherein hardening
The water in pond used is necessary for recirculated water, guarantees that water temperature is no more than 38 DEG C always.
Shown in the chemical component such as following table (table 1) of the cast steel components obtained by above-mentioned production technology:
A kind of chemical composition analysis table of the cast steel components for nuclear power unit of table 1
It is obtained shown in the mechanical property such as following table (table 2) of the cast steel components by testing:
A kind of Mechanics Performance Testing table of the cast steel components for nuclear power unit of table 2
Under 20 DEG C of experimental conditions of room temperature
Under 500 DEG C of experimental conditions of high temperature
Yield strength: 350MPa.
It is met the requirements as shown in following table (table 3) by the casting quality that non-destructive testing tests to obtain the cast steel components:
Table is tested in a kind of non-destructive testing of the cast steel components for nuclear power unit of table 3
International core cast steel components quality requirement is complied fully with non-destructive testing result of improving quality.
Embodiment two
A kind of the step of cast steel components for nuclear power unit, production technology, is as follows:
(1) the low-carbon punching briquetting of steel cuttings, rustless stain is formed into the molten steel of molten condition by electric furnace heating and melting.
(2) molten steel is sent into oxygen top-blown converter, Si, Mn, P, S, C, Ni and Cr in oxidation removal molten steel obtain low miscellaneous
Matter molten steel.
(3) by low impurity steel water with carrying out Refining in AOD refining furnace.
(4) ferrosilicon, electrolytic manganese are added in the molten steel after refining, low-carbon ferrochromium and metal zirconium carry out melting.
(5) foundry returns for the same trade mark being added after cleaning carries out melting, after molten steel melting, takes molten steel sample
Analysis of components is learned, is to carry out chemical analysis to molten steel sample with portable spectrometer in stokehold quickly to analyze.
(6) for analysis gained chemical analysis, addition is baked to 210 DEG C of alloy material, carries out ingredient progress to molten steel
Fine tuning, can meet mass percent ratio requirement.
(7) after furnace temperature being risen to 1628 DEG C, two step deoxidations are carried out, fine aluminium deoxidation is first added and carries out first step deoxidation,
The double deoxidizer that siliceous, calcium, barium and aluminium is then added carries out second step deoxidation；It is carried out electromagnetic agitation 4~5 minutes to electric furnace
Afterwards, insertion apparatus for determination of oxygen probe, measures oxygen content PPM value position 4.6PPM in molten steel, meets≤the requirement of 5PPM, comes out of the stove.
(8) ladle is toasted with ladle dryer, infrared temperature-measuring gun measures ladle middle portion temperature up to 956 DEG C, and visual backpack body is aglow.
(9) by material fragmentations such as nickel plate, molybdenum-iron, cathode copper and vanadium iron at fritter, drying is placed on ladle bottom, then will
Calcium, silicon, manganese double deoxidizer are placed in Ladle Bottom, and with pouring in packet, method carries out compound modification treatment to molten steel and final deoxidizing is handled.
(10) Argon processing carried out to molten steel, Argon pressure 0.18MPa, argon blowing time 16 minutes, and use apparatus for determination of oxygen again
Steel water oxygen level is measured and meets≤the requirement of 5PPM for 4.42PPM.
(11) it will be sent into vacuum tank through Argon treated molten steel heating and carry out vacuum outgas deoxidation, vacuum outgas deoxidation
Time is 50 minutes, vacuum degree 0.9Mbar.
(12) sand casting cast steel components are used, carry out flow coat, air-heater air cooking sand mold before mould assembling before sand mold casting
4H.It is poured using open symmetric form running gate system, pouring temperature is 1560 DEG C.
(13) casting is unpacking after solidify heat preservation in sandbox 84 hours after being poured, air-cooled cast steel components to 230 DEG C or so,
Gas flame cuttiug dead head, cleaning undesirable root, overlap, burr etc..
(14) cast steel components are quenched at 1050 DEG C, 80 DEG C -100 DEG C/H of heating rate, and soaking time is 7.5 small
When.Hardening, hardening enter water time 65S immediately after coming out of the stove, and are again heated to 250 DEG C of tempering, heat preservation, cool to the furnace 150 DEG C it is laggard
Row is air-cooled.Enter the water time and be exposed to casting in casting to open heat-treatment furnace to play casting completely into until in water.Wherein
The water in pond used in hardening is necessary for recirculated water, guarantees that water temperature is no more than 38 DEG C always.
Shown in the chemical component such as following table (table 4) of the cast steel components obtained by above-mentioned production technology:
A kind of chemical composition analysis table of the cast steel components for nuclear power unit of table 4
It is obtained shown in the mechanical property such as following table (table 5) of the cast steel components by testing:
A kind of Mechanics Performance Testing table of the cast steel components for nuclear power unit of table 5
Under 20 DEG C of experimental conditions of room temperature
Under 500 DEG C of experimental conditions of high temperature
Yield strength: 368MPa
It is met the requirements as shown in following table (table 6) by the casting quality that non-destructive testing tests to obtain the cast steel components:
Table is tested in a kind of non-destructive testing of the cast steel components for nuclear power unit of table 6
International core cast steel components quality requirement is complied fully with non-destructive testing result of improving quality.
In summary example data of mechanical it is found that by the debugging of the chemical component to cast steel components with
And the improvement of production technology, so that the cast steel components produced have good tensile strength and yield strength, and have
Higher ballistic work, toughness and wearability；Meanwhile the elongation percentage and the contraction percentage of area of cast steel components are larger, illustrate its plasticity
Preferably, it is not only convenient for carrying out various processing, and can guarantee safe handling of the cast steel components in nuclear power unit.
The cast steel components are cylinder, semi-ring casting or other components.
The above is only a specific embodiment of the present invention, but the design concept of the present invention is not limited to this, all to utilize this
Design makes a non-material change to the present invention, and should all belong to behavior that violates the scope of protection of the present invention.
Claims (6)
1. a kind of cast steel components for nuclear power unit, it is characterised in that: the weight percent of the cast steel components chemical composition
Than are as follows: C:0.18~0.20%, Si≤0.60%, Mn:0.60~0.80%, P≤0.02%, S≤0.015%, Cr:1.35~
1.50%, Ni≤0.50%, Mo:0.90~1.10%, V:0.20~0.30%, Sn≤0.025%, Zr:0.08~0.12%, remaining is
Fe and inevitable trace impurity, a kind of production technology producing the cast steel components, its step are as follows:
(1) the low-carbon punching briquetting of steel cuttings, rustless stain is formed into the molten steel of molten condition by electric furnace heating and melting；
(2) molten steel is sent into oxygen top-blown converter, Si, Mn, P, S, C, Ni and Cr in oxidation removal molten steel obtain low impurity steel
Water；
(3) by low impurity steel water with carrying out Refining in AOD refining furnace；
(4) ferrosilicon, electrolytic manganese are added in the molten steel after refining, low-carbon ferrochromium and metal zirconium carry out melting；
(5) be added by cleaning after the same trade mark foundry returns carry out melting, after molten steel melting after, take molten steel sample carry out chemistry at
Part analysis；
(6) for analysis gained chemical analysis, addition is baked to 240~260 DEG C of alloy material, carries out ingredient progress to molten steel
Fine tuning, can meet mass percent ratio requirement；
(7) after furnace temperature being risen to 1640~1650 DEG C, two step deoxidations are carried out；That is, fine aluminium deoxidation, which is first added, carries out the first step
Deoxidation, the double deoxidizer that siliceous, calcium, barium and aluminium is then added carry out second step deoxidation, carry out electromagnetic agitation 4~5 to electric furnace
After minute, whether insertion apparatus for determination of oxygen probe measures oxygen content PPM value in molten steel and comes out of the stove after the assay was approved in specified value；
(8) with ladle dryer baking ladle to 900 DEG C~1000 DEG C, backpack body is aglow；
(9) nickel plate, molybdenum-iron, cathode copper and vanadium iron are broken into fritter, drying is placed on ladle bottom, then deoxidier is placed in steel
Bottom is wrapped, method carries out compound modification treatment to molten steel and final deoxidizing is handled with pouring in packet；
(10) Argon processing, Argon pressure >=0.15MPa, argon blowing time >=15 minute are carried out to molten steel, and uses apparatus for determination of oxygen again
Steel water oxygen level is measured；
(11) it is sent into vacuum tank after heating molten steel and carries out vacuum outgas deoxidation；
(12) sand casting cast steel components are used, carry out flow coat and drying before sand mold casting, are using the casting of open symmetric form
System is poured, and pouring temperature is 1555~1565 DEG C；
(13) casting is unpacked after solidifying heat preservation 72~84 hours in sandbox after being poured, and air-cooled cast steel components are to 200~250 DEG C
Hereinafter, gas flame cuttiug dead head, cleaning undesirable root, overlap, burr etc.；
(14) cast steel components are quenched at 950~1050 DEG C, 80 DEG C of heating rate~100 DEG C/h, and soaking time is 3~8
Hour, hardening, hardening enter 45~70s of water time immediately after coming out of the stove, and are again heated to 200~250 DEG C of tempering, keep the temperature, cold with furnace
But air-cooled to carrying out after 150 DEG C, the hardening, which enters the water time and is exposed to casting in casting to open heat-treatment furnace, plays casting
Until in water, wherein the water in pond used in hardening is necessary for recirculated water, guarantees that water temperature is no more than 38 DEG C always.
2. a kind of cast steel components for nuclear power unit according to claim 1, it is characterised in that: the cast steel zero
Component is cylinder or semi-ring casting.
3. the production technology of the cast steel components according to claim 1, it is characterised in that: chemistry described in step (5)
Analysis of components is to carry out chemical analysis to molten steel sample with portable spectrometer in stokehold quickly to analyze.
4. the production technology of the cast steel components according to claim 1, it is characterised in that: with infrared survey in step (8)
Warm rifle measures ladle medium position temperature, and backpack body is aglow.
5. the production technology of the cast steel components according to claim 1, it is characterised in that: deoxidation described in step (9)
Agent is calcium, silicon, manganese double deoxidizer.
6. the production technology of the cast steel components according to claim 1, it is characterised in that: step uses flow coater in (12)
Coating flow coat sand mold is carried out to sand mold, sand mold is toasted with industrial air heater before mould assembling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610840947.2A CN106381453B (en) | 2016-09-22 | 2016-09-22 | A kind of cast steel components and its production technology for nuclear power unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610840947.2A CN106381453B (en) | 2016-09-22 | 2016-09-22 | A kind of cast steel components and its production technology for nuclear power unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106381453A CN106381453A (en) | 2017-02-08 |
| CN106381453B true CN106381453B (en) | 2018-12-07 |
Family
ID=57935786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610840947.2A Active CN106381453B (en) | 2016-09-22 | 2016-09-22 | A kind of cast steel components and its production technology for nuclear power unit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106381453B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108930002B (en) * | 2017-05-26 | 2020-08-25 | 宝山钢铁股份有限公司 | Abrasion-resistant steel plate for slurry dredging pipe with hardness of 500HB and production method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618128B2 (en) * | 1980-07-23 | 1986-03-12 | Nippon Kokan Kk | |
| JP2001131698A (en) * | 1999-10-28 | 2001-05-15 | Sumitomo Metal Ind Ltd | Steel pipe with excellent sulfide stress cracking resistance |
| CN101476085A (en) * | 2009-01-08 | 2009-07-08 | 辽宁福鞍铸业集团有限公司 | Method for foundry production of ultra-supercritical main steam control valve for nuclear power unit |
| CN102741440A (en) * | 2010-05-31 | 2012-10-17 | 新日本制铁株式会社 | Steel material for quenching and method of producing same |
| CN104878311A (en) * | 2015-06-15 | 2015-09-02 | 三明市毅君机械铸造有限公司 | Cast steel part for ultra-supercritical thermal power generating unit and production process of cast steel part |
-
2016
- 2016-09-22 CN CN201610840947.2A patent/CN106381453B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618128B2 (en) * | 1980-07-23 | 1986-03-12 | Nippon Kokan Kk | |
| JP2001131698A (en) * | 1999-10-28 | 2001-05-15 | Sumitomo Metal Ind Ltd | Steel pipe with excellent sulfide stress cracking resistance |
| CN101476085A (en) * | 2009-01-08 | 2009-07-08 | 辽宁福鞍铸业集团有限公司 | Method for foundry production of ultra-supercritical main steam control valve for nuclear power unit |
| CN102741440A (en) * | 2010-05-31 | 2012-10-17 | 新日本制铁株式会社 | Steel material for quenching and method of producing same |
| CN104878311A (en) * | 2015-06-15 | 2015-09-02 | 三明市毅君机械铸造有限公司 | Cast steel part for ultra-supercritical thermal power generating unit and production process of cast steel part |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106381453A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108251746B (en) | A kind of high durable, sea water corrosion-resistant steel with low cost muscle and production technology | |
| CN107502817B (en) | High grain size number pinion steel 20CrMnTiH and its production technology | |
| CN104878311B (en) | A kind of cast steel parts for ultra supercritical coal-fired unit and production technology thereof | |
| CN103981445B (en) | H13 hot-work die steel production technique | |
| CN106591689B (en) | A kind of hypereutectic high-chromium alloy white cast iron chute lining board and preparation method thereof | |
| CN102041437B (en) | 160mm-thick Q345E-Z35 steel plate for high-rise buildings and production method thereof | |
| CN108723091B (en) | High-chromium cast iron roller for chemical industry and preparation method thereof | |
| CN106086642B (en) | A kind of 200mm thickness resistance against hydrogen cracking steel plate of pressure vessel and its manufacture method | |
| CN102312160B (en) | 12Cr2Mo1R steel plate for ultra-thick hydrogen-contacting equipment and production method thereof | |
| CN104561837A (en) | Steel plate made of pressure vessel steel ASTMA387CL11Gr2 and production method thereof | |
| CN104762559A (en) | Method for producing steel plate for hydrogen-contacting equipment | |
| CN114032461B (en) | High-nitrogen steel with high strength, low yield ratio and high corrosion resistance for marine engineering and preparation method thereof | |
| CN109402498A (en) | A kind of high-temperature carburizing pinion steel and its manufacturing method | |
| CN108747084A (en) | A kind of welding wire for submerged-arc welding and preparation method thereof | |
| CN104911504A (en) | High-strength high-wear-resistance steel casting for super-huge type crusher and production process of steel casting | |
| CN110079726A (en) | A kind of technique improving gray cast iron engine cylinder cover room temperature drawingand pressing fatigue intensity | |
| CN102864383A (en) | Low alloy steel | |
| CN104878320B (en) | A kind of mine and the high strength casting and its production technology of mobile crushing station for building | |
| CN110983164A (en) | Microalloy element Nb-reinforced duplex stainless steel and preparation method thereof | |
| CN106381453B (en) | A kind of cast steel components and its production technology for nuclear power unit | |
| CN114457288A (en) | High-nitrogen austenitic stainless steel and preparation method of middle plate thereof | |
| CN114540716A (en) | Steel for valve body of underwater Christmas tree with wall thickness ≥600mm, high strength, toughness and long life, heat treatment method and production method thereof | |
| CN109536664A (en) | A kind of myrmekite ink cast iron scroll plate and its production technology | |
| CN103451512A (en) | Method of obtaining as-cast pearlitic ductile iron by adding alloy elements | |
| CN105088087A (en) | High-toughness optimal welding micro-alloyed cast steel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |