CN102051531A - High boron content austenite stainless steel and preparation method thereof - Google Patents
High boron content austenite stainless steel and preparation method thereof Download PDFInfo
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 27
- 239000010935 stainless steel Substances 0.000 title claims abstract description 27
- 229910001566 austenite Inorganic materials 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000005098 hot rolling Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 238000005242 forging Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
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- 238000005554 pickling Methods 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
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- 238000004512 die casting Methods 0.000 claims abstract description 5
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- 238000010438 heat treatment Methods 0.000 claims abstract description 4
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- 238000010521 absorption reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
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- 239000010959 steel Substances 0.000 description 16
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to high boron content austenite stainless steel which comprises the following chemical components in percentage by weight: no more than 0.05% of C, 1.7-2.0% of B, no more than 1.0% of Si, no more than 2.0% of Mn, no more than 0.035% of P, no more than 0.030% of S, 12.5-15.0% of Ni, 18.5-21.0% of Cr, no more than 0.5% of Mo, no more than 0.05% of N, no more than 0.15% of Ti, no more than 0.0060% of O, no more than 0.15% of Ce and balance of Fe and inevitable impurities. The preparation method comprises the following steps: the vacuum induction furnace-vacuum consumable furnace technology or vacuum induction furnace-gas-shielded electroslag furnace technology or arc furnace-argon oxygen decarburization (AOD) smelting technology is adopted to smelt stainless steel, die casting is performed, and the cooling speed is greater than 30 DEG C/min; forging and hot rolling are adopted for hot working; and heat treatment and acid pickling are performed to obtain a hot-rolled product. The produced high boron stainless steel hot-rolled product has good mechanical property and neutron absorption property; and no special technological equipment is needed, the production technology is simple and effective, and the production efficiency is high.
Description
Technical field
The present invention relates to the stainless steel manufacturing process, particularly a kind of high boron content austenitic stainless steel and manufacture method thereof.
Background technology
Along with becoming increasingly conspicuous of the serious day by day and environmental problem of world energy sources shortage problem, the pay attention to day by day that green energy resources such as nuclear power obtain countries in the world with greatly develop.High boron austenitic stainless steel has good neutron absorptive character, long service life, stable and reliable for performance and do not need the advantage of comprehensive costs such as inservice inspection and performance, replacing boron plastics, cadmium isotonic absorbing material gradually becomes the first-selected neutron absorbing materials in field such as spent fuel storage rack, the storage of nuclear waste fuel and transport container, has obtained using widely.
For guaranteeing that spent fuel keeps subcritical state, Nuclear power plants more and more tends to adopt the mode of high-density or high storage density to store nuclear fuel at present, and this just requires the thickness of boronated stainless steel more and more thinner more and more higher with boron content.But the solid solubility of boron in steel is very low, can form a large amount of low melting point boride eutectics in the high boron stainless steel, seriously isolate matrix and make grain-boundary strength weaken greatly, cause plasticity, the toughness of material to reduce significantly, thereby significantly reduce the hot workability of steel, cause the steel plate limit to be split seriously, the high and manufacturing cost rising of therefore high boron austenitic stainless steel manufacture difficulty.
For solving the big problem of high boron stainless steel manufacture difficulty; present solution mainly is to carry out processing treatment by the limit portion to high boron stainless steel casting blank or forging stock; comprise metallizing, frame protection material, weld the good dissimilar metal of plasticity etc.; guarantee to reduce in the hot procedure High Boron Steel limit portion's temperature drop and its distortion of constraint; reach minimizing or avoid the stainless limit of high boron to split and improve the purpose of lumber recovery; but such treating processes work flow is longer; some needs special tooling, causes complex process and cost higher.
Japanese Patent JP4253506 discloses a kind of hot-rolling method of high boron austenitic stainless steel, its high boron stainless steel material composition that adopts is (massfraction): boron 0.3-2.0%, carbon≤0.08%, silicon≤2.0%, manganese≤2.0%, nickel 8.0-15.0%, chromium 16.0-20.0%, molybdenum≤3.0%, nitrogen≤0.15%, all the other are iron and unavoidable impurities.The hot-rolling method of this patent is that the soldering frame material carries out hot-work around High Boron Steel ingot casting or forging stock by adopting, Heating temperature is 1100～1200 ℃, finishing temperature is greater than T=53B+700 ℃, reach the purpose that reduces or avoid high boron stainless steel hot edging to split, obtained certain effect, but it is big that this method need be prepared the frame material and the welding job amount of high precision groove, and operation of rolling center material peels off easily, causes complex manufacturing and production efficiency low.
Japanese Patent JP9269398 discloses a kind of thermal processing method that is used for the high boron austenitic stainless steel of hot rolling, concrete scheme is: adopt at boracic 0.6～2.0wt% austenitic stainless steel billets side deposited metal layer, the ferrite content of controlling this deposited metal layer is 3～12vol.%, boron-containing quantity is that 0.3wt.% is following with more than the thickness 3mm, hot rolling after 1100～1200 ℃ of insulations at last, split to reduce the hot rolling limit, but this method is for guaranteeing enough overlay cladding thickness, it is many and be easy to generate welding crack to cause welding number, when producing welding crack, to become formation of crack and cause the limit and split generation, split generation so be difficult to prevent fully the limit.
Chinese patent CN1681955A discloses a kind of stainless steel product containing B and manufacture method thereof; being characterized as of this steel plate: with efficent electronic bundle welding protection material, the chemical ingredients of welding metal need satisfy: 15≤C on the two sides at least of stainless steel plate except that machined surface of boracic 0.3～2.5wt.%
Req≤ 30,4≤Cr
Eq-Ni
Eq≤ 17, Cr
Eq=Cr+1.5 * Si+Mo-5 * B, Ni
Eq=Ni+30 * (C+N)+0.5 * Mn, carry out hot-work thus and can prevent that hot rolling material from producing the limit and splitting, but this method special welding jig of needs and cost are higher, and do not have boron content to surpass the 1.2wt% welding test among the embodiment, can not guarantee that the high boron content hot rolling material does not produce the limit and splits.
Japanese Patent JP6192792 discloses a kind of boronated stainless steel of high anti-corrosion, its chemical ingredients is (massfraction): C≤0.02%, Si≤0.5%, Mn≤2%, Ni10-22%, Cr18-26%, B≤3.0%, Mg≤0.1%, Al≤0.5%, Gd0.05-1.0%, the Ti of 0.1-5%, Zr and Nb one of them or compound interpolation, Cd≤1%, Sm≤1% and Eu≤1% one of them or compound interpolation, the Mo of 0.1-5%, W and V one of them or compound interpolation, all the other are iron and unavoidable impurities.This patent utilization increases other neutrons absorption elements such as Gd, Sm and Eu and reduces B content, thereby improved the solidity to corrosion and the hot workability of material, but this method complex chemical composition has increased the smelting difficulty, and many elements belong to rare elements, cause the raw materials cost costliness.
Japanese Patent JP11158583 discloses a kind of boronated stainless steel and hot rolled plate making process thereof, and its disclosed chemical ingredients is: C≤0.03%, Si 0.1-1.0%, Mn 0.2-2.0%, P≤0.05%, S≤0.01%, Ni 7-15%, Cr 18-25%, B 0.9-2.5%, Mo 0.1-1.0%, Al 0.3-0.8%, N≤0.04%, Ca 0-0.01%, rare earth 0-0.01%, all the other are iron and unavoidable impurities.Reduce the hot-work limit by control single pass draught and split, Rc={T (℃)/10}-20 * B (%)-35, Rc, T and B are respectively and allow draught, hot-rolled temperature and boron content.But this method has been added higher chromium and molybdenum, has increased raw materials cost, and contains higher aluminium, influences the surface quality of material.
Summary of the invention
The purpose of this invention is to provide a kind of high boron austenitic stainless steel and manufacture method thereof, the high boron stainless steel hot-rolling product of producing has good mechanical performance and neutron absorptive character, and, tooling that need not be special, production technique is simple effectively, production efficiency is high.
For achieving the above object, technical scheme of the present invention is,
A kind of high boron content austenitic stainless steel, its chemical component weight per-cent is: C:0.01～0.05%, B:1.7～2.0%, Si≤1.0%, Mn≤2.0%, P≤0.035%, S≤0.030%, Ni:12.5～15.0%, Cr:18.5～21.0%, Mo≤0.5%, N≤0.05%, Ti≤0.15%, O≤0.0060%, Ce≤0.15%, all the other are Fe and unavoidable impurities.
Preferably, C is 0.01～0.03wt%.
The manufacture method of high boron content austenitic stainless steel of the present invention may further comprise the steps:
Adopt vacuum induction furnace-consumable electrode vacuum furnace technology or vacuum induction furnace-gas shield electroslag furnace technology or electric arc furnace-AOD melting technology smelting stainless steel, the die casting slab ingot, and take speed of cooling cooling faster, make its speed of cooling greater than 30 ℃/min;
Hot-work adopts many fire to forge and hot rollings: can broken as-cast structure by forging process, thus further improve the thermoplasticity of material, forging the processing temperature scope is 900～1250 ℃, every fire time forged draught is controlled at below 80%; Further carry out hot rolling after the forging stock heating, hot rolling processing temperature scope is 900～1250 ℃, and every fire time hot rolling draught is controlled at below 80%; Many fire forge, the hot rolled number of times can be determined according to the ratio between the finished product thickness of the original depth of casting slab ingot and needs, by the control of above-mentioned thermal process parameter, can significantly reduce or avoid the limit of High Boron Steel hot-rolled sheet to split;
Solid solution temperature is 1000～1150 ℃, and solution treatment time t (min of unit)=(2～3) * h, h are thickness of slab (mm of unit), and pickling obtains the austenite stainless steel plate of neutron absorptive character excellence then.
In the chemical ingredients of austenitic stainless steel of the present invention:
Carbon: be strong austenite former, can improve the intensity of steel.Too much unsuitable, surpass at 0.05% o'clock and can reduce solidity to corrosion and hot workability variation, and preferentially 0.01～0.03%.
Boron: be the principal element of neutron absorption, when content was low, the neutron assimilation effect was undesirable, but add-on is when too much, and the boride amount of separating out too much will cause the toughness extreme difference of steel, so boron content is controlled at 1.7～2.0% and is advisable.
Silicon: add as reductor, when content is low, the mechanical property of steel is not had big influence, but add too much, then can make processing and toughness deterioration, so the adding of silicon is controlled at below 1.0% to well.
Manganese: be weak austenite element, play the effect of stable austenite, can suppress the deleterious effect of sulphur in the stainless steel, improve thermoplasticity, can increase the tendency that intermetallic compound forms, also can reduce solidity to corrosion, should be controlled at below 2.0% but surpass at 2.0% o'clock.
Phosphorus, sulphur: be the impurity element in the steel, for thermoplasticity and corrosion proof consideration, these two constituent contents are few more good more, should be controlled at P≤0.04%, S≤0.03%.
Nickel: as the element of intensive formation and expansion austenitic area,, the nickel lower limit is controlled at 12.5%, but the price of nickel is higher, should be controlled at below 15.0% for stability and the raising hot workability that guarantees austenite structure.
Chromium: improve corrosion proof important element, can improve stainless steel solidity to corrosion in oxidizing acid, improve its local corrosion ability such as anticorrosion stress-resistant, spot corrosion and crevice corrosion in chloride soln.Be lower than at 18.0% o'clock, solidity to corrosion is relatively poor, but too high increase ferrite and intermetallic compound are separated out tendency, preferably are controlled at 18.0～21.0%.
Molybdenum: can improve alloy corrosion resistance, but consider that price factor should not add, preferably be controlled at below 0.5%.
Nitrogen: be strong austenite former, improve the hardenability and the intensity of steel, also can save nickel, but add-on too much can make the hot workability variation in High Boron Steel, should be controlled at below 0.05%.
Titanium: Ti is easy to combine with N and forms TiN, so usually add with the N in the fixing steel as stabilizing element, TiN can be used as non-spontaneous core and promotes forming core, make the solidified structure refinement, but excessive Ti can increase the smelting difficulty, reduce the surface quality and the use properties of material, therefore be controlled at below 0.15%.
Cerium: add RE elements of Ce, help purifying crystal boundary, remove harmful being mingled with and thinning solidification structure, make the boride size decreases, can improve the thermoplasticity of steel, but can not be too much, should be controlled at below 0.15%, otherwise can reduce the toughness of steel on the contrary.
Split susceptibility for reducing high boron austenitic stainless steel hot-work limit, the present invention takes the method for chemical ingredients and as-cast structure control, the segregation degree is lower to obtain, the as-cast microstructure of refinement, and improve inclusion and tiny boride, improve from the source high boron austenitic stainless steel hot workability.
Particularly, the present invention is by the control oxygen level and add the rare earth element of trace, can pure steel, remove and harmfully be mingled with, improve inclusion morphology and thinning solidification structure, thus make the boride size decreases and improve the thermoplasticity of steel; Adding trace Ti in addition can stabilization N, and the TiN of formation can be used as non-spontaneous core and promotes forming core, also can make the solidified structure refinement; And the die casting slab ingot takes faster the speed of cooling cooling, makes its speed of cooling greater than 30 ℃/min, also further thinning solidification structure and improve the boride distribution of sizes.
In a word, the present invention is by the control of chemical ingredients and as-cast structure, obtained the as-cast microstructure of refinement, and boride segregation degree is low, heart portion and the equal small and dispersed of limit portion boride size, thereby improved the thermoplasticity of this steel, for hot procedure reduces or avoids the limit to split and every performance of improving material is had laid a good foundation.
Hot procedure has adopted first forging back hot rolled method, forges, guarantees suitable every fire time deflection and hot processing temperature scope in thermoplasticity comparatively high temps interval in the course of hot rolling, reduces or avoids the generation that the limit is split in the hot procedure.Particularly, forging is at first adopted in hot-work, and the forging deformation amount is little and can multi-directionly be out of shape, and has improved the texturizing condition of High Boron Steel, guarantees in the forging process that every fire time hot processing temperature scope is all within 900～1250 ℃; Temperature is too high, and eutectic phase fusing can appear in High Boron Steel, and temperature is low excessively, will cause resistance to deformation to enlarge markedly, and is unfavorable for all that heat adds to carry out.Because the existence of a large amount of borides of High Boron Steel, easy stress concentration causes crack initiation and expansion in the hot procedure, therefore every fire time hot-work draught is controlled at below 80%, in a word, can refined cast structure by forging process, thereby further improve the thermoplasticity of material, guarantee final hot rolling minimizing or avoid the limit to split; Also guarantee in the course of hot rolling every fire time hot processing temperature scope all within 900～1250 ℃, draught is controlled at below 80%; By the control of hot procedure, make the High Boron Steel limit split obviously to alleviate or avoid the limit to split fully.In 1000～1150 ℃ of temperature ranges, carry out obtaining hot-rolled product after solution treatment and the pickling at last, solution treatment time t (min of unit)=(2～3) * h wherein, h is thickness of slab (mm of unit).
The high boron austenitic stainless steel that the present invention obtains has good neutron absorptive character and mechanical property, can be applicable to spent fuel storage rack, nuclear waste fuel storage and fields such as transport container and shielding material.
Beneficial effect of the present invention:
Compare with existing other patents, the present invention does not need the limit portion of high boron stainless steel casting blank or forging stock is carried out processing treatment, tooling that need not be special, therefore the production technique that adopts is simple effectively, production efficiency is high, and the high boron stainless steel hot-rolling product of producing has good mechanical performance and neutron absorptive character.
The present invention is by chemical Composition Control and as-cast structure control, to obtain lower as-cast microstructure of segregation degree and tiny boride, improve the hot workability of this steel, guarantee that in subsequently forging, course of hot rolling suitable every fire time deflection and hot processing temperature scope are in thermoplasticity comparatively high temps interval, reduce or avoid the generation that the limit is split in the hot procedure, carry out solution treatment and pickling at last and obtain high boron austenite stainless steel hot-rolled sheet, such stainless steel has good neutron absorptive character.
Description of drawings
Fig. 1 is an embodiment of the invention solution treatment attitude typical case metallograph.
Embodiment
Detailed by the following examples explanation characteristics of the present invention.
Chemical ingredients according to high boron austenitic stainless steel embodiment of the present invention sees Table 1.
Embodiment 1～6 adopts vacuum induction furnace-consumable electrode vacuum furnace technology; or vacuum induction furnace-gas shield electroslag furnace technology or the smelting of electric arc furnace one AOD melting technology; the speed of cooling of die casting slab ingot is greater than 30 ℃/min; in 900～1250 ℃ of temperature ranges, forge and to be hot-rolled down to 5mm thick; every fire time hot-work draught is controlled at below 80%; solution treatment 10min in 1000～1150 ℃ of temperature ranges; obtain hot-rolled finished product after the last pickling; it is low that degree is split on the hot rolling limit, and this finished product has equally distributed boride; good mechanical performance and neutron absorptive character.
Fig. 1 is an embodiment of the invention solution treatment attitude typical case metallograph.As can be seen, embodiment of the invention stainless steel finished product attitude boride is tiny and be evenly distributed, and this is to plasticity of improving material and guarantee that good neutron absorptive character are very favourable.The thick embodiment hot-rolled sheet of 5mm has been carried out mechanical property and pitting potential detected that (national standard: GB/T 17897-1999), test result sees Table 2.As can be seen, the stainless unit elongation of embodiment is higher, help the following process of material, and pitting potential all is higher than 80mv, possesses corrosion resistance preferably.Owing to play the main of neutron absorption in the High Boron Steel by the B10 isotropic substance, therefore measured the isotopic content of B10, the result is as shown in table 2.This shows that embodiment has good neutron absorptive character.
Comparative Examples production path is as follows:
Comparative Examples 1: its composition is common 304L composition, and production technique is identical with content of the present invention, and the result shows, owing to only contain trace B, so its mechanical property and excellent corrosion-proof performance, but its neutron absorptive character are poor.
Comparative Examples 2: its main component is similar to Example 1, but does not add Ti, Ce, and its oxygen level is higher to be 0.008%, and production technique is identical with content of the present invention.The result shows that inclusion is more in its microstructure, the boride size is bigger, causes the hot rolling limit to split that degree increases and the finished product unit elongation is relatively poor.
Comparative Examples 3: its composition is with embodiment 2 compositions, but its hot rolling technology is different with content of the present invention: finishing temperature＜900 ℃, and every fire time hot rolling draught＞85%, other technologies are with content of the present invention.The result shows: because the low and each total reduction of hot rolling finishing temperature control is excessive, cause high boron stainless steel hot processing limit to be split seriously, make lumber recovery lower.
The high boron austenitic stainless steel of the present invention has excellent neutron absorptive character, development along with green energy resources such as world nuclear, the application prospect of high boron austenitic stainless steel will be more wide, can be applicable to spent fuel storage rack, nuclear waste fuel storage and fields such as transport container and shielding material.
Claims (3)
1. high boron content austenitic stainless steel, its chemical component weight per-cent is: C:0.01～0.05%, B:1.7～2.0%, Si≤1.0%, Mn≤2.0%, P≤0.035%, S≤0.030%, Ni:12.5～15.0%, Cr:18.5～21.0%, Mo≤0.5%, N≤0.05%, Ti≤0.15%, O≤0.0060%, Ce≤0.15%, all the other are Fe and unavoidable impurities.
2. high boron content austenitic stainless steel as claimed in claim 1 is characterized in that, preferably, C is 0.01～0.03wt%.
3. the manufacture method of high boron content austenitic stainless steel as claimed in claim 1 or 2 may further comprise the steps:
1), adopts vacuum induction furnace-consumable electrode vacuum furnace technology or vacuum induction furnace-gas shield electroslag furnace technology or electric arc furnace-AOD melting technology smelting stainless steel by claim 1 or 2 described compositions;
2) casting, die casting, and take speed of cooling cooling faster, speed of cooling is greater than 30 ℃/min;
3) hot-work adopts many fire to forge and hot rolling, and forging processing temperature is 900～1250 ℃, and every fire time forged draught is controlled at below 80%; Further carry out hot rolling after the forging stock heating, hot rolling processing temperature scope is 900～1250 ℃, and every fire time hot rolling draught is controlled at below 80%;
4) thermal treatment, pickling are carried out obtaining hot-rolled product after solution treatment, the pickling in 1000～1150 ℃ of temperature ranges, solution treatment time t (min of unit)=(2～3) * h wherein, and h is thickness of slab (mm of unit).
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