CN103352175B - A kind of control nitrogen austenitic stainless steel and manufacture method thereof - Google Patents
A kind of control nitrogen austenitic stainless steel and manufacture method thereof Download PDFInfo
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Abstract
A kind of control nitrogen austenitic stainless steel and manufacture method thereof, belong to stainless steel technical field.This stainless steel component weight percentages is: C≤0.03, Si≤0.75, Mn≤2.00, P≤0.035, S≤0.010,17.0≤Cr≤18.5,10.0≤Ni≤13.0,2.0≤Mo≤3.0,0.06≤N≤0.13,0.01≤Co≤0.08,0.01≤Cu≤0.50,? B≤0.0018, surplus is Fe, meet 1.4≤(Cr+Mo+1.5Si)/(Ni+0.5Mn+20N)≤1.8, Cr+3.3Mo+16N >=27.5 further.Its manufacture method comprises: melting, rotary casting or hot piercing or hot extrusion, hot rolling, solution heat treatment, scale removal, clod wash or hot bending, annealing thermal treatment.Advantage is, this control nitrogen austenitic stainless steel has excellent hot workability, mechanical property and corrosion resistance nature.<!--1-->
Description
Technical field
The invention belongs to stainless steel technical field, particularly one control nitrogen austenitic stainless steel and manufacture method thereof.
Background technology
In pressurized-water reactor, the main pipeline of ligation heap, vapour generator, main pump belongs to core one-level pipeline, very severe in run duration working conditions, except bearing various load combinations and low week, high-cycle fatigue, the corrosion harmfulness also will bearing the high temperature of medium, high pressure, high flow rate and chlorion atmosphere and cause, its selection with manufacture very crucial.
Current PWR main pipe line mainly adopt the Z3CN20-09M of rotary casting, forging deformation 09X18H10T, X6CrNiNb18-10,316, the material such as Z2CND18-12 and 316LN.
For standard type austenitic stainless steel, as 316, intensity can meet technical requirements, but carbon content is high, and large section postwelding easily intergranular corrosion occurs; Stabilization type austenitic stainless steel, as 09X18H10T, X6CrNiNb18-10 etc., intensity can meet the demands, but due to the existence of TiN, NbN, later stage cold working easily cracks, and welding property is poor; Ultra-low carbon type austenitic stainless steel, as Z2CND18-12, its intergranular corrosion resistance, welding, processing characteristics are all very excellent, but intensity can not meet the demands completely; Nitrogen alloying austenitic stainless steel 316 L N, although intensity easily meets the demands, owing to containing higher N, its hot workability is poor, and welding easily produces thermal crack.
Summary of the invention
The object of the present invention is to provide a kind of control nitrogen austenitic stainless steel and manufacture method thereof, there is excellent hot workability and corrosion resistance nature and mechanical property.
The component weight percentages of control nitrogen austenitic stainless steel of the present invention is: C≤0.03, Si≤1.0, Mn≤2.0, P≤0.035, S≤0.010,17.0≤Cr≤18.5,10.0≤Ni≤13.0,2.0≤Mo≤3.0,0.06≤N≤0.14,0.01≤Co≤0.08,0.01≤Cu≤0.50, B≤0.0018, surplus is Fe.
On the basis of technique scheme, the present invention can also do following improvement:
Further, control the alloying element content of above-mentioned control nitrogen austenitic stainless steel, make 1.4≤(Cr+Mo+1.5Si)/(Ni+0.5Mn+20N)≤1.8;
Further, the constituent contents such as control Cr, Mo, N, make Cr+3.3Mo+16N >=27.5
The manufacture method of control nitrogen austenitic stainless steel of the present invention, comprises following processing step:
(1) according to following elements weight percent melting molten steel: C≤0.03, Si≤1.0, Mn≤2.0, P≤0.035, S≤0.010,17.0≤Cr≤18.5,10.0≤Ni≤13.0,2.0≤Mo≤3.0,0.06≤N≤0.14,0.01≤Co≤0.08,0.01≤Cu≤0.50, B≤0.0018, surplus is Fe;
(2) rotary casting or the method such as hot piercing, hot extrusion is adopted to obtain hollow forging;
(3) hollow forging carries out hot rolling after reconditioning between 1000-1250 DEG C;
(4) hot-rolled tube carries out solution heat treatment at 1030-1150 DEG C;
(5) oxide skin of solid solution state hot-rolled tube is removed
(6) be rolled into QC and can carry out clod wash or hot bending processing, after bending, carry out annealing thermal treatment.
On the basis of technique scheme, the present invention can also do following improvement:
Further, in step (1), control alloying element content, make 1.4≤(Cr+Mo+1.5Si)/(Ni+0.5Mn+20N)≤1.8;
Further, in step (1), the alloying element contents such as control Cr, Mo, N, make Cr+3.3Mo+16N >=27.5;
Further, the hot rolling deformation in described step (3) is than between 1.7:1-6.0:1.
Further, the solution heat treatment time in described step (4) presses 0.6-2min/mm according to product wall thickness and controls.
Further, the annealing thermal treatment temp in described step (6) is 1030-1130 DEG C.
The invention has the beneficial effects as follows: by alloying element contents such as adjustment Cr, Ni, Mo, Si, Mn, N, reduce the impurity contents such as P, S, O, control the processing parameters such as hot-rolled temperature, hot rolling deformation amount, hot-rolled tube solid solubility temperature, bend pipe annealing temperature, the grain boundary of austenite under cast condition is suppressed to form low melting component, fining austenite grains, abundant solution modeling phase, makes above-mentioned control nitrogen austenitic stainless steel have good heat and adds performance, mechanical property and corrosion resistance nature.
1）C≤0.03
C is strong formation and the element of stable austenite in austenitic stainless steel, can be significantly improved the intensity of austenitic stainless steel by solution strengthening.But because C can form the Cr of high Cr with the Cr in steel in austenitic stainless steel
23c
6type carbide, thus cause the poor Cr in local, make the corrosion resistance nature particularly intergranular corrosion resistance performance decline of steel.Therefore in order to prevent corrosion among crystalline grains from reducing, the content of C element should be not more than 0.03.
2）Si≤1.0，Mn≤2.0
Si, Mn element generally adds as deoxidant element in conventional Chromiumnickel Austenite Stainless Steel.Si element can promote that the ferrite in steel and intermetallic phase (such as σ phase) are formed, thus affects the performance of steel; S element in Mn element and steel combines, and forms MnS inclusion, and the resistance to pitting attack performance of stainless steel and crevice corrosion behavior can be caused to decline.Therefore Si and the Mn element in steel controls to be advisable being not more than 1.0 and 2.0 respectively.
3）P≤0.035，S≤0.010
The solubleness of the impurity elements such as P, S in austenite is low, along with the carrying out solidified enrichment gradually in molten steel, last segregation, at austenite column crystal crystal boundary, reduces the bonding force of austenitic stainless steel crystal boundary, easily ftracture in hot procedure, reduce the hot workability of ingot casting.Therefore it is low that P, S, O content in austenitic stainless steel should be tried one's best, and P, S element in steel controls to be advisable being not more than 0.035 and 0.010 respectively.
4）17.0≤Cr≤18.5
Cr is the principal element improving stainless steel erosion resistance, therefore in order to improve erosion resistance, should carry high-Cr as far as possible.Cr is strongly formed and stablizes ferritic element, and too high ferrite content can cause stainless hot workability to worsen, and the Cr content in steel can not be too high.Therefore the Cr content in steel controls to be advisable between 17.0-18.5.
5）10.0≤Ni≤13.0
Ni is strong formation and the principal element of stable austenite in austenitic stainless steel, also can improve the corrosion resistance nature of steel in reductibility corrosive medium simultaneously; But because metallic nickel is expensive, in stainless steel, adds membership in a large number improve raw-material cost greatly.Therefore Ni content controls to be advisable between 10.0-13.0.
6）2.0≤Mo≤3.0
The ability of Mo element raising stainless steel corrosion resistance nature is 3.3 times of Cr element, and the existence of Mo element greatly improves the various corrosion resisting properties of ferritic stainless steel; But because metal molybdenum is expensive, in stainless steel, add membership in a large number improve raw-material cost greatly.Therefore Mo constituent content controls to be advisable between 2.0-3.0.
7）0.06≤N≤0.14
N element is the useful alloy element of austenitic stainless steel.Adding of appropriate nitrogen, greatly can improve the intensity of austenitic stainless steel when plasticity and the toughness of not obvious reduction material, nitrogen can also improve the corrosion resistance nature of austenitic stainless steel strongly simultaneously, and its beneficial effect is 16-30 times of Cr.But too high nitrogen content can form the nitride of low melting point at crystal boundary, cause the reduction of materials hot working performance.Therefore Control of Nitrogen Content is advisable at 0.06-0.14%.
8）0.01≤Co≤0.08，0.01≤Cu≤0.50
Co and Cu is austenite former in austenitic stainless steel, and Cu element can also reduce the preliminary work hardening rate of austenitic stainless steel and improve hydrogen and cause delayed cracking.The irradiation behaviour of Co and Cu element strong deterioration austenitic stainless steel, therefore Co, Cu constituent content should control as far as possible low; But because current stainless steel-making process is difficult to get rid of Co, Cu element, too low Co, Cu constituent content can significantly improve material cost.Therefore the Co control of element in steel is advisable between 0.01-0.08, and Cu constituent content controls to be advisable at 0.01-0.50.
9）B≤0.0018
B element is strong Grain Boundary Segregation element in austenitic stainless steel, and appropriate B adds, and the impurity elements such as P, S, O can be suppressed in the segregation of crystal boundary, purification crystal boundary, thus improves the hot workability of austenitic stainless steel.But B significantly worsens the irradiation behaviour of austenitic stainless steel, therefore in steel, B content controls to be advisable being not more than 0.0018.
10）1.4≤(Cr＋Mo＋1.5Si)/(Ni＋0.5Mn＋20N)≤1.8
Ferritic phase is second-phase tissue common in austenitic stainless steel solidified structure.A small amount of ferrite can play the effect of the impurity elements such as P, S, the O dissolved in steel, suppresses low melting component in the formation of austenite grain boundary, thus improves the hot workability of austenitic stainless steel; But due to the Deformation Resistance between ferrite and austenite two-phase and thermoplasticity inconsistent, in hot procedure, easily form crackle at two-phase interface, too high ferrite content worsens the hot workability of austenitic stainless steel.Therefore, the ferrite content be suitable for should be controlled, to improve the hot workability of steel ingot.
Ferrite content in austenitic stainless steel solidified structure mainly affects by the chemical composition of material.The elements such as Cr, Mo, Si are ferrite phase forming element, and content is higher, and the ferrite formed in solidified structure is more; Ni, Mn, N etc. are austenite formers, and content is higher, and the ferrite formed in solidified structure is fewer.For control nitrogen austenitic stainless steel, when the Ratio control of (Cr+Mo+1.5Si)/(Ni+0.5Mn+20N) is between 1.4-1.8, ferrite content in ingot casting is the most suitable, and now ingot casting can obtain best hot workability.
11）Cr＋3.3Mo＋16N≥27.5
Cr, Mo and N element can characterize with spot corrosion index (PittingResistanceEquivalentNumber, PREN) the impact of the corrosion resistance nature of austenitic stainless steel.Spot corrosion index is higher, and austenitic stainless steel has higher corrosion resistance nature.Control Cr+3.3Mo+16N >=27.5, control nitrogen austenitic stainless steel can obtain good corrosion resistance nature.
12) hot-rolled process parameter
Hot-rolled temperature is lower, deformation ratio is larger, and the energy of deformation storage of hot-rolled tube billet is more, and after solution heat treatment, Recrystallization nucleation position is more, and recrystal grain is thinner.But rolling temperature is too low, deformation ratio is too high, and one is that resistance to deformation is too large, and mill capacity is inadequate; Two is easily occur rolling crack.Hot-rolled temperature controls to be advisable between 1000-1250 DEG C, and deformation ratio controls to be advisable between 1.7:1-6:1.
13) solution heat treatment temperature
Thermal treatment temp is too high, recrystal grain abnormal growth, produces mixed crystal and coarse grain defect; Thermal treatment temp is too low, the Cr in hot procedure
23c
6, Cr
2n precipitate equal to intermetallic dissolves not exclusively, and corrosion resistance nature, the plasticity and toughness of product are poor.Final solution heat treatment temperature controls to be advisable at 1030-1150 DEG C.
Accompanying drawing explanation
Fig. 1 is 1#(0.11%N) and 7#(0.15%N) control the stretched thermoplastic curve of nitrogen austenitic stainless steel ingot casting.
Fig. 2 is the impact of (Cr+Mo+1.5Si)/(Ni+0.5Mn+20N) ratio on control nitrogen austenitic stainless steel 1250 DEG C of Tensile fracture shrinking percentages.
Fig. 3 is that rolling temperature controls the impact of nitrogen austenitic stainless steel grain fineness number to 11#.
Fig. 4 is the impact that rolling deformation comparison 12# controls nitrogen austenitic stainless steel grain fineness number.
Fig. 5 is that solid solubility temperature controls the impact of nitrogen austenitic stainless steel grain fineness number to 13#.
Fig. 6 is that 13# controls the grain structure of nitrogen austenitic stainless steel after 1090 DEG C of thermal treatment (grain fineness number 5.0 grades).
Fig. 7 is that 13# controls the grain structure of nitrogen austenitic stainless steel after 1180 DEG C of thermal treatment (grain fineness number 2.5 grades).
Fig. 8 is that solution heat treatment temperature controls the impact of nitrogen austenitic stainless steel pitting attack current potential to 13#.
Fig. 9 is the impact of pitting attack indices P REN on control nitrogen austenitic stainless steel pitting potential.
Figure 10 is the impact of nitrogen content on control nitrogen austenitic stainless steel 350 DEG C of high-temperature yield strengths.
Figure 11 is that grain fineness number controls the impact of nitrogen austenitic stainless steel high-temperature yield strength to 13#.
Figure 12 is the grain structure (grain fineness number 5.0 grades) of control nitrogen austenitic stainless steel bend pipe.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Adopt vacuum induction melting 7 stove steel (table 1).Adopt Gleeble3800 heating power processing experiment machine to determine the relative reduction in area of ingot casting tension specimen 850-1375 DEG C of temperature range, carry out the hot workability of exosyndrome material with it.
The composition of table 1 vacuum induction melting control nitrogen austenitic stainless steel sample, wt%
Note: represent that this value is not within invention scope;
Adopt electric furnace+AOD furnace+rotary casting melting to have cast 4 stove steel (table 2), each stove steel carries out hot rolling and the heat treatment process (table 3) of different technical parameters.Grain fineness number grading is carried out by GB/T6394-2002 " metal mean grain size assay method ", measure it at 30 DEG C, pitting potential in 3.5%NaCl solution by GB/T17899-1999 " stainless steel pitting potential measuring method ", measure its 350 DEG C of high temperature tensile properties by GB/T4338-2006 " Metal Materials At High Temperature stretching test method ".
The composition of table 2AOD stove melting control nitrogen austenitic stainless steel sample, wt%
Table 3 controls nitrogen austenitic stainless steel sample working process parameter and results of property
Note: 1) represent that this value is not within invention scope;
2)/represent and do not carry out this road manufacturing procedure or this inspection.
Embodiment 1: the hot workability of control nitrogen austenitic stainless steel
Figure 1 show the hot workability curve of 7# ingot casting (0.15N) and 1# ingot casting (0.11N).Compared with 1# ingot casting, the hot workability of 7# ingot casting starts obviously to decline at 1225 DEG C, and the relative reduction in area of 1250 DEG C is 43%, far below 67% of 1# ingot casting.Result shows, the high-temperature zone hot workability of too high nitrogen content to 316LN stainless steel ingot casting has disadvantageous effect.
Figure 2 illustrate (Cr+Mo+1.5Si)/(Ni+0.5Mn+20N) ratio is on the impact of the hot workability of 316LN 1250 DEG C time.When control (Cr+Mo+1.5Si)/(Ni+0.5Mn+20N) ratio is between 1.4-1.8, relative reduction in area has all exceeded 60%, and this value is lower than 1.4 or when being greater than 1.8, and relative reduction in area is lower than 40%.Result shows, the 316LN ingot casting with suitable (Cr+Mo+1.5Si)/(Ni+0.5Mn+20N) ratio has good hot workability.
Embodiment 2: the grain fineness number of control nitrogen austenitic stainless steel
11# is controlled nitrogen austenitic stainless steel and is carried out in differing temps the hot rolling that deformation ratio is 3.1:1, and then 1090 DEG C of solution treatment, accompanying drawing 3 is shown in the impact of hot-rolled temperature on grain fineness number.Result shows, reduce the grain size number that hot-rolled temperature can significantly improve control nitrogen austenitic stainless steel, hot-rolled temperature controls below 1250 DEG C, can obtain 4.5 and other grain structure of higher level.Hot-rolled temperature can not be too low, because resistance to deformation is too large 950 DEG C time, there is the problem that plug is stuck.
12# controls nitrogen austenitic stainless steel enters different distortion ratio hot rolling at 1150 DEG C, and then 1090 DEG C of solution heat treatment, accompanying drawing 4 is shown in the impact of hot rolling deformation comparison grain fineness number.Result shows, improve hot rolling deformation than the grain size number that can significantly improve control nitrogen austenitic stainless steel, hot rolling deformation ratio controls more than 1.7, can obtain 4.0 and other grain structure of higher level.Hot rolling deformation ratio can not be too high, after 6:1, there is the problem that pipe material inner wall produces thermal crack.
13# is controlled nitrogen austenitic stainless steel and has been carried out at 1150 DEG C the hot rolling that deformation ratio is 3.2:1, and then carry out solution treatment in differing temps, accompanying drawing 5 is shown in the impact of solution heat treatment temperature on grain fineness number.Result shows, solution heat treatment temperature increases, and recrystallization crystal particle dimension is larger, and solution heat treatment temperature controls below 1150 DEG C, can obtain 4.0 and other grain structure of higher level.Accompanying drawing 6 gives 13# and controls the metallographic structure of nitrogen austenitic stainless steel after 1090 DEG C of solution heat treatment (5.0 grades), and accompanying drawing 7 gives 13# and controls the metallographic structure of nitrogen austenitic stainless steel after 1180 DEG C of solution heat treatment (2.5 grades).
Embodiment 3: the corrosion resistance nature of control nitrogen austenitic stainless steel
Solution heat treatment temperature is shown in accompanying drawing 8 to the impact that 13# controls nitrogen austenitic stainless steel pitting attack current potential.Result shows, thermal treatment temp is too low, and precipitate does not dissolve completely, has disadvantageous effect to pitting attack performance.Solution heat treatment temperature should control more than 1030 DEG C.
Figure 9 shows 11#, 12#, 13#, 14# and control nitrogen austenitic stainless steel and the stainless pitting potential of 09X18H10T, Z2CND18-12.Test-results shows, the pitting potential with the control nitrogen austenitic stainless steel of high PRE value is higher, and the pitting potential of the control nitrogen austenitic stainless steel invented is higher than 09X18H10T, Z2CND18-12 stainless steel.
Embodiment 4: the mechanical property of control nitrogen austenitic stainless steel
Accompanying drawing 10 is shown in the impact of nitrogen content on control nitrogen austenitic stainless steel 350 DEG C of high-temperature yield strengths, and grain fineness number is shown in accompanying drawing 11 to the impact that 13# controls nitrogen austenitic stainless steel 350 DEG C of high-temperature yield strengths.By solution strengthening and the grain refining strengthening of nitrogen, invent control nitrogen austenitic stainless steel 350 DEG C of high-temperature yield strengths far more than 135MPa requirement in RCMM standard, reach more than 150MPa.
Embodiment 5: the grain fineness number of bend pipe controls
14# steel the 20th batch of straight tube finished product is shaped through hot bending, and the 21st batch of straight tube finished product, through cold bending, bends back elbow and heat-treat at 1080 DEG C.Compared with straight tube, bend pipe grain fineness number has almost no change, and 20 batches of bend pipe grain fineness numbers are 5.0 grades (accompanying drawings 12), and 21 batches of bend pipe grain fineness numbers are 5.5 grades.
The foregoing is only a part for all embodiments of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. control a nitrogen austenitic stainless steel, it is characterized in that, component weight percentages is: C≤0.03, Si≤1.0, Mn≤2.0, P≤0.035, S≤0.010,17.0≤Cr≤18.5,10.0≤Ni≤13.0,2.0≤Mo≤3.0,0.06≤N≤0.14,0.01≤Co≤0.08,0.01≤Cu≤0.50, B≤0.0018, surplus is Fe;
Alloying element content meets the relation of 1.6≤(Cr+Mo+1.5Si)/(Ni+0.5Mn+20N)≤1.8, Cr, Mo, N element content meet the relation of PREN=Cr+3.3Mo+16N >=27.5, and wherein PREN is the spot corrosion index of control nitrogen austenitic stainless steel.
2. a manufacture method for control nitrogen austenitic stainless steel according to claim 1, is characterized in that, processing step is:
(1) according to following elements weight percent melting molten steel: C≤0.03, Si≤1.0, Mn≤2.0, P≤0.035, S≤0.010,17.0≤Cr≤18.5,10.0≤Ni≤13.0,2.0≤Mo≤3.0,0.06≤N≤0.14,0.01≤Co≤0.08,0.01≤Cu≤0.50, B≤0.0018, surplus is Fe; Alloying element content meets the relation of 1.6≤(Cr+Mo+1.5Si)/(Ni+0.5Mn+20N)≤1.8, and Cr, Mo, N element content meet the relation of PREN=Cr+3.3Mo+16N >=27.5;
(2) adopt rotary casting or hot piercing, hot extrusion obtains hollow forging;
(3) hollow forging carries out hot rolling after reconditioning between 1000-1250 DEG C, and hot rolling deformation is than between 1.7:1-6.0:1;
(4) hot-rolled tube carries out solution heat treatment at 1030-1150 DEG C;
(5) oxide skin of solid solution state hot-rolled tube is removed;
(6) be rolled into QC and carry out clod wash or hot bending processing, after bending, carry out annealing thermal treatment.
3. manufacture method according to claim 2, is characterized in that, the solution heat treatment time in step (4) presses 0.6-2min/mm according to product wall thickness and controls.
4. manufacture method according to claim 2, is characterized in that, the annealing thermal treatment temp in step (6) is 1030-1130 DEG C.
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| CN106191405A (en) * | 2016-08-23 | 2016-12-07 | 钢铁研究总院 | A kind of heat-treatment furnace high-performance austenitic heat-resistance steel and preparation method thereof |
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| CN113201697B (en) * | 2021-04-13 | 2022-12-23 | 浙江信得达特种管业有限公司 | High-temperature concentrated sulfuric acid corrosion resistant austenitic stainless steel with excellent hot-working performance and hot-piercing method thereof |
| CN114934240B (en) * | 2022-04-25 | 2023-10-10 | 中国科学院金属研究所 | Preparation method of ultra-high-strength high-corrosion-resistance high-nitrogen austenitic stainless steel |
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