Summary of the invention
In order to overcome the above-mentioned deficiency of existing austenitic stainless steel and steel pipe thereof, the invention provides a kind of austenitic stainless steel and austenitic stainless steel pipe thereof that possesses corrosion resistance nature under high temperature creep strength and the high temperature simultaneously, the manufacture method of this steel pipe is provided simultaneously.
This austenitic stainless steel with the composition quality per distribution ratio of austenitic stainless steel pipe is:
C?0.060%~0.14% 0<Si≤0.50% 0<Mn≤1.00% P<0.040%
S<0.015% Cr?17.00%~20.00% Ni?8.00%~11.00%
Cu?2.50~4.00% Nb?0.30~0.60% Mo?0.15~0.50%
Co?0.15~0.50% N?0.05~0.14% B?0.001%~0.01%
All the other are Fe and unavoidable impurities.
This austenitic stainless steel with the preferable composition quality per distribution ratio of austenitic stainless steel pipe is:
0.070%≤C≤0.09% 0<Si≤0.30% Mn?0.50%~1.00% P<0.025%
S<0.005% Cr?17.50%~18.50% Ni?8.50%~9.50%
Cu?2.80~3.30% Nb?0.40~0.60% Mo?0.15~0.25%
Co?0.15~0.25% N?0.080~0.130% B?0.003%~0.008%
All the other are Fe and unavoidable impurities.
This austenitic stainless steel with the optimal components quality hundred good composition proportion of austenitic stainless steel pipe is:
C?0.080% Si?0.25% Mn?0.80% P0.015% S<0.001%
Cr?18.10% Ni?9.0% Cu?3.0% Nb?0.45% Mo?0.20%
All the other are Fe and unavoidable impurities for Co 0.18% N 0.011% B 0.005.
The diameter of steel pipe is generally Φ 25.4mm~Φ 101.6mm, and length is not less than 6000mm.
Describe with regard to stainless steel composition mechanism of the present invention below.
When austenitic stainless steel used under hot environment, C can significantly improve the hot strength of austenitic stainless steel as the gap solid solution element.Have again, carbon and niobium effect form Nb (CN), produce precipitation strength in the use, form tiny CrNbN (Z mutually) at intracrystalline together with Nb, Cr, N and carry out dispersion-strengthened, need enough carbon performance strengthening effect, therefore the lower control limit of carbon is brought up to more than 0.06% by traditional 0.04%; In addition because carbon and Cr form Cr easily
23C
6Compound, thus cause the poor chromium of intergranular to cause intergranular corrosion in the use easily, and therefore the upper control limit with carbon is controlled in 0.14%.Carbon is limited between 0.060% to 0.14% among the present invention.
Si adds as reductor when steel-making, but addition is excessive, then can have influence on austenitic stability, and increase formation δ reaches K mutually and is inclined to mutually, limits 0<Si<0.50% for this reason.
Deoxidation, the sweetening agent of Mn during as melting adds, and is to form austenitic element.If addition is excessive, then can have influence on separating out of CrNbN in the use (Z phase), be unfavorable for improving the creep rupture strength of material.Therefore, in this stainless steel, 0<Mn<1.00%.
Cr improves austenitic stainless steel corrosion resistance nature and the indispensable element of antioxidant property, the content of Cr is high more, and corrosion resistance nature and antioxidant property are good more, yet if add too much, then need higher Ni to guarantee the balance of organizing, manufacturing cost also can significantly increase.The present invention is decided to be 17.00%~20.0% with the content of Cr.
Ni forms as austenite and adds in the steel, adds at least structure stability and destroys, and it is too high to add excessive then manufacturing cost.Therefore, among the present invention, the content of Ni is 8.00%~11.00%.
Cu has the element of great role to improving creep-rupture strength, and the Cu that is solid-solubilized in the steel separates out with the form of the spherical rich Cu phase tiny, that disperse distributes at time of prescription, and the rich Cu phase amount of separating out, size and distribution directly have influence on the creep rupture strength of steel.Test-results shows: along with the increase of Cu content in the steel, the amount of separating out of rich Cu phase increases, and its size and disperse degree be respective change also, and creep rupture strength also constantly rises.But when Cu content added some amount to, the rich Cu that separates out met to assemble and grows up, and strengthening effect descends, because Cu is a low melting point element, can separated out and worsened the hot workability of material along crystal boundary when carrying out hot-work.The content of Cu is 2.50%~4.00% among the present invention.
Nb adds in the alloy, purpose is and C, N forms Nb (CN) compound, thereby compound in use produces the creep-resistant property that the precipitation hardening dispersion has improved material, the tiny Nb (CN) that separates out at tubulation later stage utilization secondary thus the effect refine austenite stainless steel crystal grain of pinning crystal boundary increases substantially material high temperature resistance steam corrosion performance and heat resistanceheat resistant temperature fatigue property.Have again, be solid-solubilized in Cr, Nb, N in the steel and between the usage period subsequently, form more tiny CrNbN (Z phase) and separate out M at intracrystalline
23C
6Separate out attached to CrNbN (Z phase), not only become one of main strengthening phase that improves creep-rupture strength, and improved the intergranular corrosion resistance performance of steel.The limited range of Nb is 0.30~0.60% among the present invention
Mo and Co add in the steel as trace element, except that significantly improve stainless steel hot rigid, the carbide of can also refinement separating out helps welding.The addition of Mo and Co all is limited between 0.15~0.50% among the present invention.
Nitrogen is the same with carbon, all is gap solid solution elements, except with Nb, Cr generate Nb (C, N) and NbCrN mutually beyond, also help crystal grain thinning, but nitrogen can not cause intergranular corrosion to be inclined to, so the limited range of N is between 0.05~0.14%.
B adds in the steel as trace element, mainly plays to purify the austenitic stainless steel crystal boundary, reduces the hole of crystal boundary existence in use, to improve the hot strength of alloy.Among the present invention, the limited range of B is 0.001%~0.01%.
Stainless steel tube manufacture method of the present invention comprises following step successively:
One, smelts
Molten iron as main raw material, is smelted the molten steel that becomes to meet this austenitic stainless steel pipe;
Two, pouring molten steel is become steel ingot or continuously cast bloom;
Three, bar processing
Steel ingot or continuously cast bloom is rolling or forge into round steel, round steel is cut into pipe.
Four, bore a hole or be squeezed into hollow billet
Pipe after heating, is made hollow billet after employing perforation or the extruding;
Five, steel pipe deep processing
With hollow billet cold drawing or cold rolling one-tenth hollow forging, hollow forging is through annealing, after the pickling, minimumly makes finished product again after a cold drawing or cold rolling and annealing and pickling.
Say that in detail stainless-steel seamless pipe manufacture method of the present invention comprises following key step successively:
A preprocessed molten iron B top and bottom combined blown converter smelting
The refining of C vacuum oxygen decarburization stove decarburization D ladle refining furnace
One, smelts
Pretreated molten iron through the thick refining of the compound blow converter in the end, top and the decarburization of vacuum oxygen decarburization stove and mend nitrogen and the ladle refining furnace refining after, the composition quality percentage ratio of molten steel reaches following requirement can tap, and pours into steel ingot or continuously cast bloom.
0.060%<C<0.14% 0<Si<0.50% 0<Mn<1.00%
P<0.040%S<0.015% Cr?17.00%~20.00% Ni?8.00%~11.00%
Cu?2.50~4.00% Nb?0.30~0.60% Mo?0.15~0.50%
Co?0.15~0.50% N?0.05~0.14% 0.001%<B<0.01%,
All the other are Fe and unavoidable impurities.
When top and bottom combined blown converter smelting, the decarburization second phase is adopted the nitrogen reduction, and reaches the requirement of vacuum oxygen decarburization stove decarburization to N, content ≮ 1500ppm of N;
When the decarburization of vacuum oxygen decarburization stove, vacuum tightness≤106.4Pa, target 66.5Pa avoids over-blowing in the decarburization of vacuum oxygen decarburization stove, guarantees that end point carbon hits.Carry out nitrogen alloying after the decarburization, nitrogen is adjusted in 800~1300ppm scope.
Adjust other alloying constituents in the ladle refining furnace refining and enter span of control.
Two, pouring molten steel is become steel ingot or continuously cast bloom
Guarantee at ladle refining furnace under the situation of slag good fluidity that temperature adjustment is surrendered mould and annotated or continuous casting to 1530 ± 10 ℃ of teeming temperatures.Casting blank specification is generally pressed 220mm * 220mm * 3000~3300mm control.
Three, bar processing
The A heating
In heating process, comprise the steel ingot soaking operation in the steel ingot cogging process, cogged ingot or continuously cast bloom are rolling or forge preceding heating process, and Heating temperature is: 1250~1300 ℃, steel ingot is not less than 11 hours heat-up time, and cogged ingot or continuously cast bloom are not less than 2.5 hours heat-up time.
Rolling or the forging of B
At rolling or forging process, that cogged ingot or continuously cast bloom is rolling or forge into bar.Start rolling temperature 〉=1150 ℃, finishing temperature: 〉=950 ℃.The rolling deformation passage determines that according to the bar specification initial pass deformation is not more than 30%.When guaranteeing dimensions, must not there be folding, tie rod, the ears or side handles of a utensil and serious defectives such as scuffing in the surface.
The C pipe is prepared
According to external diameter, wall thickness, the length of fished pipe, choose reasonable bar length, and the blanking of stub material cut into pipe, and behind the hole that centers, carry out peeling and handle, handling the rear surface must not have crackle, pit, casting skin, be mingled with.
Four, preparation hollow billet
The A heating of pipe blank
In the heating of pipe blank operation, 1100~1220 ℃ of Heating temperatures are no less than 1.5 hours heat-up time.
B bores a hole or is squeezed into hollow billet
In perforation or extrusion process, initial deformation temperature is no less than 1050 ℃, finishes texturing temperature and is not more than 1300 ℃.
Five, steel pipe deep processing
Cold rolling or the cold-drawn of A
Cold rolling or cold-drawn is that hollow billet cold working is the distortion operation that hollow billet is processed into the hollow forging of final dimension, and passage cold deformation amount is not less than 15% before the finished product, prevents the generation of inclined to one side wall and scuffing in the production process.Hollow forging is through annealing, pickling, finished product is made in cold rolling and annealing and pickling once more.
Operation annealing in the middle of the B
Middle operation annealing temperature in the cold working process is not less than 1100 ℃, and soaking time is determined (being no less than wall thickness 1.5min/mm) according to wall thickness, and can come out of the stove after the insulation is cooled to room temperature.
The C pickling
The hollow forging pickling is to adopt HNO
3Pickling is carried out in+HF acid, and the Acidwash solution proportioning is according to HNO
3Acid is in 15~20% scopes, and HF acid is controlled in 1~5% scope.Can carry out the surface inspection and the cleaning of pipe after the hollow forging pickling, eliminate the naked eyes visual defects.
The cold rolling once more or cold-drawn of D
Hollow forging is according to the fished pipe size after the pickling, selects the cold rolling or cold-drawn of at least one passage to be processed into trimmed size.
The E finished products
1120~1190 ℃ of solid solubility temperatures, soaking time is determined (being no less than wall thickness 2.5min/mm) according to wall thickness, insulation postcooling rate request is greater than 25 ℃/second, but water-cooled.
The F finished product acid-washing
The production tube pickling is to adopt HNO
3Pickling is carried out in+HF acid, and the Acidwash solution proportioning is according to HNO
3Acid is in 15~20% scopes, and HF acid is controlled in 1~5% scope.After the fished pipe pickling, require the pipe surfaces externally and internally not allow to exist oxide skin, surperficial residual acid, peracid, crackle, crack, folding, pipe, roll folding, layering, hairline and more serious scuffing, defective such as wound.
The invention provides out the manufacture method of a kind of high temperature resistant, high pressure resistant, austenitic stainless steel of anti-steam corrosion the and steel pipe and steel pipe, the weldless steel tube that present method is produced, have good high temperature creep-resisting performance, excellent high temperature steam corrosive nature, good thermal fatigue resistance and high temperature oxidation resistance etc., be applicable to and make pressure-containing member or the anti-oxidant parts that in high temperature, high pressure and corrosive environment, use for a long time, be particularly suitable for superheater and reheater in high-parameters, the jumbo ultra supercritical thermal power generation boiler.Solve the problem of ultra supercritical station boiler with the critical material critical shortage,
Embodiment
Describe the embodiment of the manufacture method of this austenitic stainless steel and steel pipe and steel pipe in detail below in conjunction with embodiment, but the embodiment of the manufacture method of this austenitic stainless steel and steel pipe thereof and steel pipe is not limited to following embodiment.
Austenitic stainless steel embodiment one
The composition quality percentage ratio of this austenitic stainless steel embodiment is:
C?0.080% Si?0.25% Mn?0.80% P0.015% S<0.001%
Cr?18.10% Ni?9.0% Cu?3.0% Nb?0.45% Mo?0.20%
All the other are Fe and unavoidable impurities for Co 0.18% N 0.011% B 0.005.
Austenitic stainless steel embodiment two
The composition quality percentage ratio of this austenitic stainless steel embodiment is:
C?0.08% Si?0.19% Mn?0.72% P?0.0012%
S?0.002% Cr?18.32% Ni?9.11% Cu?2.88%
Nb?0.52% Mo?0.19% Co?0.22% N?0.095%
B 0.004%, and all the other are Fe and unavoidable impurities.
Austenite stainless steel seamless steel tube embodiment one
The specification of this austenite stainless steel seamless steel tube embodiment is Φ 54 * 8mm, long 10000mm, and its composition quality percentage ratio is:
C?0.080% Si?0.25% Mn?0.80% P0.015% S<0.001%
Cr?18.10% Ni?9.0% Cu?3.0% Nb?0.45% Mo?0.20%
All the other are Fe and unavoidable impurities for Co 0.18% N 0.011% B 0.005.
Austenite stainless steel seamless steel tube embodiment two
The specification of this austenite stainless steel seamless steel tube embodiment is Φ 54 * 8mm, long 10000mm, and its composition quality percentage ratio is:
C?0.08% Si?0.19% Mn?0.72% P?0.0012%
S?0.002% Cr?18.32% Ni?9.11% Cu?2.88%
Nb?0.52% Mo?0.19% Co?0.22% N?0.095%
B 0.004%, and all the other are Fe and unavoidable impurities.
Method of manufacturing seamless steel pipe embodiment
The present embodiment manufacturing be above-mentioned austenite stainless steel seamless steel tube embodiment one, its main manufacturing step is as follows successively:
One, smelts
Pretreated molten iron is through after pushing up the compound blow converter smelting in the end and decarburization of vacuum oxygen decarburization stove and ladle refining furnace refining, and the composition quality percentage ratio of molten steel reaches following requirement can go out the punching block notes,
C?0.080% Si?0.25% Mn?0.80% P0.015% S<0.001%
Cr?18.10% Ni?9.0% Cu?3.0% Nb?0.45% Mo?0.20%
All the other are Fe and unavoidable impurities for Co 0.18% N 0.011% B 0.005.
When top and bottom combined blown converter smelting, the decarburization second phase is adopted the nitrogen reduction, and reaches the requirement of vacuum oxygen decarburization stove decarburization to N, and this moment, the content of N was 1820ppm;
When the decarburization of vacuum oxygen decarburization stove, vacuum tightness≤106.4Pa, target 66.5Pa, the decarburization to 0.082% of vacuum oxygen decarburization stove.Carry out nitrogen alloying after the decarburization, nitrogen is adjusted to the 920ppm scope.
Adjust other alloying constituents in the ladle refining furnace refining and enter span of control.
Two, pouring molten steel is become steel ingot or continuously cast bloom
Under the situation that guarantees the slag good fluidity, temperature adjustment is surrendered mould and is formed 5.8 tons of steel ingots to 1535 ℃ of teeming temperatures.Casting blank specification is 220mm * 220mm * 3150mm.
Three, bar processing
The A heating
Steel ingot carries out 14 hours heating in soaking pit, and soaking temperature has guaranteed that steel ingot burns all to grill thoroughly according to 1250~1270 ℃ of controls in the heat-processed.
Rolling or the forging of B
Become 220 through the cogging of φ 1000mm blooming mill
2The mm cogged ingot.Start rolling temperature is 1230 ℃ in the cogging process, and finishing temperature is 1012 ℃, rolls surface imperfection such as the no folding in back, the ears or side handles of a utensil.Processing back cogged ingot is of a size of 220mm * 220mm * 3000~3300mm.Cogged ingot is heated pushing away continuously in the steel heater, heating and temperature control is at 1250~1270 ℃, be 2 hours 40 minutes total heat-up time, the heating back is rolled into φ 130mm bar through 11 passage distortion on φ 650mm milling train, initial passage distortion pass is the box hole, and slubbing time deflection is 19%, and opening a sluice gate temperature is 1240 ℃, finishing temperature is 1030 ℃, rolls the no folding in bar surface, back, tie rod, the ears or side handles of a utensil and serious defectives such as scuffing.Be rolled into after the bar, sawing becomes to be of a size of the bar of φ 130mm * 6000~8000mm.
The C pipe is prepared
According to final dimension specification Φ 54mm * 8mm * 10M, consider that scaling loss in the course of processing, acid are decreased and crop influences factors such as lumber recovery, bar material is cut into φ 130mm * 1100~1250mm pipe, after surface scale is fallen in lathe turning, beat and decide the core hole.
Four, preparation hollow billet
Pipe is put into the end inlet side successively and is gone out the heating of wedged bottom stove, and Heating temperature is 1200 ℃, and be 120 minutes heat-up time, the tapping of heating back.Pipe carries out hot piercing through transmission roller-way arrival Φ 89 cone mills and makes hollow billet, and the hot piercing initial deformation temperature is 1080 ℃, and the hollow billet surface temperature is 1180 ℃ after the hot piercing, perforation back direct water-cooling.Be of a size of Φ 134mm * 14mm this moment, and the hollow billet surfaces externally and internally is good, zero defect.
Five, steel pipe deep processing
With hollow billet after pickling and reconditioning, it is cold rolling and cold drawn together to carry out twice, size becomes Φ 114mm * 11mm (cold rolling back, first road), Φ 89mm * 9.8mm (second to cold rolling back) and Φ 76mm * 9.8mm successively by hollow billet Φ 134mm * 14mm, through the cold rolling one-tenth trimmed size of a passage Φ 54mm * 8mm, again the sawing of steel pipe scale is become 10 meters/again.
Steel pipe is in cold rolling or Cold Drawing Process, and every cold deformation once must once be deoiled, middle operation annealing, aligning, Pipe Cutting, pickling, check and reconditioning, to the last solution annealing before the finished product.Middle operation annealing temperature is 1120~1130 ℃, and soaking time is respectively 40 minutes (cold rolling back, first road), 30 minutes (cold rolling back, second road), 30 minutes (first to cold drawn back).The finished product solid solubility temperature is 1130 ℃, and soaking time is 30 minutes.Steel pipe is cooled to room temperature immediately after process annealing operation and the finished product solution annealing.
Through packing warehouse-in after the process of the steel pipe after finished product solution annealing aligning, Pipe Cutting, pickling, the check.
Present embodiment is in the also available extrusion molding of step 4 middle punch moulding, the reaming temperature is 1160~1200 ℃ in the extrusion process, after the reaming, rapidly the hollow base after the reaming is heated to 1180~1200 ℃ through induction heater again, after adopting the glass powder technological lubrication, surfaces externally and internally pushes the hollow billet direct water-cooling after the extruding.
Performance comparison
1, ambient temperature mechanical properties sees Table 1
Table 1
By contrast, be not difficult to find out that stainless traditional performance of the present invention is compared with stainless material 1Cr18Ni9,1Cr19Ni11Nb with the conventional high-tension boiler, have high room temperature yield strength and room temperature tensile strength, good yield tensile ratio is suitable for pressure-containing member.
2, the instantaneous performance of high temperature
Under 600 ℃, 650 ℃, 700 ℃, steel pipe has been carried out the high-temperature short delay stretching performance measurement respectively, test-results see Table 2 with table 3
Table 2
Table 3
By contrast, be not difficult to find out, yield strength under the test temperature of stainless steel tube of the present invention all is higher than 1Cr18Ni9,1Cr19Ni11Nb, is that the test steel has higher permissible stress by 662/3% design greater than this temperature lower yield strength according to the permissible stress value.
3, high temperature endurance performance
650 ℃ rupture test is carried out in steel pipe sampling, the testing data of steel pipe embodiment one and steel pipe embodiment two see Table respectively 4 with table 5
According to 320,3101,3020,323,3030,3040 testing datas and 3050 not disconnected at that time testing datas adopt method of least squares to carry out the endurance curve of regression treatment, regression treatment result: parameter A=2.67255, B parameter=-(wherein σ is a stress to 0.11704. with A and B substitution formula lg σ=A+Blgt, t is the time), can extrapolate and test 650 ℃ of steel pipes, 100,000 hours creep rupture strength is 122.3MPa, and the creep rupture strength that the creep rupture strength that is higher than 650 ℃ of 1Cr18Ni9 among the GB5310 far away is not less than 63MPa and 1Cr19Ni11Nb650 ℃ is not less than the 82MPa requirement.
Table 4 (by the end of on January 13rd, 2009) steel pipe embodiment one
Test piece number (Test pc No.) |
Stress, MPa |
Load, N |
Rupture time, h |
Remarks |
320 |
?260 |
?3293 |
?145 |
|
3010 |
?250 |
?3332 |
?206 |
|
3020 |
?230 |
?3071 |
?501 |
|
323 |
?210 |
?2541 |
?949 |
|
3030 |
?200 |
?2681 |
?1948 |
|
3040 |
?180 |
?2440 |
?4050 |
|
3050 |
?160 |
?2197 |
7728 is not disconnected |
08.2.26 load |
Table 5 (by the end of on January 13rd, 2009) steel pipe embodiment two
Test piece number (Test pc No.) |
Stress, MPa |
Load, N |
Rupture time, h |
Remarks |
321 |
?260 |
?3293 |
?149 |
|
3011 |
?250 |
?3332 |
?204 |
|
3021 |
?230 |
?3071 |
?505 |
|
324 |
?210 |
?2541 |
?942 |
|
3031 |
?200 |
?2681 |
?1941 |
|
3041 |
?180 |
?2440 |
?4061 |
|
3051 |
?160 |
?2197 |
7728 is not disconnected |
08.2.26 load |