CN108707828B - A kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method - Google Patents
A kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- 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
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- 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
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- 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
- C21C7/072—Treatment with gases
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- 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
- C21C7/10—Handling in a vacuum
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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Abstract
The invention discloses a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container, chemical component mass percents are as follows: C:0.06-0.08%, Si:0.20-0.35%, Mn:1.15-1.35%, Ti:0.01-0.02%, Ni:0.12-0.15%, Al:0.020-0.045%, P≤0.010%, S≤0.003%, [O]≤0.0015%, [N]≤0.0050%, [H]≤0.00015%, surplus Fe.Known to from the above, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention, by accurately controlling reduction C content, strong deoxidation, refinement crystal grain are carried out using Al, alloying is carried out using Ni, Ti element, there is its performance and be applicable in lower medium temperature (- 50 DEG C ~ -55 DEG C) and higher low-temperature impact toughness compared with 09MnD steel in Q/TDGG 0040-2004, and its overall mechanical properties is also more stable.
Description
Technical field
The present invention relates to the technical fields of the low-alloy steel in steel industry, and in particular to a kind of super high impact toughness, height
Degree of purity steel for low-temperature pressure container and its production method.
Background technique
Low-temperature pressure container is one of low-temperature (low temperature) vessel.The common ferritic steel of general pressure vessel, when temperature reduces
When to a certain temperature, reach brittle transition temperature, the toughness of steel sharply declines, easily broken.Pressure vessel is lower than transformation temperature
Under conditions of degree in use, as existed because of stress raisers caused by the factors such as defect, residual stress in container, container is just very
May the non-plastic fracture in the case where not having to occur obvious plastic deformation, to lead to catastrophic failure.
For low-temperature pressure container, first have to select suitable material with bearing medium depending on the application, these materials are necessary
There is good toughness at use temperature accordingly.The low-alloy through refinement crystal grain processing can be used in -45 DEG C or more media
The steel of nickel content 2.5% can be used in steel, -45 DEG C ~ -60 DEG C media, and the steel of nickel content 3.5% can be used in -60 DEG C ~ -104 DEG C media, -
The steel of nickel content 9.0% can be used in 104 DEG C ~ -196 DEG C media, and austenitic stainless steel or aluminium can be used to close for lower than -196 DEG C media
Gold.For avoid low-temperature pressure container generate stress raisers, answer close inspection during fabrication, it is dangerous in container to prevent
Defect.Therefore the necessary stringent control of low-temperature pressure container manufacture overall process, must be strictly controlled since raw material and produced
Journey is continuously improved purity of steel, prevents inside and outside defect.
Steel for low-temperature pressure container impact flexibility is advised in China's industry internal standard Q/TDGG 0040-2004
Fixed (standard analysis of 09MnD steel is as shown in Figure 1), -50 DEG C of impact flexibility requirements of middle-low alloy steel: KV2 >=60J.State at present
The 09MnD steel inside generallyd use is difficult to stably reach above-mentioned obdurability requirement, can only ensure -45 DEG C after normalized treatment
Safe handling, to ensure that pressure vessel is used safely at -50 DEG C -55 DEG C, it is necessary to redesign ingredient and Optimal improvements technique.
Summary of the invention
It is an object of the invention to: overcome the deficiencies of the prior art and provide a kind of super high impact toughness, high cleanliness low temperature
Steels for pressure vessel use and its production method have compared with the higher low-temperature impact toughness of 09MnD steel in Q/TDGG 0040-2004.Tool
There is following mechanical property: -50 DEG C of KV2 >=250J.
The technical solution used in the present invention is:
A kind of super high impact toughness, high cleanliness steel for low-temperature pressure container, chemical component mass percent are as follows: C:
0.06-0.08%, Si:0.20-0.35%, Mn:1.15-1.35%, Ti:0.01-0.02%, Ni:0.12-0.15%, Al:0.020-
0.045%, P≤0.010%, S≤0.003%, [O]≤0.0015%, [N]≤0.0050%, [H]≤0.00015%, surplus Fe.
The restriction of super high impact toughness, high cleanliness steel for low-temperature pressure container chemical component of the present invention is specifically described below
Reason:
C: can significantly improve the intensity of steel, but also deteriorate the plasticity of steel, significantly improve the brittle transition temperature of steel.So
To guarantee that this steel grade has good low-temperature impact toughness, peritectic reaction is prevented, surface quality of steel is endangered, carbon content should control
Below 0.08%.C content of the present invention takes 0.06%-0.08%.
Si: can dissolve in ferrite in steel, can improve the intensity and hardness of steel, but reduce the plasticity and toughness of steel.Its
Minimum content can be only achieved effect for 0.18%, but excessively high Si content easily causes steel when especially coexisting with Mn element
Grain coarsening increases steel belt roof bolt brittleness, while Si is to significantly improve one of brittle transition temperature element of steel.Compound material
Si content is determined as 0.20%-0.35% by general requirement, this steel grade.
Mn: can dissolve in ferrite in steel, strengthen matrix, and pearlite can be refined in roller repairing and opposite can improve pearl
Therefore body of light content can improve intensity and hardness, and influence on the plasticity of material smaller.When Mn content is lower than 1.8%, with
Its content increases, and steel strength is continuously increased, and does not have significant harm to toughness.The general requirement of compound material, this steel grade
Mn content is determined as 1.15%-1.35%.
Ni: can be improved the intensity of steel, while keep good plasticity and toughness.Certain nickel has soda acid higher resistance to
Corrosive power.Nickel can reduce critical transition temperature and reduce the diffusion velocity of each element, significantly improve the low-temperature impact of steel
Toughness.It is expensive but since nickel is scarce resource.So the control of Ni content is in 0.12%-0.15% in the present invention.
Ti: carbide forms carbonization titanium particulate, can effectively prevent crystal grain and grow up in steel in conjunction with carbon.
While improving intensity, crystal grain can be sufficiently refined through normalizing, the plasticity of steel and impact flexibility is made to significantly improve.But
The bulky grain TiN brittle inclusion that Ti is easily formed in conjunction with N element in steel, seriously affects the impact flexibility of steel.So of the invention
Middle Ti content control is 0.01%-0.02%.
Al: improving the inoxidizability of steel, reduces gas content in steel, improves the fatigue strength of steel, while brilliant as refinement
Grain element is present in steel grade, plays the role of the cryogenic property and corrosion resisting property that improve steel.But if Al content is excessively high, it is easy shape
At hard Al2O3It is mingled with, deteriorates the impact flexibility of steel.So the present invention defines specific Composition Control range to Al content is
0.020%-0.045%。
P: making steel generate cold brittleness, reduce the impact flexibility of steel, while deteriorating the welding performance of steel, reduces plasticity, makes cold
Curved degradation.So the present invention has carried out strict control to P content, it is necessary to≤0.010%.
S: easy segregation element reduces the ductility and toughness of steel, also adversely affects to welding performance and corrosion resistance.Institute
Strict control is carried out to S content with the present invention, it is necessary to≤0.003%.
O: it is little to the intensity effect of steel in room temperature, but reduce the elongation of steel and reduction of area significantly, lower
When temperature and extremely low O content, the intensity and plasticity of material are drastically reduced with the increase of O content.In terms of impact property, with
The maximum value of the increase impact of O content gradually decreases, and brittle transition temperature but soon increases, the range of brittle transition temperature
With broadening.Meanwhile with the increase of O content, the oxide inclusion occurrence probability of material is greatly increased, to reduce material
Fatigue life.The present invention is by O content stability contorting within 0.0015%.
H: hydrogen reduces the plasticity of steel, mainly reduces low-temperature impact work.Hydrogen can generate " hairline " or be formed in steel
Stressed zone, when steel carries out forging rolling processing, hairline extends and forms crackle, deteriorates the mechanical property especially plasticity of steel, even
" white point " is presented on steel fracture in fracture.Hydrogen can also cause splitting in spot segregation, hydrogen embrittlement and weld heat-affected zone simultaneously
Seam etc..Therefore, the present invention and technique control H below 0.00015%.
N: nitrogen can be such that steel strengthen, but significantly reduce steel plasticity, toughness, increase timeliness tendency and cold brittleness.Generally want
Ask content less than 0.0080%.The present invention and production technology control N content within 0.0050%.
A kind of super high impact toughness, the production method of high cleanliness steel for low-temperature pressure container, including the following steps: by upper
The mass percent of component is stated,
1) converter smelting: smelting in 100 tons or more of top and bottom complex blowing formula converter, using molten iron and high-quality steel scrap as raw material into
Row just refining, realizes pre- de- P, and tapping is added lab-prepared refining slag, double deoxidizer and a variety of high purity alloys and carries out pre-deoxidation and ingredient
Initial adjustment；
2) it refines: carrying out molten steel deep deoxidation and alloying in 100 tons or more of LF furnace；The stirring of refining process whole process, essence
The later period is refined using weak stirring, prevents secondary oxidation of steel；
3) vacuum outgas and removal of inclusions processing vacuum outgas: are carried out using RH circulating degasification apparatus after LF refining；
4) inclusion modification and soft blow: feeding silico-calcium silk thread and to inclusion modification and carry out soft blow processing after being vacuum-treated,
The soft blow time is 30-35 minutes, is sufficiently floated, removal of inclusions；
5) continuous casting: using billet caster, using tundish covering flux, crystallizer protecting residue, carries out whole full guard and pours
Casting production continuous casting square billet；
6) steel rolling: production line of bar produces Φ 50mm ~ Φ 70mm steel for low-temperature pressure container in utilization；
7) steel surface defect finishing: is eliminated using ball blast+chamfered edge+manual inspection reconditioning finishing process.
The further improvement project of the present invention is that the step 1) stays the anti-non-return P of steel tapping using slide plate pushing off the slag.
The further improvement project of the present invention is that the step 2 makes the refining slag of basicity slag R=5 ~ 8, passes through slag-metal reaction
Strengthen de- S, go to be mingled with.
The further improvement project of the present invention is, in the step 2, the Ventilation Rate of the weak stirring is less than 200L/
min。
The further improvement project of the present invention is, in the step 3), kept for 30 minutes under a high vacuum or more, guarantee
H ]≤0.00015%, [ O ]≤0.0010%, all the components enter the range of requirement.
The further improvement project of the present invention is, in the step 6), using 1050 ~ 1080 DEG C of open rollings, 980 ~ 1000 DEG C
Finish to gauge temperature-controlled rolling sufficiently refines original grain degree.
Super high impact toughness, high cleanliness steel for low-temperature pressure container (07MnNiTi) are manufactured according to the present invention, is had super
High/low-temperature impact toughness and high cleanliness, material mechanical property after whole normalizing can achieve following level: -50 DEG C
KV2≥250J。
The beneficial effects of the present invention are:
The first, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention is led to
Crossing accurate control reduces C content, carries out strong deoxidation, refinement crystal grain using Al, carries out alloying using Ni, Ti element, make its property
Can have and be applicable in lower medium temperature (- 50 DEG C ~ -55 DEG C) and higher low temperature compared with 09MnD steel in Q/TDGG 0040-2004
Impact flexibility, and its overall mechanical properties is also more stable.
The second, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention, makes
With calcium containing alloy carry out strong deoxidation, dedicated refining slag system enhancing removal be mingled with effect, be de-gassed using RH vacuum equipment,
The cleanliness of material is improved, to improve the safety of material.
Third, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention, this
Invention uses BOF+LF+RH+CCM technique, guarantees lower P, S, H, O, N content, and material is made to have excellent synthesis mechanical property
Energy.
4th, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention, this
Invention gives full play to the work of Ti element refinement crystal grain by using 1050 ~ 1080 DEG C of open rollings, 980 ~ 1000 DEG C of finish to gauge temperature-controlled rollings
With raising material comprehensive mechanical property.
5th, a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container and its production method of the invention, this
Invention meets -50 DEG C ~ -55 DEG C of low-alloy steel of requirement by Rational Composition design and advanced technique, effectively reduces
The consumption of nickel alloy, is greatly saved cost, improves efficiency.
Detailed description of the invention
Fig. 1 is the standard analysis table of 09MnD steel.
Fig. 2 is the low-alloy steel for low-temperature pressure container 09MnD that the current country uses and chemical component of the invention compares
Table.
Fig. 3 is the chemical component contrast table of 4 groups of embodiments.
Fig. 4 is that the impact absorbing energy of 4 groups of embodiments and 09MnD steel at -50 DEG C, -52 DEG C and -55 DEG C compares
Table.
Fig. 5 is 4 groups of embodiment non-metallic inclusion controlled level tables.
Specific embodiment
As shown in Fig. 2, the comparative situation of chemical constituent of the invention and 09MnD steel chemical constituent.
And according to 4 groups of embodiments of production preparation in accordance with the following methods:
1) converter smelting: smelting in 100 tons or more of top and bottom complex blowing formula converter, using molten iron and high-quality steel scrap as raw material into
Row just refining, realizes pre- de- P, and tapping is added lab-prepared refining slag, double deoxidizer and a variety of high purity alloys and carries out pre-deoxidation and ingredient
Initial adjustment stays the anti-non-return P of steel tapping using slide plate pushing off the slag；
2) it refines: carrying out molten steel deep deoxidation and alloying in 100 tons or more of LF furnace, make the refining of basicity slag R=5 ~ 8
Slag strengthens de- S by slag-metal reaction, removal is mingled with；The stirring of refining process whole process, refining later period use weak stirring, prevent molten steel
Secondary oxidation；
3) vacuum outgas: carrying out vacuum outgas and removal of inclusions processing using RH circulating degasification apparatus after LF refining,
Kept for 30 minutes under a high vacuum or more, guarantee that [ H ]≤0.00015%, [ O ]≤0.0010%, all the components enter the model of requirement
It encloses；
4) inclusion modification and soft blow: feeding silico-calcium silk thread and to inclusion modification and carry out soft blow processing after being vacuum-treated,
The soft blow time is 30-35 minutes, is sufficiently floated, removal of inclusions；
5) continuous casting: using billet caster, using tundish covering flux, crystallizer protecting residue, carries out whole full guard and pours
Casting production continuous casting square billet；
6) steel rolling: production line of bar produces Φ 50mm ~ Φ 70mm steel for low-temperature pressure container in utilization, using 1050 ~
1080 DEG C of open rollings, 980 ~ 1000 DEG C of finish to gauge temperature-controlled rollings sufficiently refine original grain degree；
7) steel surface defect finishing: is eliminated using ball blast+chamfered edge+manual inspection reconditioning finishing process.
The process conditions limited is not added to can refer to this field routine techniques in method made above.
As shown in figure 3, the super high impact toughness of each embodiment of gained, high cleanliness steel for low-temperature pressure container
The chemical component of (07MnNiTi).
As shown in figure 4, impact absorbing energy of each embodiment of gained under the conditions of -50 DEG C, -52 DEG C and -55 DEG C and with it is existing
There is the comparative situation of technology.
As shown in figure 5, the non-metallic inclusion controlled level comparative situation of each embodiment of gained.
General superfine high-quality steel non-metallic inclusion control hierarchy be each system≤1.5 grades, and the present invention pass through it is reasonable
Technological design and process control, non-metallic inclusion stability contorting at 1.0 grades hereinafter, purity of steel is high；Moreover, wherein
C is thick and C is carefully 0 grade.
Claims (4)
1. a kind of super high impact toughness, high cleanliness steel for low-temperature pressure container, it is characterised in that: its chemical component quality percentage
Than are as follows: C:0.06 ~ 0.08%, Si:0.20 ~ 0.35%, Mn:1.15 ~ 1.35%, Ti:0.01 ~ 0.02%, Ni:
0.12 ~ 0.15%, Al:0.020 ~ 0.045%, P≤0.010%, S≤0.003%, [O]≤0.0015%, [N]≤0.0050%,
[H]≤0.00015%, surplus Fe；
Including following preparation steps:
1) converter smelting: smelting in 100 tons or more of top and bottom complex blowing formula converter, carries out just using molten iron and high-quality steel scrap as raw material
Refining, realizes pre- de- P, and tapping is added lab-prepared refining slag, double deoxidizer and a variety of high purity alloys and carries out pre-deoxidation and ingredient
Initial adjustment；
2) it refines: carrying out molten steel deep deoxidation and alloying in 100 tons or more of LF furnace, make the refining slag that basicity is R=5 ~ 8,
The Ventilation Rate of the stirring of refining process whole process, the stirring of refining later period is less than 200L/min, prevents secondary oxidation of steel；
3) vacuum outgas: vacuum outgas and removal of inclusions processing are carried out using RH circulating degasification apparatus after LF refining, in height
It is kept for 30 minutes or more under vacuum；
4) inclusion modification and soft blow: silico-calcium silk thread is fed after being vacuum-treated and to inclusion modification and carries out soft blow processing, soft blow
Time is 30 ~ 35 minutes, is sufficiently floated, removal of inclusions；
5) continuous casting: using billet caster, using tundish covering flux, crystallizer protecting residue, carries out whole full guard casting life
Produce continuous casting square billet；
6) steel rolling: production line of bar produces Φ 50mm ~ Φ 70mm steel for low-temperature pressure container in utilization, using 1050 ~
1080 DEG C of open rollings, 980 ~ 1000 DEG C of finish to gauge temperature-controlled rollings；
7) steel surface defect finishing: is eliminated using ball blast+chamfered edge+manual inspection reconditioning finishing process.
2. a kind of super high impact toughness as described in claim 1, the production method of high cleanliness steel for low-temperature pressure container,
It is characterized in that: in the step 1), the anti-non-return P of steel tapping being stayed using slide plate pushing off the slag.
3. a kind of super high impact toughness as described in claim 1, the production method of high cleanliness steel for low-temperature pressure container,
It is characterized in that: in the step 2, de- S being strengthened by slag-metal reaction, removal is mingled with.
4. a kind of super high impact toughness as described in claim 1, the production method of high cleanliness steel for low-temperature pressure container,
It is characterized in that: in the step 3), should ensure that [ H ]≤0 .00015%, [ O ]≤0.0010%, all the components enter requirement
Range.
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