CN103757554B - A kind of electronic gas Large Copacity gas vessel and preparation method thereof - Google Patents

Abstract

The invention provides a kind of electronic gas Large Copacity gas vessel and preparation method thereof.nullDescribed preparation method designs by optimizing the composition of steel、Steel purification and smelting process control，Obtain the chemical composition of electronic gas Large Copacity gas vessel by weight percentage for C:0.40～0.45%，Si:0.25～0.35%，Mn:0.85～1.00%，P≤0.013%，S≤0.008%，Cr:1.00～1.10%，Mo:0.20～0.25%，Ti≤0.015%，Ni≤0.18%，Cu≤0.18%，Sn≤0.010%，As≤0.025%，Al:0.015～0.040%，[H]≤0.0002%，[N]≤0.0070%，T[O]≤0.0020%，Surplus is ferrum and inevitable impurity，And meet the intensity that electronic gas high-capacity packaging gas cylinder is good、The serviceability requirements such as toughness.

Description

A kind of electronic gas Large Copacity gas vessel and preparation method thereof

Technical field

The present invention relates to metallurgy industry steelmaking technical field, high more particularly to a kind of electronic gas Large Copacity Air bottle steel alloy and preparation method thereof.

Background technology

Electronic gas be widely used in the powerful electron trade of growth momentum in recent years, solaode, The numerous areas such as mobile communication, Aero-Space, war industry, be super large-scale integration, plane show Show that the electronics industry IC industries such as device, compound semiconductor device, solaode, optical fiber produce Indispensable raw material, be widely used in thin film, etch, adulterate, vapour deposition, the technique such as diffusion； It is the manufacture basis of electronic devices and components, is referred to as " blood " and " grain " of IC industry.

There is the danger such as asphyxiating, corrosivity, toxicity, inflammable and explosive property in electronic gas.Therefore, it Produce and application is desirable that the high-quality gas packed packaging storage-transport vessel of use, to avoid the generation of secondary pollution. Along with the upgrading of consumer electronics, product manufacturing size is increasing, finished product rate and defect control System is increasingly stricter, and the requirement to stopping induction system secondary pollution is more and more harsher.And use big packaging (Large Copacity, big volume) container ensure that the seriality of GAS QUALITY, reduces and repeatedly fills pollution wind Danger, is conducive to improving Environmental capacity.Simultaneously as in big specification integrated circuit production process, it is necessary to make With multiple unit electronic gas, it is desirable to compound concentration and the stability of concentration of electronic gas are the highest, for protecting Card fills the long stability of electronic gas concentration, it is necessary to electronics gas cylinder inner surface imposes coating and processes, Make to be formed between inventory of gas and steel cylinder bottle that one layer smooth, imporosity, protective layer in uniform thickness, with Reduce gas absorption and prevent Metal ion release etc..And before armor coated, it is necessary to bottle Inner surface carries out mirror-polishing process.

As the gas cylinder of the big packing container of electronic gas, there is asphyxiating, corrosion because it fills medium Property, the danger such as toxicity, inflammable and explosive property, should have a highest security performance, and require simultaneously steel cylinder from Body is lightweight；The main raw material(s) manufacturing it is the thin-wall seamless steel pipe of big specification overlength degree, it is desirable to it is strong Degree height, good toughness, dimensional accuracy are high.Thus it requires steel cylinder body not only purity of steel is high, metallographic group Knit fine uniform and meet the low temperature storage performance of electronic gas.

Due to electronics gas cylinder use bad environments, it is desirable to the performance of steel used except meet room temperature performance detection in addition to, Also requiring the low temperature impact properties of-40 DEG C, sample performance after Analog heat-treating meets index of correlation requirement.

In order to make reaching of Large Copacity electronic gas steel cylinder master raw-material great diameter and long thin-wall seamless steel pipe To above-mentioned combination property requirement, it is necessary to use the combination property such as processing characteristics and serviceability to require strict Raw steel base.Existing gas cylinder steel and general smelting process can not meet the quality of this product Requirement.

Summary of the invention

For the deficiencies in the prior art, an object of the present invention is to solve above-mentioned prior art Present in one or more problems.

An object of the present invention is to provide a kind of electronic gas Large Copacity gas vessel and preparation side thereof Method, meets electronic gas steel cylinder and has intensity height, good toughness, bright and clean smooth, the guarantee metallographic of inner surface Organize the requirement of the combination properties such as careful homogeneous and low-temperature impact toughness, to ensure that electronic gas stores and makes Safety during with.

To achieve these goals, an aspect of of the present present invention provides a kind of electronic gas Large Copacity gas cylinder use The preparation method of steel.Said method comprising the steps of: at the beginning of electric furnace, make steel water, control endpoint molten steel composition Include by weight percentage: C:0.12～0.20%, P:0.001～0.007%, As≤0.023%, Sn≤0.010%, tapping temperature is 1620～1660 DEG C, and carries out pre-de-during tapping to ladle Oxygen and Alloying Treatment；Molten steel is carried out LF refine, and controls molten steel composition that LF refine obtains with weight Amount percentages includes: C:0.40～0.44%, Si:0.27～0.32%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.023%, Sn≤0.010%, Al:0.035～0.060%, to steel Water carries out vacuum refining, and controls the molten steel composition that vacuum refining obtains and include by weight percentage: C: 0.40～0.44%, Si:0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.025%, Sn≤0.010%, Al:0.015～0.040%, H≤0.0002%, [O]≤0.0018%, N≤0.0050%；Continuous casting, in casting process, two cold (i.e. cooling twice) use weak chill formula and incite somebody to action It is 0.20～0.27L/Kg that the specific water of two cold-zones controls, and by weight percentage, continuous casting obtains The chemical composition of electronic gas Large Copacity gas vessel is C:0.40～0.45%, Si:0.25～0.35%, Mn:0.85～1.00%, P≤0.013%, S≤0.008%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.015%, Ni≤0.18%, Cu≤0.18%, Sn≤0.010%, As≤0.025%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, surplus is ferrum and inevitable impurity.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, preferably Ground, by weight percentage, the chemical composition of described electronic gas Large Copacity gas vessel be C:0.41～ 0.44%, Si:0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr: 1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, Sn≤0.010%, As≤0.025%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, Surplus is ferrum and inevitable impurity.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, described The strand that continuous casting step obtains is the round base of a diameter of Φ 350～388mm.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute Stating in casting process, the cooling water of the two each cooling sections in cold-zone is assigned as: two cooling water inflows of cold I section account for two Cold-zone cooling water total Water 16～19%, two the cooling water inflow of cold II section account for two cold-zones cooling water total Waters 20～22%, two the cooling water inflow of cold III section account for the 9～12%, two cold IV of two cold-zones cooling water total Waters The cooling water inflow of section account for two cold-zones cooling water total Waters 27～31% and two the cooling water inflow of cold V section account for The 17～21% of two cold-zone cooling water total Waters.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute Stating in casting process, controlling the Metal in Tundish degree of superheat is 15～35 DEG C, and crystallizer uses electromagnetic agitation also Controlling cooling water flow is 1400～1600L/min, and casting speed is 0.40～0.55m/min.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute During stating electric furnace steel tapping, when tap reaches the 1/3 of one heat steel water inventory, add in ladle Deoxidizer CaBaAlSi carries out pre-deoxidation, and adds Al and manganeisen carries out alloying.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute State in continuous casting step, control middle unwrapping and water liquid level >=650mm, process cast liquid level >=700mm, even waters liquid level >=450mm, finally stops to water liquid level >=300mm.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute State in vacuum refining step, keep vacuum≤66.7Pa, retention time >=15 minute, until slag is no longer Foam and continue to keep more than 2 minutes；After vacuum breaker, feed Si-Ca line 0.5～0.8Kg/t steel, the most right Molten steel carries out quiet blowing, and quiet blows the time >=12 minutes.

One embodiment of the preparation method of the electronic gas Large Copacity gas vessel according to the present invention, in institute State in LF refinement step, add reducing agent and make white slag, and make the white slag retention time at more than 20min, Wherein, by weight percentage, described reducing agent consist of 30～70 parts carbide, 5～20 parts SiCa and the aluminum slag of 25～50 parts.

Another aspect provides a kind of electronic gas Large Copacity gas vessel.With percentage by weight Meter, the chemical composition of described electronic gas Large Copacity gas vessel is C:0.40～0.45%, Si:0.25～ 0.35%, Mn:0.85～1.00%, P≤0.013%, S≤0.008%, Cr:1.00～1.10%, Mo: 0.20～0.25%, Ti≤0.015%, Ni≤0.18%, Cu≤0.18%, Sn≤0.010%, As≤0.025%, Al:0.15～0.40%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, surplus is ferrum With inevitable impurity.

One embodiment of the electronic gas Large Copacity gas vessel according to the present invention, it is preferable that with weight Percentages, the chemical composition of described electronic gas Large Copacity gas vessel is C:0.41～0.44%, Si: 0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, Sn≤0.010%, As≤0.023%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, surplus is ferrum With inevitable impurity.

Compared with prior art, the beneficial effect comprise that

1. the impurity element such as P, As, Sn that would potentially result in temper embrittlement, the S causing toughness to reduce are to the greatest extent Minimum may be reduced to.

2. ensure that purity of steel, according to field trash rating scale GB/T10561 evaluate: A, B, C, D all≤1 grade, steel pipe finished product gas ［ N ］≤70PPm, ［ O ］≤18PPm, ［ H ］≤2.0PPm, Al Content 0.015～0.040%.

The most reasonably control round billet continuous casting machine cooling twice water distribution and two cold specific waters, prevent strand from producing Underbead crack and reduction central pipe and center porosity.And use M-EMS, it is ensured that strand Crystallographic texture (as Center Equiaxial Crystal district expand) ensure that strand center mass, roll for next step Pipe and following process ensure that gas cylinder inner surface is bright and clean and smooth provide preferable precondition.

The most not only ensure that electronic gas gas cylinder large diameter thin wall seamless steel pipe and gas cylinder manufacture multiple tracks The manufacturing property of secondary processing (cold and hot), it is often more important that meet electronic gas large-volume packing high pressure The safety in utilization such as intensity that gas cylinder is good, toughness.

Accompanying drawing explanation

Will be become by the description carried out below in conjunction with the accompanying drawings, the above and other purpose of the present invention and feature Obtain clearer, wherein:

Fig. 1 is the scattergram of different parts carbon content detection sample point on a certain cross section of strand.

Detailed description of the invention

Hereinafter, accompanying drawing will be combined and exemplary embodiment describes the electron gas according to the present invention in detail Body Large Copacity gas vessel and preparation method thereof.In the present invention, without the statement of exception, then lead to In the material often mentioned, the content of each element or composition is all weight percentage.

The electronic gas Large Copacity gas vessel provided according to an aspect of the present invention, be by weight percentage C:0.40～0.45%, Si:0.25～0.35%, Mn:0.85～1.00%, P≤0.013%, S≤0.008%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.015%, Ni≤0.18%, Cu≤0.18%, Sn≤0.010%, As≤0.025%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, The ferrum (Fe) of T [O]≤0.0020% and surplus and inevitable impurity.

In the present invention, the content of essential element C, Mn, Cr, Mo is controlled the most not only The intensity of steel, hardness and quenching degree can be improved, make steel have favorable low-temperature impact toughness, also can make gas Higher temper resistance, fatigue strength and anti-repeat impact ability is had after bottle steel is conditioned；Cr is also simultaneously The wearability of steel can be improved, after making the surface treatments such as ground, the polishing of gas cylinder process, easily obtain higher Surface smoothness；And Al not only acts as deoxidation in steel, also that Al is first as alloy in the present invention The gentle bottle surface of element, beneficially crystal grain thinning is bright and clean.

The degree of purity of steel is the important guarantee of electronic gas Large Copacity gas cylinder safety.Reduce steel as far as possible The harmful elements such as middle P, S, As, Sn, H, N, O gas and inclusion content not only can improve electronics The manufacturing process performance of gas Large Copacity gas cylinder steel → each operation of seamless steel pipe → gas cylinder, the most anti- Only steel produces the various defects such as cold working crackle, fire check and lamellar tearing in the course of processing, more important Be the usage safety performance that can significantly improve electronic gas Large Copacity high-pressure electronic gas cylinder.

Controlling remaining Ti content no more than 0.015% is in order to avoid too high Ti forms TiN brittle inclusion Thing, forms surface defect during steel pipe cold deformation and gas cylinder surface finish is brought adverse effect, no The requirement of gas cylinder inner surface applying coating can be met, it is preferable that controlled below 0.010% by Ti content； Controlling Cu constituent content no more than 0.18% is in order to avoid the Cu constituent content of excess makes steel produce hot tearing, Preferably, Cu content is controlled below 0.15%；Control Ni constituent content no more than 0.18% be for Avoid affecting the surface quality of steel after heating because Ni constituent content is too high, it is preferable that by Ni content Control below 0.15%.

Preferably, the chemical composition of above-mentioned electronic gas Large Copacity gas vessel is C by weight percentage: 0.41～0.44%, Si:0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, Sn≤0.010%, As≤0.023%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, surplus is ferrum and inevitable impurity.

The production of the smelting process of the electronic gas Large Copacity gas vessel according to another part of face offer of the present invention Technological process includes: electric arc furnace smelting → LF stove refine → vacuum refining → continuous casting cheat cold → surface inspection and Finishing.Specifically:

(1) water is made steel at the beginning of electric furnace

Optimize electric furnace and enter the main raw material of stove and dispensing, select high-quality steel scrap, improve the addition of molten iron as far as possible Amount and the amount of allocating into of the pig iron, it is achieved to (As, Sn, Pb, Sb, Bi etc.) harmful element and remnants unit Effective control of element.Preferably, molten iron (or pig iron) consumption is 30～50% into stove iron and steel stock gross weight. Smelting process uses lasting, good foam slag burialing arc operate, reduce the nitrogen in air because of electric arc electricity From and dissolve in steel.Electric furnace smelting terminal point control: C:0.12～0.20%, P:0.001～0.007%, As≤0.023%, Sn≤0.010%；Tapping temperature is in the range of 1620～1660 DEG C.And use eccentric furnace bottom Slag free tapping (EBT).Compound pre-deoxidation and alloying operation is carried out during tapping.In tapping process, when During tap about 1/3, be initially added into deoxidizer CaBaAlSi2.0～3.5Kg/t steel, add Al block 1.2～ 1.5Kg/t steel and suitable manganeisen.

(2) LF refine

Ladle is transported to LF refine station, during transporting, ladle is carried out argon bottom-blowing and is blowing Argon feeds aluminum steel after starting, and feed quantity is 3～5m/t steel.

Molten steel is carried out LF refine, uses big quantity of slag arc-covering slag operation at refining process, to reduce molten steel with big The contact of gas, can reduce molten steel air-breathing；Meanwhile, it is dividedly in some parts reducing agent and makes white slag, and make white slag keep Time at more than 20min, to ensure purity of steel.Wherein, the composition of reducing agent is by weight: Carbide: 30～70 parts, SiCa powder: 5～20 parts and aluminum slag: 25～50 parts.

LF refine obtain molten steel composition include by weight percentage: C:0.40～0.44%, Si:0.27～ 0.32%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo: 0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.023%, Sn≤0.010% And Al:0.035～0.060%.

(3) vacuum refining

Ladle hanging in vacuum tank and carries out vacuum outgas, evacuation is to keep vacuum≤66.7Pa, during holding Between >=15 minutes, until slag the most substantially foams and continues to keep more than 2 minutes.In order to promote to be mingled with The abundant floating of thing, notes molten steel boiling situation at any time, and adjusts Ar atmospheric pressure in time in vacuum. After vacuum breaker, feed SiCa line 0.5～0.8Kg/t steel, then molten steel carried out quiet blowing, quiet blow the time >=12min, When quiet blowing, keep molten steel face to wriggle and molten steel must not be exposed.

Control the liquid steel temperature of coming out of the stove of vacuum degassing furnace, wherein, connect and water the first stove: 1570～1585 DEG C, Even water the second stove and later heat can reduce by 5～10 DEG C.

The molten steel composition that vacuum refining obtains includes by weight percentage: C:0.40～0.44%, Si: 0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.025%, Sn≤0.010%, Al:0.015～0.040%, H≤0.0002%, [O]≤0.0018% and N≤0.0050%.

(4) continuous casting

Molten steel after VD application of vacuum is delivered to round billet continuous casting machine and is cast.

In order to ensure the slab quality of curved circular billet continuous casting machine and being smoothed out of cast, below major control Several aspects:

A. baking of tundish is good, baking temperature >=1100 DEG C.

B. casting implementation Process whole process protection cast molten steel is used " Ar gas+close by the long nozzle of ladle to tundish Packing " protective casting, to prevent the scaling loss of secondary oxidation of steel and Al, it is ensured that purity of steel.

C. tundish Liquid level requires:

In casting process the moment note in bag liquid level, improve as far as possible in the middle of unwrap and water liquid level, Open and water liquid level >=650mm, to ensure uniformity and the purity of steel of molten steel composition.Process potting syrup Face height >=700mm, even waters liquid level >=450mm, and tundish finally stops to water liquid level >=300mm.

D. continuous casting production uses double-deck coverture to protect, and bottom ash efficient alkaline coverture pushes up slag Employing carbonization rice husk is incubated, and casting process observes the covering situation of pouring basket liquid level at any time, in preventing Between Baogang liquid level cover bad or that molten steel is exposed phenomenon.

The most each tundish casting sequence is not more than 7 stoves.The Metal in Tundish degree of superheat is 15～35 DEG C.

F. use M-EMS, it is ensured that the densification of strand center crystalline structure, uniformly, increase center Equiaxial crystal ratio.M-EMS parameter is as shown in table 1.

Table 1 M-EMS parameter

Specification	Stirring frequency, Hz	Alr mode	Stir current, A
				Φ350mm	2.5	Turn 8s-clockwise and stop 2s-counterclockwise rotation 8s	300A
Φ388mm	2.5	Turn 8s-clockwise and stop 2s-counterclockwise rotation 8s	260A

G. continuous casting cooling uses weak cold.

The casting blank specification that continuous casting obtains is Φ 350～Φ 388mm.Crystallizer cooling water flow be 1400～ 1600L/min.Secondary cooling water uses weak chill formula, Φ 350mm and the specific water of Φ 388mm specification strand And two the cooling moisture of each cooling section in cold-zone join and see table 2, and, use low pulling rate to pour into a mould, throwing speed Degree Φ 350mm:0.45～0.55m/min, Φ 388mm:0.40～0.50m/min.

The cooling moisture of each cooling section of the cold specific water of table 2 two and two cold-zones is joined

Suitable intensity of cooling and casting speed can avoid and alleviate the various defects of strand.The two of strand are cold Intensity has important impact to cc billet surface quality and internal soundness, if intensity of secondary cooling is excessive, then can Making strand in cooling procedure, solidified shell produces backheat, makes strand produce underbead crack；On the other hand Strand surface temperature when aligning also can be made less than the brittleness temperature of steel, to reduce the ductility of steel, be easily generated Face crack；If intensity of secondary cooling is the most weak in turn, then strand can be made to solidify the most completely before aligning, easily Produce straightening cracks.

The selection strand to be ensured of the casting speed shell thickness in crystallizer exit, also to ensure Slab quality and the production capacity giving full play to conticaster.If casting speed is too fast, one is to cause casting Base is the thinnest at crystallizer exit shell thickness, is easily generated bleed-out and face crack；Two is also to make strand Wick-containing extends, and on the one hand strand can be made to solidify the most completely before aligning, be easily generated straightening cracks, the opposing party Face also makes strand be easily generated centre burst, shrinkage cavity, the internal flaw such as loose, affects slab quality.If Casting speed is crossed and the reduction of casting machine production efficiency or stove machine production capacity then can be made slowly not to mate.

H. strand is taked to cheat cold mode and is carried out slow cooling.Enter to cheat temperature >=500 DEG C, go out to cheat temperature≤100 DEG C.

In order to be more fully understood that the above-mentioned exemplary embodiment of the present invention, below in conjunction with concrete example, it is entered Row further illustrates.

Example 1

In the EBT-electric furnace that nominal capacity is 70 tons, add molten iron and the steel scrap of 70% of 30%, Using foam slag burialing arc technique in smelting process, the nitrogen reduced in air dissolves in steel because of electric arc ionization. Use eccentric furnace bottom slag free tapping (EBT).The chemical composition of electric furnace smelting molten steel is as shown in table 3, and controls As≤0.023% processed, Sn≤0.010%.

Tapping when reaching above-mentioned tapping condition, tapping temperature is 1620 DEG C.When tap about 1/3 Time, it is initially added into deoxidizer CaBaAlSi2.0Kg/t steel, adds Al block 1.5Kg/t steel and suitable ferromanganese Alloy carries out alloying.After tapping and before entering LF, feed Al line 3m/t steel.

Ladle enters LF refine station, uses big quantity of slag arc-covering slag operation, to reduce contacting of molten steel and air, And reduce molten steel air-breathing；Meanwhile, it is dividedly in some parts reducing agent and makes white slag, and make the white slag retention time at 20min Above.Wherein, the composition of reducing agent is by weight: the carbide of 50 parts, the SiCa powder of 10 parts and The aluminum slag of 40 parts.The molten steel composition that LF refine obtains is as shown in table 4.

Then, molten steel is performed Fruit storage.That is, ladle is hung in VD tank and carries out vacuum outgas, 18 minutes retention times under the vacuum of≤66.7Pa.After vacuum breaker, feed Si-Ca line 0.76Kg/t steel Steel inclusion is carried out degenerative treatments, then molten steel is carried out quiet blowing, quiet blow time 14min, quiet When blowing, keep molten steel face to wriggle and molten steel must not be exposed.Controlling VD opening temperature is 1580 DEG C.Vacuum The main molten steel composition that refine obtains is as shown in table 4, and after vacuum refining, the H in molten steel is 0.00018%, [O] is 0.0016% and N to be 0.0039%.

Finally, molten steel being delivered to round billet continuous casting machine and casts, cast specification is Φ 350mm.Ladle arrives The long nozzle whole process of tundish uses " Ar gas+sealing ring " molding casting.The temperature that tundish is toasted Degree is 1115 DEG C, controls to open to water liquid level 700mm, process liquid level 710mm, and uses bilayer to cover Lid agent is protected, bottom ash efficient alkaline coverture, and top slag uses carbonization rice husk insulation, in continuous casting mistake Journey is observed the covering situation of pouring basket liquid level at any time, prevents tundish molten steel face and cover bad or steel The phenomenon that liquid is exposed, it addition, the Metal in Tundish degree of superheat is 20 DEG C.Crystallizer cooling water is 1433L/min, Crystallizer mixing parametric is as shown in table 1.The specific water of cooling twice is 0.27L/Kg, and secondary coolingwater distributes For: two cold I section 19%, two cold II section 22%, two cold III section 11.5%, two cold IV section 29.5%, two Cold V section 18%.Casting speed is 0.45m/min.And the strand obtained is taked to cheat cold mode carry out slow cooling, It is 512 DEG C that strand enters to cheat temperature, and going out to cheat temperature is 96 DEG C.Obtain pipe.

Carbon content detection sample point scattergram different parts sampling on the same cross section of strand as shown in Figure 1 And C element content in computational analysis steel, carbon segregation index and carbon content extreme difference value (C extreme difference), result is such as Shown in table 5.It addition, by GB/T226 standard strand carried out macrostructure inspection and by Macro defect is graded by YB/T4149-2006 appendix A judge picture, and strand macro defect is graded and low Times histological test result is as shown in table 6.It addition, table 4 shows the change of sample analysis on steel pipe finished product Studying a point result, table 7 shows steel pipe finished product gas content testing result, and table 8 shows on steel pipe Sampling and the mechanics properties testing result of sample after simulation is quenched, table 9 shows and samples also on steel pipe After simulation is quenched, sample is according to field trash rating scale GB/T10561 rating result.

Example 2

In the EBT-electric furnace that nominal capacity is 70 tons, add molten iron and the steel scrap of 55% of 45%, Using foam slag burialing arc technique in smelting process, the nitrogen that can reduce in air dissolves in steel because of electric arc ionization. Use eccentric furnace bottom slag free tapping (EBT).The chemical composition of electric furnace smelting molten steel is as shown in table 3, and controls As≤0.023% processed, Sn≤0.010%.

Tapping when reaching above-mentioned tapping condition, tapping temperature is 1640 DEG C.When tap about 1/3 Time, it is initially added into deoxidizer CaBaAlSi3.5Kg/t steel, adds Al block 1.2Kg/t steel and suitable ferromanganese Alloy carries out alloying.After tapping and before entering LF, feed Al line 4m/t steel.

Ladle enters LF refine station, uses big quantity of slag arc-covering slag operation, to reduce contacting of molten steel and air, And reduce molten steel air-breathing；Meanwhile, it is dividedly in some parts reducing agent and makes white slag, and make the white slag retention time at 20min Above.Wherein, the composition of reducing agent is by weight: the carbide of 70 parts, the SiCa powder and 25 of 5 parts The aluminum slag of part.The molten steel composition that LF refine obtains is as shown in table 4.

Then, molten steel is performed Fruit storage.That is, ladle is hung in VD tank and carries out vacuum outgas, 20 minutes retention times under the vacuum of≤66.7Pa.After vacuum breaker, feed 0.56Kg/t pair, Si-Ca line Steel inclusion carries out degenerative treatments, and then molten steel carry out quiet blowing, and quiet blows time 15min, blows quiet Time, keep molten steel face to wriggle and molten steel must not be exposed.Controlling VD opening temperature is 1571 DEG C.Vacuum fine The molten steel main component that refining obtains is as shown in table 4, and after vacuum refining, the H in molten steel is 0.00016%, [O] is 0.0017% and N to be 0.0049%.

Finally, molten steel being delivered to round billet continuous casting machine and casts, cast specification is Φ 350mm.Ladle arrives The long nozzle whole process of tundish uses " Ar gas+sealing ring " molding casting.The temperature that tundish is toasted Degree is 1100 DEG C, controls even to water liquid level 680mm, process liquid level 710mm, stops watering liquid level 300mm, and use double-deck coverture to protect, bottom ash efficient alkaline coverture, top slag uses carbon Change rice husk thermal insulation, casting process is observed the covering situation of pouring basket liquid level at any time, prevents centre Baogang's liquid level covers bad or that molten steel is exposed phenomenon, it addition, the Metal in Tundish degree of superheat is 15 DEG C.Knot Brilliant device cooling water is 1443L/min, and crystallizer mixing parametric is as shown in table 1.The specific water of cooling twice is 0.22L/Kg, secondary coolingwater is assigned as: two cold I section 16%, two cold II section 22%, two cold III section 11%, Two cold IV section 30%, two cold V section 21%.Casting speed is 0.55m/min.And the strand obtained is adopted Taking the cold mode in hole and carry out slow cooling, it is 515 DEG C that strand enters to cheat temperature, and going out to cheat temperature is 97 DEG C.Obtain pipe.

Fig. 1 shows the scattergram of different parts carbon content detection sample point on a certain cross section of strand, Wherein the direction of arrow A instruction is strand inner arc side.Carbon content detection sample point scattergram as shown in Figure 1 On the same cross section of strand, different parts samples and C element content in computational analysis steel, carbon segregation index And carbon content extreme difference value (C extreme difference), result is as shown in table 5.It addition, press GB/T226 standard to strand Carry out macrostructure inspection and by YB/T4149-2006 appendix A judge picture, macro defect graded, The grading of strand macro defect and macrostructure assay are as shown in table 6.It addition, table 4 shows at steel The chemical composition result of sample analysis on pipe finished product, table 7 shows steel pipe finished product gas content testing result, Table 8 shows and samples on steel pipe and the mechanics properties testing result of sample after simulation is quenched, and table 9 shows Gone out on steel pipe sampling and after simulation is quenched sample grade according to field trash rating scale GB/T10561 Result.

Example 3

In the EBT-electric furnace that nominal capacity is 70 tons, add molten iron and the steel scrap of 65% of 35%, Using foam slag burialing arc technique in smelting process, the nitrogen that can reduce in air dissolves in steel because of electric arc ionization. Use eccentric furnace bottom slag free tapping (EBT).The chemical composition of electric furnace smelting molten steel is as shown in table 3, and controls As≤0.023% processed, Sn≤0.010%.

Tapping when reaching above-mentioned tapping condition, tapping temperature is 1660 DEG C.When tap about 1/3 Time, it is initially added into deoxidizer CaBaAlSi2.5Kg/t steel, adds Al1.3Kg/t steel and suitable manganeisen Carry out alloying.After tapping and before entering LF, feed Al line 5m/t steel.

Ladle enters LF refine station, uses big quantity of slag arc-covering slag operation, to reduce contacting of molten steel and air, And reduce molten steel air-breathing；Meanwhile, it is dividedly in some parts reducing agent and makes white slag, and make the white slag retention time at 20min Above.Wherein, the composition of reducing agent is carbide, the SiCa of 20 parts and 50 of 30 parts by weight The aluminum slag of part.The molten steel composition that LF refine obtains is as shown in table 4.

Then, molten steel is performed Fruit storage.That is, ladle is hung in VD tank and carries out vacuum outgas, 22 minutes retention times under the vacuum of≤66.7Pa.After vacuum breaker, feed 0.70Kg/t pair, Si-Ca line Steel inclusion carries out degenerative treatments, and then molten steel carry out quiet blowing, and quiet blows time 16min, blows quiet Time, keep molten steel face to wriggle and molten steel must not be exposed.Controlling VD opening temperature is 1575 DEG C.Vacuum fine The molten steel composition that refining obtains is mainly as shown in table 4, and after vacuum refining, the H in molten steel is 0.00017%, [O] is 0.0013% and N to be 0.0035%.

Finally, molten steel being delivered to round billet continuous casting machine and casts, cast specification is Φ 388mm.Ladle arrives The long nozzle whole process of tundish uses " Ar gas+sealing ring " molding casting.The temperature that tundish is toasted Degree is 1105 DEG C, controls even to water liquid level 500mm, process liquid level 700mm, and uses bilayer to cover Lid agent is protected, bottom ash efficient alkaline coverture, and top slag uses carbonization rice husk insulation, in continuous casting mistake Journey is observed the covering situation of pouring basket liquid level at any time, prevents tundish molten steel face and cover bad or steel The phenomenon that liquid is exposed, it addition, the Metal in Tundish degree of superheat is 30 DEG C.Crystallizer cooling water is 1550L/min, Crystallizer mixing parametric is as shown in table 1.The specific water of cooling twice is 0.20L/Kg, and secondary coolingwater distributes For: two cold I section 17%, two cold II section 22%, two cold III section 11%, two cold IV section 29%, two cold V Section 21%.Casting speed is 0.45m/min.And the strand obtained is taked to cheat cold mode carry out slow cooling, casting It is 505 DEG C that base enters to cheat temperature, and going out to cheat temperature is 95 DEG C.Obtain pipe.

Carbon content detection sample point scattergram different parts sampling on the same cross section of strand as shown in Figure 1 And C element content in computational analysis steel, carbon segregation index and carbon content extreme difference value (C extreme difference), result is such as Shown in table 5.It addition, by GB/T226 standard strand carried out macrostructure inspection and by Macro defect is graded by YB/T4149-2006 appendix A judge picture, and strand macro defect is graded and low Times histological test result is as shown in table 6.It addition, table 4 shows the change of sample analysis on steel pipe finished product Studying a point result, table 7 shows steel pipe finished product gas content testing result, and table 8 shows on steel pipe Sampling and the mechanics properties testing result of sample after simulation is quenched, table 9 shows and samples also on steel pipe After simulation is quenched, sample is according to field trash rating scale GB/T10561 rating result.

Electric furnace smelting tapping ladle chemistry (wt%) of table 3 example 1 to 3

Constituent content	C	P
			Example 1	0.20	0.007
Example 2	0.15	0.005
			Example 3	0.12	0.001

The molten steel obtained and steel pipe one-tenth are refined in molten steel, vacuum refining that the LF refine of table 4 example 1 to 3 obtains The chemical composition (wt%) of product

Table 5 sample point as shown in Figure 1 detects strand carbon content, carbon segregation index and the C extreme difference obtained

Table 6 example 1 is to example 3 strand macro defect rating result

The gas content (wt%) of the steel pipe finished product of table 7 example 1 to 3

	[H]	[O]	[N]
				Example 1	0.00007	0.0018	0.0049
Example 2	0.00003	0.0016	0.0061
				Example 3	0.00005	0.0015	0.0043

The field trash high power rating result of the steel pipe finished product of table 8 example 1 to 3

The mechanical property of the steel pipe finished product of table 9 example 1 to 3

Table 5 is visible, analyzes different parts sample analysis and obtain carbon content in steel, carbon on strand transverse section Segregation index and extreme difference value are less, illustrate that strand composition is uniform, and then can ensure that steel tube performance stablizes group Knit uniformly；From table 6, carry out macrostructure inspection by GB/T226 standard, by YB/T4149-2006 Appendix A judge picture carries out rating result to macro defect and shows, the continuous casting circular tube blank strand that the present invention provides Center mass is good, and central defect is few, and Center Equiaxial Crystal is wider, processes for follow-up tubulation and bottle multi-pass processed Ensure inner surface quality, final ensure that steel cylinder inner surface is bright and clean and smooth provide good precondition.By Table 7 to table 9 it can be seen that the present invention provide electronic gas Large Copacity gas vessel, its steel pipe finished product Steel is pure, evaluates according to field trash rating scale GB/T10561: A, B, C, D all≤1 grade；Steel Pipe finished product gas ［ N ］≤70PPm, ［ O ］≤18PPm, ［ H ］≤2.0PPm；Al content 0.015～ 0.040wt%, steel pipe sample is tissue grain size >=7 grade after simulation is quenched, and yield strength at normal temperatures is not Less than 800MPa, tensile strength (tensile strength) not less than 935MPa, elongation percentage not less than 17%, Hardness is not less than 285HB and ballistic work >=75AKV/J when-40 DEG C, and i.e. sample is after Analog heat-treating Tensile property and-40 DEG C of low-temperature impact toughness meet technology requirement.

The method of the present invention, by optimizing composition design and the steel purification technology of steel, will cause toughness possible The impurity elements such as As, Sn, S, P, Ti, Cu, the Ni reduced and residual elements are reduced to minimum as far as possible Limit；And ensure that electronics gas vessel high cleanliness, low gas, the metallurgical quality of low inclusion content are wanted Ask, so that the property indices of electronic gas gas cylinder seamless large-diameter pipes meets correlation technique and wants Ask；It addition, reasonably control the cold specific water of round billet continuous casting machine two, pulling rate and cooling twice water distribution, anti- Only strand produces underbead crack and reduces central pipe and center porosity, and uses M-EMS, Ensure that the crystallographic texture (as Center Equiaxial Crystal district expands) of strand ensure that strand center mass, Preferable precondition is provided for next step tube rolling and following process.The method of the present invention not only ensure that Electronic gas gas cylinder large diameter thin wall seamless steel pipe and gas cylinder manufacture the manufacturing of multi-pass processing Can, it is often more important that meet electronic gas large-volume packing gas cylinder have intensity height, good toughness, Metallographic grain size is careful and the requirement of the combination property such as low-temperature impact toughness, it is ensured that electronic gas store and Safety during use.Here, in strand, composition is uniformly to ensure that steel tube performance stabilizing tissue is uniform Premise, strand center mass, composition are uniformly and purity of steel is to inside and outside during tube rolling and following process Surface quality (defect) impact is very big, composition uniformly (carbon content on above-mentioned strand cross section Extreme difference and segregation are little), strand center mass is good, steel purity height is to ensure that in the multi-pass course of processing few product Raw defect or defect the most do not affect final products surface quality, have been particularly ensured that gas cylinder inner surface is smooth； On the other hand, the anti-wear performance of steel is the best, and the thinnest steel of crystal grain of steel is the finest and close, makes air bottle steel surface pass through After the surface treatment such as surface grinding, polishing processes, the most easily improve surface smoothness.

Although the most describe the present invention by combining exemplary embodiment, but people in the art Member, can be to the present invention it should be clear that in the case of the spirit and scope limited without departing from claim Exemplary embodiment carry out various modifications and changes.

Claims (2)

1. the preparation method of an electronic gas Large Copacity gas vessel, it is characterised in that described method bag Include following steps:

Make steel water at the beginning of electric furnace, control endpoint molten steel composition and include by weight percentage: C:0.12～0.20%, P:0.001～0.007%, As≤0.023%, Sn≤0.010%, tapping temperature is 1620～1660 DEG C, and To ladle, pre-deoxidation and Alloying Treatment is carried out in tapping；

Molten steel is carried out LF refine, and controls the molten steel composition that LF refine obtains and wrap by weight percentage Include: C:0.40～0.44%, Si:0.27～0.32%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.023%, Sn≤0.010% and Al:0.035～0.060%；

Molten steel is carried out VD vacuum refining, and controls molten steel composition that vacuum refining obtains with weight percent Include than meter: C:0.40～0.44%, Si:0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.010%, Ni≤0.15%, Cu≤0.15%, As≤0.025%, Sn≤0.010%, Al:0.015～0.040%, H≤0.0002%, [O]≤0.0018% and N≤0.0050%；

Continuous casting, in casting process, two cold employing weak chill formulas and the specific water of two cold-zones is controlled be 0.20～0.27L/Kg, and by weight percentage, the chemical composition of the strand that continuous casting obtains is C: 0.40～0.45%, Si:0.25～0.35%, Mn:0.85～1.00%, P≤0.013%, S≤0.008%, Cr:1.00～1.10%, Mo:0.20～0.25%, Ti≤0.006%, Ni≤0.04%, Cu≤0.08%, Sn≤0.007%, 0 ＜ As≤0.025%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, surplus is ferrum and inevitable impurity；

Non-metallic inclusion A class, B class, C class and the D class of described electronic gas Large Copacity gas vessel No more than 1.0 grades, yield strength at normal temperatures is not less than not less than 800MPa, tensile strength 935MPa, elongation percentage not less than 17%, hardness is not less than 285HB and ballistic work >=75 when-40 DEG C AKV/J,

Wherein, the strand that described continuous casting step obtains is the round base of a diameter of Φ 350～388mm,

In described casting process, the cooling water of the two each cooling sections in cold-zone is assigned as: two coolings of cold I section The water yield account for two cold-zones cooling water total Waters 16～19%, two the cooling water inflow of cold II section account for two cold-zones coolings The 20 of water total Water～22%, two the cooling water inflow of cold III section account for two cold-zones cooling water total Waters 9～ 12%, two cooling water inflows of cold IV section account for the 27～31% and two cold V section of two cold-zones cooling water total Waters Cooling water inflow account for two cold-zones cooling water total Waters 17～21%,

In described casting process, controlling the Metal in Tundish degree of superheat is 15～35 DEG C, and crystallizer uses electricity Magnetic stirs and controls cooling water flow is 1400～1600L/min, and casting speed is 0.40～0.55m/min,

In described LF refinement step, add reducing agent and make white slag, and make the white slag retention time at 20min Above, wherein, by weight percentage, described reducing agent consist of 30～70 parts carbide, 5～ The SiCa of 20 parts and the aluminum slag of 25～50 parts,

In described VD vacuum refining step, holding vacuum≤66.7Pa, retention time >=15 minute, Until slag no longer foams and continues to keep more than 2 minutes, and after vacuum breaker, feed Si-Ca line 0.5～ 0.8Kg/t steel, then carries out quiet blowing to molten steel,

In described continuous casting step, controlling middle unwrapping and water liquid level >=650mm, process cast liquid level is high Degree >=700mm, even waters liquid level >=450mm and finally stops to water liquid level >=300mm.

The preparation method of electronic gas Large Copacity gas vessel the most according to claim 1, its feature Be, by weight percentage, the chemical composition of described electronic gas Large Copacity gas vessel be C:0.41～ 0.44%, Si:0.27～0.33%, Mn:0.86～0.98%, P≤0.011%, S≤0.005%, Cr: 1.00～1.10%, Mo:0.20～0.25%, Ti≤0.006%, Ni≤0.04%, Cu≤0.08%, Sn≤0.007%, As≤0.023%, Al:0.015～0.040%, [H]≤0.0002%, [N]≤0.0070%, T [O]≤0.0020%, Surplus is ferrum and inevitable impurity.