CN102409242A - Alloy steel for high-strength gas cylinder, gas cylinder and manufacturing method thereof - Google Patents
Alloy steel for high-strength gas cylinder, gas cylinder and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to alloy steel for a high-strength gas cylinder. The alloy steel consists of the following chemical components in percentage by weight: 0.30-0.38 percent of C, 0.15-0.37 percent of Si, 0.60-0.90 percent of Mn, 0.80-1.20 percent of Cr, 0.15-0.30 percent of Mo, 0.01-0.05 percent of Al, 0.00-0.25 percent of Ti, 0.02-0.25 percent of Nb, 0.03-0.20 percent of W, less than or equal to 0.010 percent of P, less than or equal to 0.010 percent of S, 0.002-0.004 percent of Ca, less than or equal to 0.0035 percent of N and the balance of Fe and inevitable impurities, wherein Ti+Nb is more than or equal to 0.07 percent; and the total quantity of impurity elements is less than 0.05 percent. A manufacturing method of the high-strength gas cylinder comprises the following steps of: smelting, refining, performing VD (Vacuum Distillation) treatment, controlling the content of elements P and S in the steel, and adjusting the content of N simultaneously; before tapping, feeding Si-Ca wires in an amount of 2-3 meters into every ton of steel for denaturalizing inclusions; pouring a square billet with a large square billet continuous casting machine under the protection of argon gas, blooming at the temperature 1,050-1,090 DEG C, and cogging to obtain a square billet material; manufacturing a seamless gas cylinder; preserving the heat of the seamless gas cylinder at the temperature 800-940 DEG C for 30-60 minutes, and performing water quenching treatment; and tempering at the temperature 500-650 DEG C, and preserving heat for 30-120 minutes. The obtained gas cylinder steel has a tempered sorbite structure, the tensile strength is over 1,100 MPa, and the low-temperature impact toughness at the temperature 50 DEG C below zero is over 45 J/cm<2>.
Description
Technical field
The present invention relates to gas cylinder and use low alloy steel, particularly relate to a kind of high-strength low-alloy steel that is used to produce high-pressure seamless gas cylinder and preparation method thereof.
Background technology
Gas cylinder is meant the transportable pressure vessel of but repeated inflation is used under home splendid attire permanent gases, liquefied gas or gas dissolved etc.Steel tank has been widely used in fields such as industry, mining industry, military affairs, medicine, diving, automobile as a kind of gas storage container.Can be divided into two types of welded gas cylinder and seamless gas cylinders again according to the different steel tanks of ME.Welded gas cylinder is to be raw material with the steel plate, the steel cylinder that the weldering of punching press volume is made.Seamless gas cylinder is to be raw material with the steel billet, is material through the punching stretch manufacturing or with the weldless steel tube, close up to receive the end and makes through hot spinning.Seamless gas cylinder fundamentally eliminated traditional gas cylinder in producing relevant with weld seam discontinuous, intensity reduction, embrittlement and tensile stress defective such as concentrate, the resistance to air loss of gas cylinder and withstand voltage properties have had significantly raising.
Along with the progress of industrial technology, people have higher requirement to WP, nominal volume, the bottle weight of steel seamless gas cylinder.At present, the common charge pressure of seamless steel gas cylinder is 15-20MPa, and few part adopts the 30MPa high pressure to fill.According to statistics, the ratio of external 30MPa high pressure gas cylinder is 10% average annual speed increment.The nominal volume that increases gas cylinder equally also is beneficial to and improves the gas cylinder gas storage capability, but the volume increase will cause the gas cylinder diameter to increase, and is the safe handling that guarantees gas cylinder, will have in the design improve a bottle wall thickness, certainly will increase gas cylinder weight.Current, the development of society is just carried out towards the direction of resource-conserving, advocates the light-weight design notion of product, structure energetically.For high charge pressure, big volume seamless gas cylinder, only under the prerequisite that the billet material performance guarantees, the wall thickness of gas cylinder just might reduce, thereby makes the weight of single gas cylinder reduce, and both reaches to economize on resources, and alleviates the purpose of transportation cost again.The gas cylinder Steel Alloy Tensile strength that present industrial production is used always all below 1100MPa, if further improve its intensity through heat treating method, will make the gas cylinder low-temperature impact toughness guarantee.
CN101818309A has introduced a kind of gas cylinder steel and method of manufacture thereof; Main through improving in the steel more than the Mo content to 0.40%; Add a spot of Ti element reinforced alloys simultaneously, steel billet tensile strength after Q-tempering is handled reaches more than the 1120MPa, and elongation after fracture is more than 14%.
CN101560631A provides a kind of billet material for manufacturing steel seamless gas cylinder; Main through P, S, V, Nb, Ti, B, Zr, Cu, Al constituent content in the control material; Optimize C, Si, Mn, Cr content simultaneously; When this billet material through punching press and after processing seamless gas cylinder tensile strength reach 920MPa when above, still can pass through H
2The S stress corrosion (cracking) test can be used for storing in the automobile dynamic system compressed natural gas.
US4461657 provides the method for manufacture of a kind of plow-steel and gas cylinder; Main through adding the V element strengthening material of 0.04-0.10%; Add Ca and REE according to S constituent content in the steel simultaneously, this Tensile strength can reach more than the 1069MPa after the optimization thermal treatment process.
US5133928 provides a kind of gas cylinder composition of steel, is less than 0.25% Ni through reducing in the steel below the S content to 0.005%, adding simultaneously, to improve the intensity and the toughness of steel.
Above-mentioned patent or apply for that related low-alloy steel grade takes to add the mode that the Ni element improves Mo content simultaneously mostly; Reach the purpose that improves the strength of materials, toughness and temper resistance; But the interpolation of Ni, Mo element will make the material alloys cost increase, thereby make final gas cylinder price improve.
Along with the progress of industrial technology, improve gas and transmit the purpose with efficiency of storage for reaching, the requirement of steel seamless gas cylinder has higher WP, big nominal volume and light bottle weight.This has higher requirement for the material property that is used to make seamless gas cylinder, particularly its intensity and toughness.Therefore, the high-pressure seamless gas cylinder of research and development HS, high impact toughness is significant with low alloy steel.
Summary of the invention
The object of the present invention is to provide a kind of tensile strength more than 1100MPa ,-50 ℃ of low-temperature impact toughness are at 45J/cm
2More than, need not simultaneously to add the Ni element, and the economical HS gas cylinder that Mo content is controlled at below 0.30% is used steel alloy.
For realizing above-mentioned purpose, HS gas cylinder of the present invention is used steel alloy, and its chemical ingredients proportioning (weight percent) is: C:0.30-0.38%, Si:0.15-0.37%; Mn:0.60-0.90%, Cr:0.80-1.20%, Mo:0.15-0.30%, Al:0.01-0.05%; Ti:0.00-0.25%, Nb:0.02-0.25%, W:0.03-0.20%, Ca:0.002-0.004%; P≤0.010%, S≤0.010%, and Ti+Nb>=0.07%, Ca:0.002-0.004%; N≤0.0035%, all the other are Fe and unavoidable impurities, the total amount of impurity element is lower than 0.05%.
Above-mentioned HS gas cylinder of the present invention is organized as the tempered sorbite tissue with steel alloy.
The tensile strength that above-mentioned HS gas cylinder of the present invention uses steel alloy is as more than the 1100MPa, and-50 ℃ of low-temperature impact toughness are higher than 45J/cm
2Preferably, the tensile strength of said steel alloy is 1150-1305MPa, and-50 ℃ of low-temperature impact toughness are 50-90J/cm
2
Another object of the present invention provides the steel tank of being made by above-mentioned steel alloy.
Another purpose of the present invention provides the method for manufacture of HS gas cylinder, and this method comprises:
Behind electric furnace or converter smelting, carry out refining of LF stove and VD and handle, P, S constituent content are adjusted N content (≤0.0035%) simultaneously in the control steel;
Feeding Si-Ca line carries out the inclusion modification processing before the tapping, and feed quantity is a 2-3m/ ton steel;
After adopting continuous caster under argon shield, to pour into a mould square billet, the breaking down cogging is a square billet under 1050-1090 ℃ of temperature; Square billet through cutting, heating, dash the seamless steel gas cylinder of processing each specification after pulling out, closing up;
Seamless gas cylinder, carries out water quenching and handles after 30-60 minute 800-940 ℃ of insulation; Tempering under 500-650 ℃ of temperature subsequently, soaking time is 30-120 minute.
Preferably, the employing bloom caster pours into the 300-425mm square billet under argon shield after, the breaking down cogging is the 150-250mm square billet under 1050-1090 ℃ of temperature.
The gas cylinder that adopts mentioned component and method of manufacture to produce can reach more than the 1100MPa with steel alloy intensity, has enough toughness simultaneously, thereby reaches the requirement of gas cylinder safe handling.Because this gas cylinder steel intensity is high, can be used for making high pressure, big volume, lightweight gas cylinder, thereby improve the service efficiency of gas cylinder.
Because this composition gas cylinder adds the purpose that reaches refined crystalline strengthening and precipitation strength with steel alloy through Ti, Nb; Add the temper brittleness of W element reduction steel simultaneously; Need not to add the Ni element, and Mo content is lower than under 0.30% condition, intensity still can reach more than the 1100MPa; Can effectively reduce the cost of alloy of material, thereby make the gas cylinder cost for preparing by this alloy reduce.
Embodiment
Below the present invention is carried out comparatively detailed explanation.
Among the present invention, unless otherwise, content all refers to weight percent content.
For realizing the tensile strength that provides of the present invention more than 1100MPa ,-50 ℃ of low-temperature impact toughness are at 45J/cm
2More than, need not simultaneously to add the Ni element, and Mo content is controlled at the purpose of the economical HS gas cylinder steel below 0.30%, be not subject to any theory, the chemical ingredients of steel alloy of the present invention is selected as follows and is controlled:
C guarantees gas cylinder steel room temperature strength and the necessary composition of hardening capacity.Under this composition system, the insufficient strength of steel when carbon content is lower than 0.30% is higher than at 0.38% o'clock and can makes that then toughness of material is too poor, can't satisfy the requirement of gas cylinder safety in utilization.Therefore, C content is controlled at 0.30-0.38% in the steel of the present invention.
Si adds the purpose that mainly plays deoxidation and reinforced ferrite phase in the steel, and DeGrain when the Si constituent content is lower than 0.15% in the alloy after content surpasses 0.37%, worsens processibility that makes steel and toughness.Therefore, Si content is controlled at 0.15-0.37% in the steel of the present invention, preferably, and Si:0.15-0.30%, more preferably Si:0.15-0.25%.
Through the interaction of Mn, Cr, Mo element, guarantee that material does not ftracture under the shrend condition, obtain the martensite heterogeneous microstructure simultaneously.Mn, Cr, Mo element improve the strength of materials and toughness through solution strengthening and precipitation strength effect, improve the material temper resistance simultaneously.In addition; The interpolation of Mn element also helps the deleterious effect of eliminating S in the steel, avoids forming low-melting FeS, but will reduce toughness of material during too high levels; Therefore Mn content is controlled at 0.90% below and more than 0.60% among the present invention, preferably Mn:0.75-0.90%.The raising of Mo element will make cost of alloy increase, and be to guarantee economical property, be controlled at Mo content 0.30% below among the present invention and more than 0.15%, Cr content will be controlled to be 0.80-1.20%, be preferably 0.90-1.10%.
Al has mainly played the effect of desoxydatoin and crystal grain thinning in steel; When add-on is lower than 0.01%, DeGrain, but add-on is prone to form brittle aluminate when too much; Toughness to steel is harmful, so the present invention controls its content below 0.05% and more than 0.01%.
Ti, Nb element have strong nitride and carbide formation tendency, and the nitride of Ti, Nb and carbide are separated out material hardness and intensity are increased in this composition alloy temper process, and secondary hardening takes place, so need interpolation Ti and Nb total amount to be higher than 0.07% in the steel.If Ti that adds in the alloy and Nb too high levels will make its carbide and nitride separate out too early, and size are thick, so among the present invention its content are controlled at respectively and are lower than 0.25%.Preferably, Nb:0.05-0.25%; More preferably, Ti:0.07-0.25%.
Being added with of W element is beneficial to hardening capacity and the intensity that improves steel, also can prevent brittle generation in the drawing process simultaneously, so adds the W of 0.03-0.20% among the present invention.
Ca handles form and the character that will improve brittle inclusion in the steel, helps improving the low-temperature impact toughness of gas cylinder steel, and the scope of therefore controlling Ca element in the steel is 0.002-0.004%.
For the toughness that guarantees material is controlled at deleterious P, S constituent content in the steel of the present invention below 0.010%.
Above-mentioned HS gas cylinder steel of the present invention, according to following method manufacturing:
Behind electric furnace or converter smelting, carry out refining of LF stove and VD and handle, P, S constituent content are adjusted N content (≤0.0035%) simultaneously in the control steel;
Feeding Si-Ca line carries out the inclusion modification processing before the tapping, and feed quantity is a 2-3m/ ton steel;
After adopting bloom caster under argon shield, to be cast for the 300-425mm square billet, the breaking down cogging is the 150-250mm square billet under 1050-1090 ℃ of temperature; Square billet through cutting, heating, dash the seamless steel gas cylinder of processing each specification after pulling out, closing up;
The thermal treatment process of seamless gas cylinder is 800-940 ℃ of insulation after 30-60 minute, carries out water quenching and handles; Tempering under 500-650 ℃ of temperature subsequently, soaking time is 30-120 minute.
Thermal treatment temp before quenching is high more, under the prerequisite that guarantees tensile strength, suitably improves tempering temperature simultaneously, all will help improving the impelling strength of steel.Therefore, the thermal treatment process of seamless gas cylinder optimization is 880-940 ℃, and tempering process is 550-630 ℃.
The gas cylinder hardness of steel that adopts mentioned component and method of manufacture to produce can reach more than the 1100MPa, has enough toughness simultaneously, thereby reaches the requirement of gas cylinder safe handling.Because this gas cylinder steel intensity is high, can be used for making high pressure, big volume, lightweight gas cylinder, thereby improve the service efficiency of gas cylinder.
Because this composition gas cylinder steel adds the purpose that reaches refined crystalline strengthening and precipitation strength through Ti, Nb; Add the temper brittleness of W element reduction steel simultaneously; Need not to add the Ni element, and Mo content is lower than under 0.30% condition, intensity still can reach more than the 1100MPa; Can effectively reduce the cost of alloy of material, thereby make the gas cylinder cost for preparing by this alloy reduce.
Embodiment
Shown in the chemical ingredients such as following table 1 of the gas cylinder product made from steel of embodiments of the invention 1-10.
The chemical ingredients of table 1 embodiment of the invention gas cylinder steel, wt%
| Grade of steel | C | Si | Mn | Cr | Mo | Al | Ti | Nb | W | Ca | N | P | S |
| A1 | 0.30 | 0.25 | 0.90 | 1.10 | 0.25 | 0.01 | 0.25 | 0.06 | 0.03 | 0.002 | 0.0035 | 0.008 | 0.004 |
| A2 | 0.30 | 0.25 | 0.90 | 1.10 | 0.30 | 0.02 | 0.15 | 0.05 | 0.05 | 0.003 | 0.0030 | 0.008 | 0.006 |
| A3 | 0.34 | 0.20 | 0.75 | 1.05 | 0.20 | 0.01 | 0.02 | 0.20 | 0.03 | 0.002 | 0.0032 | 0.009 | 0.004 |
| A4 | 0.34 | 0.22 | 0.75 | 1.03 | 0.20 | 0.02 | 0.08 | 0.05 | 0.06 | 0.004 | 0.0034 | 0.010 | 0.010 |
| A5 | 0.35 | 0.24 | 0.80 | 0.80 | 0.15 | 0.03 | 0.15 | 0.05 | 0.10 | 0.003 | 0.0035 | 0.008 | 0.006 |
| A6 | 0.35 | 0.24 | 0.80 | 0.90 | 0.15 | 0.03 | 0.10 | 0.07 | 0.03 | 0.003 | 0.0029 | 0.007 | 0.003 |
| A7 | 0.37 | 0.15 | 0.69 | 0.95 | 0.15 | 0.03 | 0.07 | 0.09 | 0.05 | 0.002 | 0.0023 | 0.009 | 0.005 |
| A8 | 0.38 | 0.15 | 0.75 | 0.95 | 0.22 | 0.05 | 0.07 | 0.25 | 0.03 | 0.004 | 0.0028 | 0.008 | 0.009 |
| A9 | 0.33 | 0.25 | 0.90 | 1.10 | 0.25 | 0.01 | 0.25 | 0.06 | 0.15 | 0.002 | 0.0020 | 0.008 | 0.004 |
| A10 | 0.31 | 0.15 | 0.75 | 0.95 | 0.22 | 0.05 | 0.07 | 0.25 | 0.20 | 0.003 | 0.0031 | 0.008 | 0.009 |
| A11 | 0.35 | 0.20 | 0.80 | 1.00 | 0.25 | 0.02 | 0.00 | 0.13 | 0.08 | 0.003 | 0.0035 | 0.007 | 0.004 |
The preparation method of the gas cylinder product made from steel of embodiment 1-11 is following:
1) this gas cylinder steel carries out refining of LF stove and VD processing behind electric furnace or converter smelting, P, S constituent content (as shown in table 1) in the control steel.Feeding Si-Ca line carries out the inclusion modification processing before the tapping, and feed quantity is a 3m/ ton steel.
2) after the employing bloom caster was cast for 340 * 425mm square billet under argon shield, the breaking down cogging was the 200mm square billet under 1070 ℃ of temperature.Square billet is through cutting, heat, after pulling out, closing up, processing seamless steel gas cylinder, and its thickness is 4-7.5mm.Usually the thickness of steel cylinder is 5-10mm.
Shown in the thermal treatment process such as following table 2 of the gas cylinder product made from steel of embodiment 1-11.
Test Example 1: mechanical property
According to GB/T 228, GB/T 2106, measure the mechanical property of embodiment of the invention gas cylinder steel, and its result is as shown in table 2.
The processing parameter and the mechanical property of table 2 embodiment of the invention gas cylinder steel
Can find out from above result, gas cylinder steel of the present invention, its tensile strength reaches 1150-1305MPa, and-50 ℃ of low-temperature impact toughness reach 50-90J/cm
2
The gas cylinder hardness of steel that adopts mentioned component and method of manufacture to produce can reach more than the 1100MPa, has enough toughness simultaneously, thereby reaches the requirement of gas cylinder safe handling.Because this gas cylinder steel intensity is high, can be used for making high pressure, big volume, lightweight gas cylinder, thereby improve the service efficiency of gas cylinder.
Because this composition gas cylinder steel adds the purpose that reaches refined crystalline strengthening and precipitation strength through Ti, Nb; Add the temper brittleness of W element reduction steel simultaneously; Need not to add the Ni element, and Mo content is lower than under 0.30% condition, intensity still can reach more than the 1100MPa; Can effectively reduce the cost of alloy of material, thereby make the gas cylinder cost for preparing by this alloy reduce.
Steel alloy of the present invention, because its intensity is high, good toughness, low price can be widely used in fields such as industry, mining industry, military affairs, medicine, diving, departure with its gas cylinder that produces.
Claims (16)
1. high strength alloy steel, its weight percent chemical ingredients is: C:0.30-0.38%, Si:0.15-0.37%, Mn:0.60-0.90%; Cr:0.80-1.20%, Mo:0.15-0.30%, Al:0.01-0.05%, Ti:0.00-0.25%; Nb:0.02-0.25%, W:0.03-0.20%, P≤0.010%; S≤0.010%, and Ti+Nb>=0.07%, Ca:0.002-0.004%; N≤0.0035%, all the other are Fe and unavoidable impurities, the total amount of impurity element is lower than 0.05%.
2. high strength alloy steel as claimed in claim 1 is characterized in that, Si:0.15-0.30%, preferably, Si:0.15-0.25%.
3. according to claim 1 or claim 2 high strength alloy steel is characterized in that, Mn:0.70-0.90%, preferably, Mn:0.75-0.90%.
4. like the arbitrary described high strength alloy steel of claim 1-3, it is characterized in that Cr:0.90-1.10%.
5. like the arbitrary described high strength alloy steel of claim 1-4, it is characterized in that Ti:0.07-0.25%.
6. like the arbitrary described high strength alloy steel of claim 1-5, it is characterized in that Nb:0.05-0.25%.
7. like the arbitrary described high strength alloy steel of claim 1-6, it is characterized in that Ti+Nb >=0.13%.
8. like the arbitrary described high strength alloy steel of claim 1-7, it is characterized in that N:0.0020-0.0035%.
9. like the arbitrary described high strength alloy steel of claim 1-8, it is characterized in that, be organized as tempered sorbite.
10. like the arbitrary described high strength alloy steel of claim 1-9, it is characterized in that the tensile strength of said steel is more than the 1100MPa ,-50 ℃ of low-temperature impact toughness are higher than 45J/cm
2
11. high strength alloy steel as claimed in claim 10 is characterized in that, the tensile strength of said steel is 1150-1305MPa, and-50 ℃ of low-temperature impact toughness are 50-90J/cm
2
12. steel tank like the arbitrary described high strength alloy steel manufacturing of claim 1-11.
13. the method for manufacture of HS steel gas cylinder as claimed in claim 12 comprises:
Behind electric furnace or converter smelting, carry out refining of LF stove and VD and handle, P, S constituent content are adjusted N content simultaneously in the control steel;
Feeding Si-Ca line carries out the inclusion modification processing before the tapping, and feed quantity is a 2-3m/ ton steel;
After adopting continuous caster under argon shield, to pour into a mould square billet, the breaking down cogging is a square billet under 1050-1090 ℃ of temperature; Square billet through cutting, heating, dash the seamless steel gas cylinder of processing each specification after pulling out, closing up;
Seamless gas cylinder, carries out water quenching and handles after 30-60 minute 800-940 ℃ of insulation; Tempering under 500-650 ℃ of temperature subsequently, soaking time is 30-120 minute.
14. method as claimed in claim 13 is characterized in that, seamless gas cylinder is incubated after 30-60 minute at 880-940 ℃, carries out water quenching and handles; Tempering under 550-630 ℃ of temperature subsequently, soaking time is 30-120 minute.
15. like claim 13 or 14 described methods, it is characterized in that, be cast for the 300-425mm square billet.
16., it is characterized in that the breaking down cogging is the 150-250mm square billet like the arbitrary described method of claim 13-15.
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| WO2022112607A1 (en) | 2020-11-30 | 2022-06-02 | Dalmine S.P.A. | Steel composition, wrought article and manufacturing method of a seamless pressure vessel for compressed gas |
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| CN105619085B (en) * | 2016-02-29 | 2018-11-06 | 扬州诚德钢管有限公司 | The big volume seamless steel gas cylinder production technologies of diameter 914mm |
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| CN114086083B (en) * | 2020-08-25 | 2023-01-20 | 宝山钢铁股份有限公司 | 1100 MPa-grade sulfur-resistant high-pressure gas cylinder steel, high-pressure gas cylinder and manufacturing method thereof |
| WO2022112607A1 (en) | 2020-11-30 | 2022-06-02 | Dalmine S.P.A. | Steel composition, wrought article and manufacturing method of a seamless pressure vessel for compressed gas |
| CN115305394A (en) * | 2022-08-17 | 2022-11-08 | 上海锴朴机电有限公司 | Aluminum alloy material for high-pressure gas cylinder and preparation method thereof |
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