CN101497961B - Low-temperature flexibility 1.5Ni steel and method of manufacturing the same - Google Patents
Low-temperature flexibility 1.5Ni steel and method of manufacturing the same Download PDFInfo
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Abstract
The invention discloses low-temperature ductility 1.5Ni steel and a manufacturing method thereof, wherein the low-temperature ductility 1.5Ni steel comprises the chemical components according to percentages by weight of 0.02-0.10 percent of C, 0.22-0.30 percent of Si, 1.00-1.50 percent of Mn, less than or equal to 0.08 percent of V, 1.20-1.60 percent of Ni, less than or equal to 0.005 percent of S, less than or equal to 0.010 percent of P, less than or equal to 0.03 percent of Nb, less than or equal to 0.04 percent of Ti, less than or equal to 0.04 percent of Al, 0.002-0.005 percent of N and the rest of Fe and unavoidable impurities. The manufacturing method comprises the following steps of smelting and casting into a casting blank, heating the casting blank, controlled rolling and heat treatment. In the invention, after the micro alloy steel finishes the controlled rolling, a high-strength low-temperature pressure vessel steel plate which has yield strength of more than 400MPa, tensile strength of more than 500MPa and satisfies the low-temperature impact ductility requirement of 100 DEG C below is produced through adopting a thermal refining method. The invention is suitable for manufacturing vessels, such as a low-temperature pressure vessel, a liquefied natural gas storage tank, a liquefied petroleum gas storage tank, a petrochemical storage tank, and the like.
Description
Technical field
The present invention relates to a kind of Ni steel, belong to low-temperature flexibility 1.5Ni steel and manufacture method thereof especially.
Background technology
Low-temperature steel is mainly used in makes pressurized vessel and the storage tank that stores and transport all kinds of liquefied gas.Ni is an important element in the development low-temperature steel, developed the low-temperature steel of different stages such as 1.5Ni, 3.5Ni, 5Ni, 9Ni according to the difference of Ni content, to be applicable to different low temperature environments and medium, wherein the 1.5Ni steel is widely used in chemical industry and field of petrochemical industry-45 ℃～-80 ℃ of steel for low-temperature pressure container, ethylene unit as chemical enterprise, low temperature washing device for methanol in the coal pressure gasification of city etc., the needs that also can satisfy LPG (liquefied petroleum gas (LPG)) storage and carry.As low-temperature steel, a very important technical indicator is exactly a low-temperature impact toughness, alloying element Ni adds in the steel, solid solution is significantly improved the low-temperature flexibility of matrix in ferrite, but Ni is a kind of than noble element, about 280000 yuan/ton, when increasing cost, the strand that contains the Ni steel forms the fine and close iron scale that is difficult to remove easily when heating, bring difficulty for the heating rolling operation.Therefore explore and reduce the low-temperature steel production cost and guarantee that the production technique of good low-temperature flexibility will play an important role for the development of low-temperature (low temperature) vessel with the 1.5Ni steel.
Through domestic, international online retrieval, this patent of patent No. JP2000001735 has been set forth a kind of good low alloy steel of nitriding ability and hot strength and low-temperature flexibility that has, by intensity and the low-temperature impact toughness under the size raising high temperature that increases Ni content and control recrystal grain, and hardening capacity is enhanced, the suitable large-size workpiece of making.This patent of patent No. JP2002129280 JP09302445A has been set forth a kind of pressurized vessel with the production method that contains the Ni steel plate, can realize low temperature welding, satisfies the requirement about intensity in the various steel for low-temperature pressure container standards.It adopts low carbon component design, and Ni content contains 1.5% to 9.5%, and contains 0.02～0.08%Mo, and steel plate is through quenching temper.In order to obtain the tissue of grain refining, 750～850 ℃ add up deformation rate greater than 50% rolling, roll the back and be cooled to more than 400 ℃ with cooling rate greater than 2 ℃/s, perhaps be cooled to below 400 ℃, again in the Ac1 temperature or followingly carry out tempering.Patent No. US4137104A has set forth a kind of manufacture method of Arctic region pipeline with high strength, good low-temperature toughness steel plate that be used to make, wherein Ni content is 0.8～2.0%Ni, and inclusion is carried out modification handle by adding 0.0005～0.0040%Ca, its goal of the invention is to provide a kind of low-temperature steel of cheapness, be used to make the pipe line steel of large size bore, to substitute the 3.5Ni steel.Patent No. JP54071714A has set forth the production method of a kind of high strength, high arrest toughness steel.Comprising 0.03～0.18%C, 0.05～0.60%Si and 0.6～2.0%Mn fundamental element, but added elements comprises one or more: Nb≤0.15%, V≤0.15%, Cu≤0.7%, Cr≤0.7%, Mo≤0.3%, Ni≤2.0% and Al≤0.1%.Patent No. JP60103118A patent has been set forth a kind of inexpensive but bar steel making method of excellent in low temperature toughness.It has added this more valuable alloying element of Mo, and composition system and this patent are distinguished to some extent, and concrete composition contrast is as shown in table 1.Its rolling technology is: greater than 60% distortion, finish finish to gauge below 880 ℃ in the amount of being rolled below 850 ℃, roll the back air cooling to room temperature or further carry out tempering between 500 ℃～700 ℃.Patent No. CN99109124.8 has set forth a kind of controlled rolling technology for microally steel with superfine structure, the main technique flow process is as follows: at first, steel billet is heated to 1150 ℃～1220 ℃ fully dissolves microalloy element, steel billet is come out of the stove the back in 900 ℃～1150 ℃ temperature ranges, implement twice time controlled rolling, the deflection of each passage is between 20～40%, it is rolling in 800 ℃～840 ℃ temperature ranges steel billet to be implemented continuous three passage strain inducings then, every time deflection is 30～50%, the pitch time of each passage was less than 10 seconds, finish above-mentioned strain inducing rolling after, with the speed of cooling of 〉=10 ℃/s steel plate is implemented to quicken cooling.Patent No. CN98812439. has set forth a kind of containing and has been less than the production technique that 9%Ni content has the high-strength steel of excellent low-temperature flexibility.Rolling technology is: at austenite the temperature range of recrystallize can take place, adopt one or more passages; Be lower than austenite recrystallization temperature but be higher than Ar
3The temperature range of transition point adopts one or more passages.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of low-temperature flexibility 1.5Ni steel and manufacture method thereof, to remedy the deficiencies in the prior art, improves high low temperature flexible excellent properties.The present invention adopts austenite recrystallization district and non-recrystallization district rolling, and carried out little rolling of deflection at two-phase region, obtains a kind of bainite type acicular ferrite structure.Compare with above-mentioned patent of having applied in the past, the alloy formula of this patent is simple relatively, only adds content and is no more than 0.10% alloying element, has reduced manufacturing cost and has increased the manufacturability of producing; Adopt low carbon component design, can guarantee good welding property; Utilized the effect of Nb in controlled rolling, effectively crystal grain thinning has improved The comprehensive performance, and can take flexible and changeable rolling technology, enhances productivity, reduces mill load.
The technical scheme that the present invention addresses the above problem is: a kind of low-temperature flexibility 1.5Ni steel, the weight percent proportioning of its chemical ingredients is: C 0.02～0.10wt%, Si 0.22～0.30wt%, Mn 1.00～1.50wt%, V≤0.08wt%, Ni 1.20～1.60wt%, S≤0.005wt%, P≤0.010wt%, Nb≤0.03wt%, Ti≤0.04wt%, Al≤0.04wt%, N 0.002～0.005wt%, all the other are Fe and unavoidable impurities, Ni+Mn=2.40～3.00wt% in the described composition.
Selectively, have at least among Nb, V, the Ti in the described composition a kind of non-vanishing.
Preferably, Nb+V+Ti≤0.10wt% in the described composition.
Carbon C: be strengthening element most economical, the most basic in the steel, the intensity that improves steel had obvious effect, ductility, toughness and the weldability of steel had negative impact but improve C content by solution strengthening and precipitation strength.Low-temperature steel when making pressurized vessel to the strictness of welding performance requriements, so C content can not be too high, the span of control of design carbon is 0.02% to 0.10% in the steel of the present invention, mainly be based on the obdurability coupling and the welding property of steel, do not have enough carbide and solid solution carbon in the too low then steel of carbon content, thereby be unfavorable for that in the austenitic transformation process forming enough strengthening phases obtains required intensity; Otherwise the plasticity of the too high then steel of carbon content and toughness reduce, and weldability is variation also.
Silicon Si: silicon plays the solution strengthening effect in steel, also be simultaneously the deoxidant element in the steel, but too high levels can worsen the welding property of steel.
Manganese Mn: the same with Ni, N, manganese can stop growing up of austenite crystal in the temper process, improve the toughness and the intensity of ferrite matrix, manganese can improve stabilization of austenite and reduce the austenite phase transformation temperature in addition, manganese is weak carbide forming element, in steel, mainly play the solution strengthening effect, help improving the austenitic transformation tissue intensity.In addition, Mn is the useful element that substitutes Ni, so nickel content is depended in the interpolation of manganese content, the span of control of design manganese is 1.00% to 1.50% in the steel of the present invention, and Ni+Mn=2.40～3.00%, too high levels, with increasing the probability that carbide forms, unfavorable to toughness.
Sulphur S and phosphorus P: be inevitable harmful element in the steel, unfavorable to the plasticity and the toughness of steel.Reduce sulphur, phosphorus content during smelting as far as possible, improve the steel purity.
Niobium Nb: niobium is strong carbon and nitrogen compound forming element, and is fairly obvious to the effect of grain refining.Separate out the austenitic answer of obstruction deformation, recrystallize by NbC strain inducing in the course of hot rolling, when making the rolling deformation austenite structure in non-recrystallization zone of finish rolling stage in phase transformation, controlled rolling and controlled chilling change tiny phase-change product into, so that steel has high strength and high tenacity, suitable content is given full play to the effect of controlled rolling.Height is too high not to have further effect and contain, so steel grade Nb content of the present invention is controlled in 0.030%.
Titanium Ti: be a kind of intensive carbonitride forming element, the not molten carbonitride of Ti can stop growing up of austenite crystal when steel heats, TiN that separates out when the roughing of high temperature austenite district and TiC can effectively suppress austenite crystal and grow up, and improve the solid solubility of Nb in austenite simultaneously.In welding process, TiN in the steel and TiC particle can significantly stop the heat affected zone grain growth in addition, thereby the welding property of improving steel plate has obvious effect to the impelling strength of improving welded heat affecting zone simultaneously.But titanium content is too high, and the titanium nitride of formation is thick, and the minimizing of the carbon amount of solid solution in the steel, is unfavorable for obtaining good obdurability coupling.
Vanadium V:V is by forming VN or the fine precipitation particles of V (CN) with C and N, and the reinforcement of steel is contributed.Simultaneously, V helps improving the stability of modified back hardness.But too high as content, then cost increases significantly.
Aluminium Al: aluminium is the main deoxidant element in the steel, helps crystal grain thinning, all adds a certain amount of aluminium in the general steel.
Nitrogen N: in adding the steel of titanium, an amount of nitrogen and titanium form titanium nitride, and this second phase particle is easily separated out at high temperature and helped strengthening matrix, and titanium nitride is highly stable, but when soaking stable existence, effectively stop austenite crystal to be grown up.
The manufacture method of described a kind of low-temperature flexibility 1.5Ni steel, it comprises following steps:
(1) smelts according to following proportioning and be cast into strand: C 0.02～0.10wt%, Si 0.22～0.30wt%, Mn 1.00～1.50wt%, V≤0.08wt%, Ni 1.20～1.60wt%, S≤0.005wt%, P≤0.010wt%, Nb≤0.03wt%, Ti≤0.04wt%, Al≤0.04wt%, N 0.002～0.005wt%, and Ni+Mn=2.40～3.00wt%, all the other are Fe and unavoidable impurities;
(2) strand heating, 1150～1250 ℃ of Heating temperatures;
(3) controlled rolling, 900 ℃～1100 ℃ of the rolling final temperatures of recrystallization zone controlled rolling; 850 ℃～950 ℃ of the rolling beginning temperature of non-recrystallization zone controlled rolling; 800～850 ℃ of two-phase region rolling temperatures;
(4) cooling stops cooling temperature≤300 ℃;
(5) thermal treatment, 850 ℃～950 ℃ of quenching temperatures, 550 ℃～660 ℃ of tempering temperatures.
Selectively, in the step (1), have at least a kind of weight percent non-vanishing among the Nb of adding, V, the Ti.
Preferably, in the step (1), the Nb+V+Ti≤0.10wt% of adding.
Preferably, in the step (3), accumulative total draft 〉=50% of recrystallize controlled rolling; Accumulative total draft 〉=20% of non-recrystallization controlled rolling; Accumulative total draft≤10% of two-phase region controlled rolling.
Preferably, each stage soaking time calculates according to 1～3.5min/mm according to thickness of slab.
Advantage of the present invention and effect are: the composition design of high low-temperature flexibility 1.5Ni steel is with low-carbon (LC), microalloying, reduces Ni content and adds micro-grain refining element nb, Ti, V by increasing Mn; In conjunction with the hot rolling cooling controlling and rolling controlling process, obtained a kind of bainite type acicular ferrite structure, effectively guaranteed the low-temperature flexibility of 1.5Ni steel.The suitable for making low-temperature pressure container.With existing Ni is that low-temperature steel steel grade 3.5Ni steel is compared, and the performance of the 1.5Ni steel that the present invention produces reaches following requirement: tensile property (laterally): target: Rm=490～640MPa; Rp
0.2〉=355MPa; A 〉=22%.
V-notch impact property: target: test temperature-80 ℃, the ballistic work mean value 〉=200J of 10 * 10 * 55mm sample;-100 ℃, the ballistic work mean value 〉=150J of 10 * 10 * 55mm sample.Metallographic structure target: bainite type acicular ferrite structure.
Description of drawings
Fig. 1 is the metallographic structure synoptic diagram of the embodiment of the invention.
Embodiment
A kind of low-temperature flexibility 1.5Ni steel and manufacture method thereof, the weight percent proportioning of its chemical ingredients is: C0.02-0.10wt%, Si 0.22-0.30wt%, Mn 1.00-1.50wt% ,≤V 0.08wt%, Ni1.20-1.60wt%, S≤0.005wt%, P≤0.010wt%, Nb≤0.03wt%, Ti≤0.04wt%, Al≤0.04wt%, N 0.002-0.005wt%, all the other are Fe.
Table 1 is domestic and international patent and the present invention's contrast of 1.5Ni steel: chemical ingredients (wt%)
More than be more approaching domestic and international patent contrast, chemical ingredients sees Table 1 in detail.Can find by contrasting above-mentioned patent: seldom have patent to be designed into the production of 1.5Ni steel, study two kinds of more situations and be: Ni content greater than 1.5% until 12.0%; Less than 1.2%, only usually use as the auxiliary unit that adds, relate to less to the low-temperature steel that contains 1.20%～1.60%Ni content.Most of patent has all been added alloying elements such as Cr, Mo, has also improved manufacturing cost when improving performance, and contrast finds that the present invention only adds one or more among micro-Nb, Ti, the V, and gross weight is no more than 0.1%, greatly reduces manufacturing cost.All related to the technology of controlled rolling among patent JP54071714A, JP60103118A, CN99109124.8, CN200510024776.8, the CN98812439.4, compare with the present invention, the technology of the controlled rolling of being adopted is distinguished to some extent, above patent all requires to carry out in the austenitic area the rolling of different distortion amount, the present invention adopts austenite recrystallization district and non-recrystallization district rolling, and carried out little rolling of deflection at two-phase region, obtain a kind of bainite type acicular ferrite structure.
A kind of manufacture method of low-temperature flexibility 1.5Ni steel, it comprises following steps: smelt and be cast into strand; The strand heating, controlled rolling, thermal treatment.
Table 1
img wi="276" he="829" file="1.GIF" img-format="GIF" img-content="drawing" orientation="portrait" inline="no"/>
Because alloy formula is simple relatively, only add among Nb, Ti, the V one or more, total content is no more than 0.10%, has reduced manufacturing cost and has increased the manufacturability of producing; With the low-carbon (LC) is characteristics, adds about 1.5% Ni, has increased low-temperature impact toughness and good welding property, makes the 1.5Ni low-temperature steel have good crack arrest characteristic, is fit to make low-temperature pressure container.Utilize the effect of Nb in controlled rolling, play the crystal grain thinning effect by generating NbC with C, Nb can suppress the ausforming recrystallize, improved austenite recrystallization temperature, help in austenite non-recrystallization zone rollingly, effectively crystal grain thinning has improved The comprehensive performance, and can take flexible and changeable rolling technology, enhance productivity, reduce mill load.Through after the appropriate heat treatment, (80 ℃ of following Charpy-V impact powers reach more than the 200J to have obtained higher low-temperature impact toughness, 100 ℃ of following Charpy-V impact powers reach more than the 150J), substantially exceed in the EN10028-1 standard about the requirement (Charpy-V impact power under 100 ℃ is greater than 40J) of 3.5Ni steel low-temperature flexibility, alternative 3.5Ni steel uses.
Embodiment 1-5
Table 2 is Chemical Composition of embodiment 1-5
Table 2
According to hot rolling and thermal treatment process, embodiment 1-5 rolling (the thick 20mm of Finished Steel) and heat treatment process parameter scope are as follows:
Slab heating temperature: 1150～1250 ℃; Recrystallize controlled rolling temperature: 950～1100 ℃, accumulative total draft 〉=50%; Non-recrystallization controlled rolling temperature: 870～920 ℃, accumulative total draft 〉=20%; Two-phase region controlled rolling temperature: 800～850 ℃, accumulative total draft≤10%; Stop cooling temperature :≤300 ℃; Quenching temperature: 850～950 ℃; Tempering temperature: 600～660 ℃.
Each stage soaking time calculates according to 1～3.5min/mm according to thickness of slab.
The concrete processing parameter of table 3 embodiment 1-5
Table 3
As shown in Figure 1, the metallographic structure of embodiment after by above-mentioned technology.
Embodiment 1-5 is carried out mechanical property test, and specimen size is 10 * 10 * 55mm, stretches, impacts for horizontal.Table 4 is mechanical properties of embodiment 1-5
Table 4
| Example | Thickness/mm | Yield strength/MPa | Tensile strength/MPa | Unit elongation/% | Akv/J -80℃ | Akv/J -100℃ |
| 1 | 20 | 420 | 540 | 31.0 | 250 | 195 |
| 2 | 20 | 433 | 548 | 30.5 | 283 | 211 |
| 3 | 20 | 460 | 560 | 30.8 | 266 | 221 |
| 4 | 20 | 433 | 555 | 33.5 | 220 | 152 |
| 5 | 20 | 485 | 587 | 30.0 | 280 | 208 |
After controlled rolling, produce a kind of yield strength and reach the method that 400MPa is above, tensile strength 500MPa is above, low-temperature impact toughness satisfies the high strength low-temperature pressure vessel steel plate of-100 ℃ of requirements by the method for modifier treatment with micro-alloyed steel for steel of the present invention.
Claims (8)
1. low-temperature flexibility 1.5Ni steel, it is characterized in that, the attitude metallographic structure of rolling of described low-temperature flexibility 1.5Ni steel is a bainite type acicular ferrite structure, the chemical ingredients per distribution ratio of described low-temperature flexibility 1.5Ni steel is: C 0.02～0.10wt%, Si 0.22～0.30wt%, Mn 1.00～1.50wt%, V≤0.08wt%, Ni 1.20～1.60wt%, S≤0.005wt%, P≤0.010wt%, Nb≤0.03wt%, Ti≤0.04wt%, Al≤0.04wt%, N 0.002～0.005wt%, and Ni+Mn=2.40～3.00wt%, all the other are Fe and unavoidable impurities.
2. low-temperature flexibility 1.5Ni steel as claimed in claim 1 is characterized in that having at least among Nb, V, the Ti in the described composition a kind of non-vanishing.
3. low-temperature flexibility 1.5Ni steel as claimed in claim 1 or 2 is characterized in that Nb+V+Ti≤0.10wt% in the described composition.
4. the manufacture method of a low-temperature flexibility 1.5Ni steel is characterized in that comprising following steps:
(1) smelts according to following proportioning and be cast into strand: C 0.02～0.10wt%, Si 0.22～0.30wt%, Mn 1.00～1.50wt%, V≤0.08wt%, Ni 1.20～1.60wt%, S≤0.005wt%, P≤0.010wt%, Nb≤0.03wt%, Ti≤0.04wt%, Al≤0.04wt%, N 0.002～0.005wt%, and Ni+Mn=2.40～3.00wt%, all the other are Fe and unavoidable impurities;
(2) strand heating, 1150～1250 ℃ of Heating temperatures;
(3) controlled rolling, 900 ℃～1100 ℃ of the rolling final temperatures of recrystallization zone controlled rolling; 850 ℃～950 ℃ of the rolling beginning temperature of non-recrystallization zone controlled rolling; 800～850 ℃ of two-phase region rolling temperatures;
(4) cooling stops cooling temperature≤300 ℃, forms bainite type acicular ferrite structure;
(5) thermal treatment, 850 ℃～950 ℃ of quenching temperatures, 550 ℃～660 ℃ of tempering temperatures.
5. the manufacture method of low-temperature flexibility 1.5Ni steel as claimed in claim 4 is characterized in that in the described step (1), has at least a kind of weight percent non-vanishing among the Nb of adding, V, the Ti.
6. the manufacture method of low-temperature flexibility 1.5Ni steel as claimed in claim 4 is characterized in that in the described step (1) Nb+V+Ti≤0.10wt% of adding.
7. the manufacture method of low-temperature flexibility 1.5Ni steel as claimed in claim 4 is characterized in that in the described step (3) accumulative total draft 〉=50% of recrystallization zone controlled rolling; Accumulative total draft 〉=20% of non-recrystallization zone controlled rolling; Accumulative total draft≤10% of two-phase region controlled rolling.
8. the manufacture method of low-temperature flexibility 1.5Ni steel as claimed in claim 4 is characterized in that in the described step that each stage soaking time calculates according to 1～3.5min/mm according to thickness of slab.
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| CN102954906B (en) * | 2011-08-19 | 2015-05-06 | 鞍钢股份有限公司 | Method for removing nickel steel hot acid etching oxides |
| CN103103452A (en) * | 2013-03-05 | 2013-05-15 | 北京科技大学 | Low-yield-ratio high-strength high-toughness steel with low temperature use and preparation method of low-yield-ratio high-strength high-toughness steel |
| CN105506457A (en) * | 2015-12-28 | 2016-04-20 | 二重集团（德阳）重型装备股份有限公司 | Low-temperature forged steel manufacturing method and product thereof |
| CN107287530B (en) * | 2016-03-31 | 2019-03-26 | 鞍钢股份有限公司 | A kind of high-strength and high ductility Micro Alloying type steel for low-temperature pressure container and its manufacturing method |
| CN107287526B (en) * | 2016-03-31 | 2019-02-26 | 鞍钢股份有限公司 | A kind of low-cost high-toughness low-temperature (low temperature) vessel thick steel plate and its production method |
| CN110923413B (en) * | 2019-12-16 | 2021-07-13 | 马鞍山钢铁股份有限公司 | Steel for vanadium microalloyed 600 MPa-grade low-temperature steel bar and production method thereof |
| CN110904390B (en) * | 2019-12-16 | 2021-05-07 | 马鞍山钢铁股份有限公司 | Niobium-vanadium composite microalloyed steel for 600 MPa-grade low-temperature steel bar and production method thereof |
| CN115505848B (en) * | 2022-09-28 | 2023-08-11 | 马鞍山钢铁股份有限公司 | V-Nb-Ti composite microalloyed 500 MPa-165 ℃ low-temperature anti-seismic steel bar and production method thereof |
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