CN100396808C - Cold rolling glass-lined steel having excellent scale cracking resistance and extra-deep drawing property and manufacturing method thereof - Google Patents
Cold rolling glass-lined steel having excellent scale cracking resistance and extra-deep drawing property and manufacturing method thereof Download PDFInfo
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- CN100396808C CN100396808C CNB2004100247585A CN200410024758A CN100396808C CN 100396808 C CN100396808 C CN 100396808C CN B2004100247585 A CNB2004100247585 A CN B2004100247585A CN 200410024758 A CN200410024758 A CN 200410024758A CN 100396808 C CN100396808 C CN 100396808C
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Abstract
The present invention relates to cold rolling glassed steel and a manufacturing method thereof, particularly to cold rolling glassed steel with extra low carbon, excellent scale cracking resistance and excellent extra deep drawing performance, and a manufacturing method thereof, which solves the defect that the existing cold rolling glassed steel has poor scale cracking resistance and extra deep drawing performance. The cold rolling glassed steel has the components by the weight percentages of at most 0.005% of carbon, at most 0.030% of silicon, 0.10 to 0.30% of manganese, at most 0.015% of phosphorus, 0.010 to 0.050% of sulfur, 0.020 to 0.050% of aluminium, 0.004 to 0.015% of nitrogen, titanium (4C+3.42N+1.5S+0.02 to 0.04%), Fe and other unavoidable impurities, wherein Fe and the other unavoidable impurities account for the rest weight percentage; the C+0.5S+0.886N is controlled to be larger than or equal to 0.01%, and is less than or equal to 0.035. In the vacuum degassing process, a new nitrogen circulation method is used for controlling the nitrogen content in steel, and the technology of annealing in a hood type annealing furnace in the atmosphere fully containing hydrogen or containing extra low nitrogen gas is adopted; and the technology is mainly used for manufacturing the cold rolling glassed steel with excellent scale cracking resistance and excellent extra deep drawing performance.
Description
Technical field
The present invention relates to a kind of cold rolling Glassed Steel and manufacture method thereof, particularly a kind of Ultra-low carbon has the cold rolling Glassed Steel and the manufacture method thereof of good scaling resistance and super deep drawing quality.
Background technology
The Ultra-low carbon Glassed Steel is the enamel steel of new generation of the eighties exploitation, and it can satisfy the needs that the enamelware complex-shaped, that the punching press difficulty big, the enamel specification of quality is high is produced.
The major vendor that produces super deep-punching glassed steel plate in the world has the NKK of Japan, Nippon Steel and the German base of a fruit gloomy etc., does not domesticly see that relevant patent is arranged.External producer is in the Glassed Steel manufacturing processed, and the technology that is adopted all is based on the ultra low-carbon steel of aluminium deoxidation, realizes that by chemical ingredients scope and working process parameter in the control steel steel plate has good scaling resistance and super deep drawing quality.Chinese patent CN95191701.3 has introduced " manufacturing has the method for the cold-rolled steel sheet of excellent enamel adherence ", this patent is the method for cold-rolled steel sheet of the enamelware of a kind of manufacturing outer disk parts, gas range and bathtub of being used for tableware, building panelling, microwave oven, having increased the excellent enamel adherence between enamel layer and steel plate in this method and having improved the required formability of complicated shape product greatly, provide a kind of method of making the cold-rolled steel sheet of the fabulous high formability of enamel adherence.Aspect the method for using Al deoxidization steel manufacturing enamel coating cold-rolled steel sheet, this patent is a kind of method of making the cold-rolled steel sheet of the fabulous high formability of tight adhesion character, in this method, Al deoxidization steel contains carbon:＜0.01%, manganese: 0.1～0.4%, sulphur: 0.03～0.09%, titanium: 0.04～0.1% and nitrogen:＜0.019%, represent with weight percent, atom ratio by Ti/ (C+N+0.4S) definition adjusts to 1.0～2.0, other unavoidable impurities is made of and is comprised to rest part iron, this steel of hot rolling also makes finish rolling carry out above under the temperature of Ar3 transition temperature, batch then, cold rolling by 50～85% drafts, last continuous annealing.This patent makes that its scaling resistance and super deep drawing quality are not very desirable because the content of carbon and sulphur is high slightly.
The Glassed Steel quality problems of easy generation is exactly a cracking and to produce squama when enamel quick-fried when punching press, and cracking and the quick-fried loss that causes to the user of squama are very big.Producing the quick-fried reason of squama is not have enough traps in the steel to be stored in the hydrogen that generates in the enamel firing process.Hydrogen trap in the steel comprises crystal boundary, dislocation, micro-cavity, inclusion and the second phase particle etc.The described second phase particle is the metallic compound that arrives at transmission electron microscope observing, and in super deep-punching glassed steel, the quantity of the second phase particle is the key factor of decision steel plate scaling resistance and plasticity.If impurity contents such as carbon, nitrogen and sulphur are low in the steel, steel is pure, and the plasticity of steel plate is good, but owing to does not have the second enough phase particle, the scaling resistance variation of steel plate in the steel.Otherwise if the impurity content height in the steel, the plasticity of steel plate is just poor so, the requirement that does not reach super deep drawing quality.Therefore, from the control of alloying element, improving scaling resistance and improving stampability is conflicting and restriction.Solve this a pair of contradiction, realize the good comprehensive performances coupling, the control of reasonable component design and processes is crucial.
Summary of the invention
The technical issues that need to address of the present invention are: improve its scaling resistance when guaranteeing the high stampability of cold rolling Glassed Steel.From composition design, prior art is controlled the content of carbon in the steel, nitrogen and sulphur respectively when adding the titanium ultra low-carbon steel and carry out alloy designs, adds excessive titanium (being effective titanium+excessive titanium) on this basis.Thinking of the present invention is, in control carbon, nitrogen, sulphur composition range separately, total weight range of importantly controlling carbon, nitrogen and sulphur is to guarantee to have in the steel enough second particle mutually.
On production technique, the production method of existing Ultra-low carbon Glassed Steel be adopt bessemerize, technical process such as vacuum outgas, continuous casting, hot rolling, cold rolling, high temperature continuous annealing, but in these production methods, do not mentioned the method that in vacuum outgas is handled, adopts new azo-cycle stream control in the steel nitrogen and with perhydro or contain the use of annealed technology in the bell type annealing furnace in the atmosphere of extremely low nitrogen.The thinking that the present invention adopts is, dependence nitrogen circulation method is controlled the nitrogen content in the steel when vacuum-treat, nitrogen in the steel can be controlled at like this in the strict scope, also overcome the influence of unfavorable factors such as the carburetting that causes when traditional dependence adds the nitrogenized manganese alloy and molten steel cooling, promotion helps the formation of the texture of punching press, the size of control and even ferrite crystal grain, this also is the distinctive feature of this patent.In addition, the control furnace atmosphere is perhydro or contains a spot of nitrogen when adopting bell-type annealing, can prevent the generation of surface of steel plate nitrogen pick-up when long term annealing on the one hand, because the plasticity of nitrogen pick-up meeting infringement steel plate; Can produce steel plate with bell-type annealing on the other hand than the wideer specification limit of continuous annealing.
Technical scheme of the present invention is: have the cold rolling Glassed Steel of good scaling resistance and super deep drawing quality, by weight percentage, the composition proportion of its composition is:
Carbon≤0.005%, silicon≤0.030%, manganese 0.10～0.30%, phosphorus≤0.015%, sulphur 0.010～0.050%, aluminium 0.020～0.050%, nitrogen 0.004～0.015%, titanium=(4C+3.42N+1.5S)+(0.02～0.04%), surplus is iron and other unavoidable impurities.
And control 0.01%≤C+0.5S+0.886N≤0.03%.
Its processing process is as follows: (using nitrogen circulation) → continuous casting → hot rolling → pickling → cold rolling → bell-type annealing → finishing is handled in smelting → vacuum outgas.
Bessemerize: oxygen blowing;
Vacuum-treat: recycle stream whole process is that nitrogen is with the nitrogen content in the control molten steel;
The hot rolled main technologic parameters is: Heating temperature: 1100～1250 ℃; Finishing temperature: greater than Ar3,860～920 ℃; Coiling temperature: 680～760 ℃.
Cold rolling total draft is more than 65%.
Bell-type annealing: adopt tight volume annealing, the atmosphere of annealing furnace is perhydro atmosphere, allows a spot of nitrogen, and nitrogen is controlled at and is not more than 10%.Annealing temperature is 680～750 ℃.
Mainly realize: 1. in super deep-punching glassed steel, control the content of carbon, nitrogen and sulphur respectively based on following aspect.Emphasis reduces the carbon content in the steel, and rely on when vacuum-treat that nitrogen circulation improves and stabilized steel in nitrogen content, overcome disadvantageous effects such as the carburetting that causes when traditional dependence adds the nitrogenized manganese alloy and molten steel temperature drop are big.2. control the add-on of titanium, and the total amount of impurity elements such as control carbon, nitrogen and sulphur, with the total amount of the second phase particle in the stabilized steel, guarantee the scaling resistance of Finished Steel and the matched well of plasticity.This is because when adding excessive titanium, the total content of carbon, nitrogen and sulphur has promptly determined in the steel second quantity of particle mutually, thereby the total content of carbon, nitrogen and sulphur has directly influenced the scaling resistance and the plasticity of steel plate.3. reasonably hot rolling, cold rolling and annealing process are to produce to have the prerequisite of good scaling resistance and plasticity steel plate.
Chemical ingredients and technology are to the influence of plate property:
1, the influence of chemical ingredients
Carbon: carbon content reduces, and the unit elongation of steel plate improves, and n value and r value also improve, so the Ultra-low carbon level is the prerequisite of production extra-deep drawing sheet steel, need carry out the vacuum outgas processing after smelting.The controlled levels of carbon depends on metallurgical equipment and state of the art.But, also have manufacturer in steel, to keep the carbon (gloomy) of high level as the base of a fruit.
Nitrogen and sulphur: nitrogen and sulphur also are impurity elements in traditional steel plate, the plasticity of infringement steel plate, thereby its content is low as much as possible, reduces to 80ppm respectively and below the 40ppm as the content of sulphur and nitrogen in traditional ultra low-carbon steel (adding the titanium ultra low-carbon steel).In Glassed Steel, if the content of these elements (comprising carbon) is all very low, just can not generate enough compounds improves the scaling resistance of steel plate in the steel.Show that according to experimental study the comparable traditional suitable raising of ultra low-carbon steel of the content of sulphur and nitrogen is complementary with alloying element in the steel, forms the second phase particle of capacity.
Titanium: titanium is the forming element of strong carbon, nitrogen and sulfide.The add-on of titanium should be suitable excessive, to be completely fixed carbon, nitrogen and the element sulphur in the steel.Effectively the calculating of titanium is pressed: Ti*=4C+3.42N+1.5S always adds titanium: Ti=Ti*+ Δ Ti, wherein excessive titanium Δ Ti=0.02～0.04%.
2, technological factor is to the influence of product performance:
Smelt: in traditional external refining process, [N] content in the control steel generally is to contain [N] alloy by interpolation to finish, and mainly is the nitrogenized manganese alloy.But the interpolation of nitrogen-containing alloy can cause the increase of carburetting and other harmful element for ultra low-carbon steel.Simultaneously, when adding nitrogenized manganese under vacuum state, the recovery rate of nitrogen element has only about 25%.The nitrogenized manganese alloy that adds also can cause exceeding standard of manganese content above a certain amount of.The present invention adopts nitrogen circulation technology, can stably control nitrogen in the scope of strictness, has also eliminated the disadvantageous effect of bringing when adding nitrogenized manganese.
Hot rolling: slab reheat temperature improves, the r of finished product steel plate
mValue descends.But on the other hand, Heating temperature improves, and helps forming thick inclusiones such as TiS.Owing to when the hole of formation is at enamel firing around inclusion, can become the trap of catching hydrogen, prevent that squama is quick-fried.
Finishing temperature raises, the r of cold-reduced sheet
mValue, δ all improve.Coiling temperature improves, and can make the recrystallization temperature of cold-reduced sheet descend r
mValue, δ also improve thereupon.
Pickling: the purpose of pickling is to remove the iron scale of surface of steel plate.In acid cleaning process, guarantee the surface of steel plate zero defect.
Cold rolling: cold rolling draft has very big influence to the performance of finished product steel plate.On the one hand, draft increases, and the recrystallization temperature of steel plate reduces; On the other hand, draft improves, and helps fully developing in the annealing recrystallization process punching press texture.Therefore, in cold-rolled process, cold rolling total draft is one of key process parameter that influences end properties, under the situation of mill capacity permission, improve draft and not only can slow down the pressure that simple dependence annealing temperature is brought, improve the punching performance of finished product steel plate, and draft improves, increase in the space that forms around inclusion and precipitated phase, these spaces to steel plate in application of slip process, prevent squama quick-fried play a part certain.
Annealing: steel plate is annealed through full-hydrogen hood-type annealing furnace, can prevent the generation of nitrogen pick-up phenomenon in the steel plate.Adopt higher annealing temperature during annealing, promote the development of favorable texture on the one hand, guarantee that on the other hand cold rolling microstructure finishes fully growing up of recrystallize and crystal grain, to improve the plasticity of finished product.
Smooth: the steel plate after the annealing need satisfy user's needs through smooth to improve surface quality.
Beneficial effect of the present invention is:
The cold-rolled steel sheet and the steel band that adopt mentioned component design and processes control method to produce, have super deep drawing quality and good scaling resistance, and the wide adaptability of stable performance, product, can be widely used in the production of sanitary equipment, kitchen tools, household electrical appliances and building panel etc., satisfy deep-draw and twice enamel, burn till for twice or the needs of twice enamel, once-firing.
Embodiment
Embodiment 1-10 is referring to table 1, and increases by a Comparative Examples, and surplus is iron and other unavoidable impurities.Smelt and process by the technology of technical scheme, 1150 ℃ of embodiment 1-5 hot rolling Heating temperatures, 880 ℃ of finishing temperatures, 700 ℃ of coiling temperatures, cold rolling draft 66%, the bell-type annealing temperature: 700 ℃, bell-type annealing a nitrogen content 6%.1200 ℃ of embodiment 6-10 hot rolling Heating temperatures, 900 ℃ of finishing temperatures, 730 ℃ of coiling temperatures, cold rolling draft 67.5%, the bell-type annealing temperature: 700 ℃, bell-type annealing nitrogen amount 8%.Its end properties sees Table 1.As seen from Table 1, adopt above-mentioned composition and processing parameter to process, the unit elongation of its end properties reaches 43～53% (gauge length 80mm), average out to 47%, three-dimensional r
mValue is 1.82～2.33, and average out to 2.05 reaches the level of super deep-draw fully, and steel plate takes place for no avulsion such as user's punching out enamel bathtubs, adopts two to ward off two burnings or two to ward off none example of a firing technique fish-scaling effect, and the effect after the enforcement is fairly obvious.
Estimate feasibility and prospect that invention is applied:
On technology, produce cold rolling super deep-punching glassed steel plate and will possess smelting and vacuum outgas equipment, continuous casting, hot continuous mill, pickling, cold continuous rolling and annealing machine etc.
Cold rolling super deep-punching glassed steel plate can be used for producing enamelwares such as enamel bathtub, kitchen range, sanitary equipment and building fancy face plate, and demand at home has tens thousand of tons, has bright development prospect.
Claims (3)
1. the cold rolling Glassed Steel that has good scaling resistance and super deep drawing quality, by weight percentage, the composition proportion of its composition is:
Carbon≤0.005%, silicon≤0.030%, manganese 0.10～0.30%, phosphorus≤0.015%, sulphur 0.010～0.050%, aluminium 0.020～0.050%, nitrogen 0.004～0.015%, titanium=(4C+3.42N+1.5S)+(0.02～0.04%), surplus is iron and other unavoidable impurities, in described proportioning, 0.01%≤C+0.5S+0.886N≤0.03%.
2. described cold rolling Glassed Steel manufacture method of claim 1 with good scaling resistance and super deep drawing quality, processing step comprises successively: smelting, vacuum outgas processing, continuous casting, hot rolling, pickling, cold rolling, annealing, finishing, it is characterized in that: the treatment stage of vacuum outgas, adopt nitrogen circulation, adopt bell-type annealing at annealing stage.
3. the cold rolling Glassed Steel manufacture method with good scaling resistance and super deep drawing quality according to claim 2, it is characterized in that: bell-type annealing adopts tight volume annealing, the atmosphere of annealing furnace is perhydro atmosphere, allows to be no more than 10% nitrogen, and annealing temperature is 680～750 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100247585A CN100396808C (en) | 2004-05-28 | 2004-05-28 | Cold rolling glass-lined steel having excellent scale cracking resistance and extra-deep drawing property and manufacturing method thereof |
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| CNB2004100247585A CN100396808C (en) | 2004-05-28 | 2004-05-28 | Cold rolling glass-lined steel having excellent scale cracking resistance and extra-deep drawing property and manufacturing method thereof |
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| CN100396808C true CN100396808C (en) | 2008-06-25 |
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