CN102899565A - Steel for cold rolling enamel, and manufacturing method thereof - Google Patents
Steel for cold rolling enamel, and manufacturing method thereof Download PDFInfo
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Abstract
The present invention relates to an enamel steel, which comprises the following chemical components, by mass, 0.002-0.010% of C, less than or equal to 0.03% of Si, 0.1-0.4% of Mn, less than or equal to 0.015% of P, 0.018-0.035% of S, 0.020-0.070% of Al, 0.004-0.010% of N, Ti, 0.005-0.05% of Nb, 0.01-0.05% of Cu, and the balance of Fe and unavoidable impurity elements, wherein Ti meets the following formula: Ti=4C+3.42N+1.5S+deltaTi, the deltaTi is 0-0.02%, and Nb+deltaTi is more than or equal to 0.02%. According to the present invention, a nitrogen circulation process is adopted to improve and precisely control nitrogen content in the steel and reduce production cost, such that the obtained enamel steel sheet has characteristics of excellent fish-scaling resistance, excellent adherence resistance and excellent high temperature deformation resistance, has high yield strength after high temperature firing, is especially suitable for manufacture of building decorative panels, and can be generalized for appliance parts, sanitary product, cookers, and the like.
Description
Technical field
The present invention relates to the enamel steel, particularly relate to cold rolling enamel steel and the manufacture method thereof of higher yield strength.
Background technology
The Ultra-low carbon Glassed Steel is the enamel steel of new generation of the eighties exploitation in last century, and it can satisfy needs complex-shaped, that the punching press difficulty large, the demanding enamelware of enamel quality is produced.Produce in the world the ultra low-carbon steel that technology that super deep-punching glassed steel plate adopts all is based on aluminium deoxidation, realize that by chemical ingredients scope and the working process parameter controlled in the steel steel plate has good scaling resistance and super deep drawing quality.
Main dependence adds the alloying element titanium in the steel of CN 1141604A, CN1704494A and CN 101082107A, the titanium that adds is excessive with respect to carbon, nitrogen and sulphur, to guarantee carbon, nitrogen and sulphur all and titanium formation compound, the carbon and the nitrogen that are not solid solution condition in the steel, improve deep drawability and non-ageing purpose to reach, the compound of capacity be guarantee that steel plate has good scaling resistance can be necessary.
But US 3761324A relate to a kind of without timeliness, without the cold-rolled steel sheet of yield extension not only deep-draw with, but also can be zinc-plated or enamel use.Because simple dependence adds niobium (0.02-0.3%) in the steel, if therefore be used for the enamel purpose, the add-on of niobium must be very high, otherwise steel plate is easy to produce squama in the enamel process quick-fried.
The yield strength of this class steel generally only has 140MPa or following in the prior art, is being out of shape easily when burning till through high temperature (such as 870 ℃), particularly is cooled to intensity after the room temperature and usually can be down to and only has 90-120MPa.
Therefore, need a kind of have good scaling resistance energy and adhesion property, particularly have good high temperature deformation resistance ability, and pass through the cold rolling enamel steel that still has higher yield strength after high temperature burns till.
Summary of the invention
The object of the present invention is to provide a kind of enamel steel, this steel has good scaling resistance energy and adhesion property, particularly has good high temperature deformation resistance ability, and still has higher yield strength through high temperature after burning till.This invention steel not only is applicable to twice enamel technology but also is applicable to enamel once technique, is applicable to make decorative panel for building, also can be used for the enamel products such as other household electrical appliances, kitchen tools and bathroom.
To achieve these goals, Glassed Steel of the present invention, its chemical ingredients by mass percentage is: C:0.002-0.010%, Si≤0.03%, Mn:0.1-0.4%, P≤0.015%, S:0.018-0.035%, Al:0.020-0.070%, N:0.004-0.010%, Ti:0.06-0.10%, Nb:0.005-0.05%, Cu:0.01-0.05%, satisfy simultaneously Δ Ti:0-0.02%, Nb+ Δ Ti 〉=0.02%, all the other are Fe and inevitable impurity element.
Preferably, Si:0.005-0.03%, more preferably 0.007-0.027%.
Preferably, Ti:0.06-0.10%.
Unless otherwise, the content among the present invention is weight percent content.
Another object of the present invention provides the manufacture method that above-mentioned enamel is used steel.
The manufacturing process of this Glassed Steel comprises: smelt, refining is controlled the nitrogen content in the steel or is added nitrogen-containing alloy with nitrogen circulation, continuous casting, and hot rolling, finishing temperature is 700-930 ℃, coiling temperature is 600-750 ℃; Cold rolling, draft is more than 60%; Continuous annealing or bell-type annealing, annealing temperature are 650-900 ℃, and annealing time is 1 minute-20 hours.
The control furnace atmosphere is perhydro or contains a small amount of nitrogen when preferably, adopting bell-type annealing.
Preferably, the time of bell-type annealing is 3-20 hour.
Preferably, the time of continuous annealing is 1-10 minute.
The Glassed Steel cold-reduced sheet that obtains like this has good scaling resistance, adherence and high temperature deformation resistance ability, and still has higher yield strength through high temperature after burning till, and is suitable for making household electrical appliances parts, sanitary equipment, kitchen tools and building decoration panel etc.
The Glassed Steel quality problems of easy generation is exactly in the enamel process or to produce squama after cooling quick-fried.Because the quick-fried loss that causes of squama is very large and is difficult to retrieve, thus steel plate to have good scaling resistance can be substantially the most also to be most important performance requriements to Glassed Steel.Producing the quick-fried reason of squama has a lot, but according to the result that the inventor studies, and producing the quick-fried reason of squama and mainly be owing to not having enough traps in the steel is that so-called storage hydrogen trap is caused to be stored in the hydrogen that generates in the enamel firing process.The hydrogen in steel trap has a variety of, comprises crystal boundary, dislocation, microvoid, inclusion and second phase particles etc.Described second phase particles is the nonmetallic compound that arrives at transmission electron microscope observing, and the quantity of second phase particles is the key factor that determines steel plate scaling resistance and plasticity in the Glassed Steel.Traditional super deep-punching glassed steel all is based on ultra low-carbon steel, and the second phase particles that forms capacity by the alloying element that adds capacity improves the scaling resistance energy.But the yield strength of traditional super deep-punching glassed steel is lower, and the high temperature deformation resistance ability when burning till of the high temperature about 870 ℃, very easily distortion, and the intensity after burning till can obviously reduce, and therefore this steel plate is not suitable for the making of heavy construction decorative sheet.
The present invention is directed to the above-mentioned technical problem of prior art, in order to make Glassed Steel guarantee to have under the prerequisite of good scaling resistance and adherence, also has the higher rear intensity of burning till, the inventor is at control carbon, nitrogen, sulphur, in the time of separately the composition range such as titanium and niobium, also control carbon, total weight range of nitrogen and sulphur is to guarantee that enough second phase particles such as TiN are arranged in the steel, TiS, TiC, NbC or their mixture, thereby improve the scaling resistance energy, if carbon in the steel, the impurity content such as nitrogen and sulphur is low, steel is pure, the plasticity of steel plate is good, but owing to there are not enough second phase particles, the scaling resistance variation of steel plate in the steel.Otherwise if the impurity content in the steel is high, the plasticity of steel plate is just poor so, the requirement that does not reach super deep drawing quality; Also by after adding titanium and niobium, the pickling speed of steel plate can slow down in the present invention, therefore adds pickling speed that an amount of copper regulates steel plate to suitable scope, thereby is conducive to improve the adhesion property between steel plate and the enamel.The present invention again by add titanium can be mainly fixing nitrogen, sulphur and the part carbon in the steel, and niobium is because it forms nitrogen and carbon compound temperature the low of titanium that compare, thereby the existence form of niobium is main and part carbon forms NbC, some is solid solution condition, through the high temperature niobium of tiny NbC particle and solid solution intensity of steel plate that is significantly increased after burning till, thereby improve intensity behind the steel high temperature enamel firing of the present invention.
Technique produced according to the invention, when vacuum-treat, carry out nitrogen circulation and control nitrogen content in the steel, nitrogen in the steel can be controlled in the strict scope like this, also overcome the impact of the unfavorable factors such as traditional carburetting that causes when adding the nitrogenized manganese alloy and molten steel cooling.In addition, the control furnace atmosphere is perhydro or contains a small amount of nitrogen when adopting bell-type annealing, can prevent on the one hand the generation of surface of steel plate nitrogen pick-up when long term annealing, because the plasticity of nitrogen pick-up meeting infringement steel plate; Can produce steel plate than the wider specification limit of continuous annealing with bell-type annealing on the other hand.
Embodiment
Below characteristics of the present invention and beneficial effect are described in detail.
Chemical ingredients is on the impact of plate property among the present invention:
C: the plasticity of the lower steel plate of carbon is higher, and still, the yield strength of the lower steel plate of carbon is also lower, particularly when the high temperature enamel firing or the intensity behind the enamel firing lower, very easily produce distortion.Carbon among the present invention is controlled at 0.002-0.010%, and add titanium and adding carbon and titanium, niobium generation titanium carbide and niobium carbide in the niobium steel, or compound compound.Preferred carbon: 0.002-0.008%.
N: be impurity element at traditional nitrogen in steel, the nitrogen more plasticity of Gao Gang is poorer.But nitrogen and titanium reaction generate titanium nitride, and the titanium nitride particle is conducive to improve the scaling resistance energy, and because the generation temperature of titanium nitride is very high, sometimes will generate in molten steel, so it is relatively stable, easily control.If nitrogen content is too high, then damage the plasticity of steel, so the nitrogen span of control is among the present invention: 0.004-0.010%.
Si: silicone content high when being higher than 0.03% (as) can the infringement enamel property particularly cause adherence bad, if silicone content is crossed low difficulty and the cost that can increase smelting simultaneously, therefore, control silicone content≤0.03% among the present invention, preferred silicone content is controlled in the 0.005-0.03% scope, more preferably 0.007-0.027%.
S: sulphur is impurity element, mainly exists with the manganese sulfide inclusion thing in conventional steel, and this inclusion is the strip form through after rolling, and the plasticity that seriously reduces steel plate particularly reduces the horizontal plastic property of steel plate.In Glassed Steel, by adding titanium, can avoid forming simple manganese sulfide inclusion thing, but sulphur and titanium, manganese etc. form compound inclusion, this inclusion is spherical more, can reduce the infringement to plasticity, but is conducive to improve the scaling resistance energy of steel.The scope of sulphur is: 0.018-0.035%.
Ti: 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=0-0.02%.The add-on of titanium is pressed Ti=4C+3.42N+1.5S+ (0-0.02) %, is preferably 0.06-0.10%.
Nb: niobium also is strong carbon, nitride forming element, and niobium also can the solid solution form be present in the steel.Usually, the carbon of niobium, the Precipitation Temperature of nitride are lower than carbon, the nitride of titanium, so the main and titanizing of nitrogen is closed among the present invention, and carbon and titanium, niobium all can form compound, and the part niobium is solid solution in addition.The add-on of niobium is 0.005-0.05%, and satisfies Nb+ Δ Ti 〉=0.02%.
Al: in aluminium killed steel, aluminium is strong deoxidant element.In addition, aluminium and nitrogen reaction generate aluminium nitride, and aluminium nitride can play a role the scaling resistance that improves steel.Al content is 0.020-0.070% among the present invention.
Cu: copper can improve the solidity to corrosion of steel plate, thereby affects the pickling speed of steel plate, and an amount of copper is conducive to improve the adherence between the embryo and enamel at the bottom of the steel plate.But the copper too high levels, the intensity that can improve steel is damaged the formability of steel.The content of copper is 0.01-0.05%.
P: phosphorus is harmful element.Phosphorus content is too high, and segregation on crystal boundary affects the enamel quality easily.Phosphorus≤0.015%.
Technological factor of the present invention is on the impact of plate property:
Smelt: in traditional external refining process, the N content in the control steel generally is to contain the 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 only has 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 scope accurately, has eliminated the disadvantageous effect of bringing when adding nitrogenized manganese.
Hot rolling: heating and temperature control is at 1100-1250 ℃.Adopt higher Heating temperature, so that continuously cast bloom makes on the one hand the austenite structure homogenizing in the steel in heat-processed, make on the other hand in the compound of titanium and niobium some or most of dissolving.In hot rolling and process of cooling, they can be separated out again with the form of compound, are the small and dispersed distributions in matrix.The finishing temperature of hot rolling is controlled at 700-950 ℃, and coiling temperature is controlled at 550-750 ℃.
Pickling and cold rolling: steel plate carries out cold rolling after iron scale is removed in pickling, so the purpose of pickling mainly is the iron scale that eliminates the hot-rolled sheet surface, guarantees the surface of steel plate zero defect.
Cold rolling: cold rolling total reduction is more than 60%.Cold rolling draft has a great impact the performance of finished steel plate.On the one hand, draft increases, and the recrystallization temperature of steel plate reduces; On the other hand, draft improves, and is conducive to fully develop in the annealing recrystallization process punching press texture.Therefore, in cold-rolled process, cold rolling total reduction is one of key process parameter that affects end properties, in the situation of mill capacity license, improve draft and not only can slow down the pressure that simple dependence annealing temperature is brought, improve the punching performance of finished steel plate, and draft improves, increase in the space that forms around inclusion and precipitated phase, and these spaces prevent to steel plate that squama is quick-fried in application of slip process and play a role.Cold rolling draft is more than 60% among the present invention.Cold rolling draft is preferably more than 75%.
Cold rolling after annealing: steel plate is realized the recrystallize of the ferritic structure in the cold rolling attitude steel plate through continuous annealing or bell-type annealing, promotes the development of grain growing and recrystallization texture.Main technologic parameters during annealing comprises temperature and time, adopts higher annealing temperature, is conducive to promote the development of favorable texture, also is conducive to finish the abundant development of recrystallize and recrystallization texture, to improve the plasticity of finished product.Annealing temperature is 650-900 ℃, and annealing time is 1 minute-20 hours.The time of continuous annealing is 1-10 minute, and the time of bell-type annealing is 3-20 hour.
Smooth: the steel plate after the annealing needs through smooth to improve surface quality, the satisfied needs that use.
Embodiment
The chemical ingredients of the industrial embodiment 1-10 of the present invention is referring to table 1, and increases by 2 Comparative Examples.
The manufacturing process of the embodiment of the invention: smelt and process by the technique of technical scheme, adopt top and bottom combined blown converter smelting and the refining of Fruit storage device, molten steel is through continuous casting Cheng Houwei 200 to 230mm slabs, slab carries out hot rolling at the hot continuous rolling unit after heating, hot-rolled sheet carries out cold rolling after pickling, cold rollingly carry out at five Stands Cold Tandem Mills, it is continuous annealing and bell-type annealing that the annealing of cold-reduced sheet is divided into two kinds of annealing way, 1150 ℃ of embodiment 1-5 hot rolling Heating temperatures, 880 ℃ of finishing temperatures, 700 ℃ of coiling temperatures, hot rolling thickness are 4.0mm, cold rolling draft 75%, cold-rolled steel sheet thickness are 1.0mm.The bell-type annealing temperature: 700 ℃, 20 hours bell-type annealing time.1200 ℃ of embodiment 6-10 hot rolling Heating temperatures, 900 ℃ of finishing temperatures, 730 ℃ of coiling temperatures, cold rolling draft 67.5%, the continuous annealing temperature: 870 ℃, annealing time 5 minutes.
Test example 1: mechanical property
Tension specimen is pressed the dimensioned of JIS 13B, i.e. parallel portion width 20mm, gauge length 80mm.Record the finished product mechanical property of cold rolled annealed plate of the present invention, it the results are shown in Table 2.
The performance of table 2 embodiment of the invention
Annotate: A
80Be unit elongation, R
P0.2Be yield strength, Rm is tensile strength.
Test example 2: application of slip test and hydrogen permeability test
The model of getting 200mm * 200mm size carries out application of slip test.Application of slip test is finished in the laboratory.The enameling process (two ward off two burnings) that adopts general enamel, twice application of slip to burn till for twice perhaps adopts twice application of slip single firing process (two ward off a burning), then burns till in 850 to 870 ℃ stove, in-furnace time 5 to 7 minutes.Steel plate after burning till at room temperature place 48 hours to observe the surface whether to produce squama quick-fried, and carry out the adherence check.The hydrogen permeability test adopts conventional electrochemical method.
After measured, the hydrogen permeation time of all embodiment steel plates is all between 10-25min, adopt two ward off two burn or two ward off a firing technique after none example fish-scaling effect, adherence all reaches 1 grade.
Test example 3: simulated annealing experiment
Mechanical property behind the steel plate process simulated annealing (annealing process is 870 ℃ * 10min+ air cooling) sees Table 2.
As seen data still keep higher yield strength behind the above-mentioned simulated annealing of cold rolled annealed steel plate process of the present invention from table.
From above explanation by embodiment as seen, steel of the present invention not only has good scaling resistance, adherence, particularly has good high temperature deformation resistance ability, still has higher yield strength after burning till through high temperature.Steel of the present invention not only is applicable to twice enamel technology but also is applicable to enamel once technique, is applicable to make decorative panel for building, also can be used for the enamel products such as other household electrical appliances, kitchen tools and bathroom.
Claims (7)
1. Glassed Steel, its chemical ingredients by mass percentage is: C:0.002-0.010%, Si≤0.03%, Mn:0.1-0.4%, P≤0.015%, S:0.018-0.035%, Al:0.020-0.070%, N:0.004-0.010%, Ti=4C+3.42N+1.5S+ Δ Ti, Nb:0.005-0.05%, Cu:0.01-0.05%, satisfy simultaneously Δ Ti:0-0.02%, Nb+ Δ Ti 〉=0.02%, all the other are Fe and inevitable impurity element.
2. Glassed Steel as claimed in claim 1 is characterized in that, Si:0.005-0.03% is preferably 0.007-0.027%.
3. Glassed Steel as claimed in claim 1 or 2 is characterized in that, Ti:0.06-0.10%.
4. such as the manufacture method of the arbitrary described enamel of claim 1-3 with steel, comprising:
Smelt, refining is controlled the nitrogen content in the steel or is added nitrogen-containing alloy with nitrogen circulation, continuous casting, and hot rolling, finishing temperature is 700-930 ℃, coiling temperature is 600-750 ℃;
Cold rolling, draft is more than 60%;
Cold rolling rear continuous annealing or bell-type annealing, annealing temperature are 650-900 ℃, and annealing time is 1 minute-20 hours.
5. method as claimed in claim 4 is characterized in that, the control furnace atmosphere is perhydro or contains a small amount of nitrogen when adopting bell-type annealing.
6. such as claim 4 or 5 described methods, the time of bell-type annealing is 3-20 hour.
7. method as claimed in claim 4 is characterized in that, the time of continuous annealing is 1-10 minute.
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CN108796380A (en) * | 2017-04-26 | 2018-11-13 | 宝山钢铁股份有限公司 | Pole low-carbon cold rolling enamel sheet and its manufacturing method of the yield strength in 210MPa or more after firing |
CN112941418A (en) * | 2021-02-07 | 2021-06-11 | 首钢集团有限公司 | High-strength steel for cold rolling enamel and preparation method thereof |
CN113025907A (en) * | 2021-03-09 | 2021-06-25 | 马鞍山钢铁股份有限公司 | Cold-rolled enameled steel plate for anti-pressing and anti-explosion porcelain water heater liner and production method thereof |
CN114015947A (en) * | 2021-10-09 | 2022-02-08 | 包头钢铁(集团)有限责任公司 | Cold-rolled enamel steel for stamping and manufacturing method thereof |
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