CN104419874A - Hot rolled double-faced enamel steel with excellent fish scaling resistance and manufacture method of hot rolled double-faced enamel steel - Google Patents
Hot rolled double-faced enamel steel with excellent fish scaling resistance and manufacture method of hot rolled double-faced enamel steel Download PDFInfo
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- CN104419874A CN104419874A CN201310398942.5A CN201310398942A CN104419874A CN 104419874 A CN104419874 A CN 104419874A CN 201310398942 A CN201310398942 A CN 201310398942A CN 104419874 A CN104419874 A CN 104419874A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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Abstract
The invention provides hot rolled double-faced enamel steel with excellent fish scaling resistance and a manufacture method of the hot rolled double-faced enamel steel. A steel plate comprises the following components in percentage by mass: 0.02%-0.06% of C, no more than 0.10% of Si, 0.50%-1.0% of Mn, no more than 0.025% of P, 0.010%-0.045% of S, 0.003%-0.009% of N, 0.05%-0.15% of Ti, 0.005%-0.050% of Als, 1.5%-3.0% of Ti/C, 0.05%-0.20% of Cr, and the balance of iron and impurities. The method comprises the following steps: smelting the components, and continuously casting, wherein the casting blank heating temperature is 1180-1260 DEG C; removing scales with high pressure water; roughly rolling to form a middle blank, wherein the thickness of the middle blank is over three times of the thickness of a finished product; rolling for 5-7 passes to obtain the target thickness, wherein the initial finish rolling temperature is 960-1080 DEG C, and the final finish rolling temperature is 820-900 DEG C; and rapidly cooling to coiling temperature of 550-650 DEG C at the cooling speed of no smaller than 40 DEG C/S within 8S. Through reasonable component design and process control, an enough hydrogen storage trap is formed in the steel, and the fish scaling resistance is improved.
Description
Technical field
The invention belongs to Glassed Steel field, particularly relate to counterenamel steel Glassed Steel and manufacture method thereof.
Background technology
Squama is quick-fried is the critical defect of enamelware, greatly the quality of harm enamelware.Enamel fish scaling causes due to the hydrogen dissolved in steel plate.Enamelware experienced by the process of twice suction hydrogen in process of production, and one is be in enamel firing process at acid cleaning process, two.First be iron scale and sour reaction during pickling, mainly sour and metal generation chemical reaction produces hydrogen, a part of hydrogen evolution afterwards, and a part of hydrogen is dissolved in steel plate with atomic form.When high temperature enamel firing subsequently, water vapour and surface of steel plate iron in the crystal water in porcelain slurry and heating furnace gas and carbon react, and generation hydrogen atom, is dissolved in iron with the form of atom and molecule.Along with steel plate cooling, the hurried decline (20 of the solubleness of hydrogen in solid iron
hydrogen solubleness in steel is only 900
thousandth), so hydrogen atom effusion, be subject on steel surface enamel layer intercept, be gathered in steel plate and enamel interface with molecularity.When hydrogen atom constantly overflow, hydrogen pressure increases to a certain degree, the pressure of generation exceedes the breakdown point of enamel layer and the breakage of enamel layer occurs.This breakage is the some form in hole generally, and shape, as scale, is called that squama is quick-fried.In pickling and enamel firing process, mainly enter steel plate owing to producing the quick-fried hydrogen of squama, therefore except improving the enamel technology of goods, also should improve the fish scaling resistance of steel plate itself.
The material of main part of enamel assembling structure is the hot-rolled steel sheet with good counterenamel performance.For meeting Structural Design Requirement, the thickness of steel plate generally at 3.0mm ~ 16mm, and has high yield strength.Cold rolling enameling sheet thickness specification is mostly at below 3mm, and yield strength is not enough, and specification and intensity two aspect all can not meet the matching requirements of large-scale enamel assembling component.In hot-rolled steel sheet, for ensureing the fish scaling resistance of steel plate, often Ti/C ratio will be brought up to more than 4, as with the addition of the Ti element of 0.1 ~ 0.5% in Japanese Patent technology " JP 55-152127 ", cost is high, and production difficulty is not suitable with greatly continuous casting and produces.Japanese Patent " Unexamined Patent 10-121141 ", " flat 2-305926 " and " clear 58-1013 " all propose to add B, N, Cu alloying, produce wayward, and are not enough to ensure counterenamel performance requriements.Chinese patent CN101353758A " a kind of hot rolling high strength steel plate for two-sided porcelain enamel and manufacture method thereof ", C content higher (0.05 ~ 0.15%), easily gas hole defect occurs, fish scaling resistance is poor, excessively adds V(0.02 ~ 0.2%), cost is high.Owing to rolling rear cooling rate low (cooling rate≤50 DEG C/S), the easy coarsening of compound of V and Ti, unfavorable to fish scaling resistance.
In porcelain enamel industry, for avoiding squama quick-fried, the general low-carbon cold rolling steel plate that adopts carries out counterenamel.This is owing to there is a large amount of tiny cementite phases in cold-rolled steel sheet, and some hard particles produce the defect interface between a large amount of and matrix in Pressing Deformation process, become the trap of Chu Qing.
Patent CN101535517A describes " enamel sheet that fishscale resistance is significantly excellent and manufacture method thereof ", in this method, C:0.003 ~ 0.010%, Si:0.001 ~ 0.100%, Mn:0.03 ~ 1.30%, P :≤0.035%, S :≤0.08%, Nb:0.055 ~ 0.250%, O:0.005 ~ 0.085%, Al:0.0002 ~ 0.010%, below N:0.0055%, B:0.0003 ~ 0.0030%, V:0.003 ~ 0.15%, Ni:0.0001 ~ 0.05%, Ti:0.0001 ~ 0.05%, also containing Ta, W, Mo, La, Ce, Ca, more than a kind in Mg, add up to less than 1.0%, and As, Se, Sn, more than a kind in Sb, add up to less than 1.0%, surplus is made up of Fe and inevitable impurity.This invention is produced according to common melting, continuous casting, hot rolling, cold rolling, annealing operation.This patent requirements strictly controls cooling rate≤10 DEG C when slab thickness 1/4 layer of place solidifies
control the diameter dimension of the composite oxides in strand more than 10 μm, and in ratio>=1.2 of the Nb mass concentration in this oxide compound middle and high concentration portion with the Nb mass concentration in lower concentration portion, it is very large that this controls difficulty in process of production.And a large amount of macrobead oxide compounds can have a negative impact to the performance of steel.This patent interalloy element kind is many, particularly with the addition of a large amount of noble metal Nb, the cost of steel is increased.
Patent CN101356295A describes " the continuous casting enamel sheet that scaling resistance is significantly excellent and manufacture method thereof ", its production method and scaling resistance principle identical with a upper patent, just this patent with the addition of a large amount of B element, and a large amount of B can cause the hot-short phenomenon of steel, destroys the performance of steel.Above two patents are all produce with cold rolling, method for annealing, and production process is many, and cost is high.
Patent CN1704494A describes " having cold rolling Glassed Steel and the rolling method thereof of excellent scaling resistance and super deep drawing quality ", and its chemical composition per-cent is: C :≤0.005%, Si≤0.030%, Mn:0.10 ~ 0.30%, P≤0.015%, S:0.010 ~ 0.050%, Al:0.020 ~ 0.050%, N:0.004 ~ 0.015%, Ti=4C+3.42N+1.5S+0.02 ~ 0.04% and control 0.01%≤C+0.5S+0.886N≤0.03%.This patent carries out alloy designs based on adding titanium ultra low-carbon steel on Composition Design, controls the content of carbon, nitrogen and sulphur in steel respectively, adds excessive titanium on this basis, guarantee there are enough second-phases in steel.Its processing step comprises: smelting, Fruit storage, continuous casting, hot rolling, pickling, cold rolling, annealing, finishing, particularly adopt nitrogen circulation in the Fruit storage stage, adopt bell-type annealing at annealing stage.In this patent, C, Mn content is on the low side, can not meet the requirement of strength of enamel assembling structural part, and employing is cold rolling, annealing process, and production process is many, and cost is high.
Summary of the invention
The object of the invention is to overcome the problems referred to above and not enough and provide a kind of hot-rolled double-side enamel steel and manufacture method thereof of fish scaling resistance excellence, the manufacture for large-scale enamel assembling component provides the steel plate materials of fish scaling resistance excellence.
The present invention seeks to realize like this:
The hot-rolled double-side enamel steel of fish scaling resistance excellence, the composition of this steel plate is as follows by weight percentage: C:0.02 ~ 0.06%, Si≤0.10%, Mn:0.50 ~ 1.0%, P :≤0.025%, S:0.010 ~ 0.045%, N:0.003 ~ 0.009%, Ti:0.05 ~ 0.15%, Als:0.005 ~ 0.050%, Ti/C:1.5 ~ 3.0, Cr:0.05 ~ 0.20%, and all the other are iron and inevitable impurity.
Present component design reason is as follows:
(1) C is the element promoting that the particle of Ti is separated out, and lower than 0.02%, is unfavorable for the precipitation of the TiCx particle as hydrogen trap.Higher than 0.06%, under the prerequisite of equal Ti content, that can reduce precipitated phase catches hydrogen activity, unfavorable to enamel property.Therefore select 0.02 ~ 0.06%.
(2) Si element can generate oxide film in advance in enamel firing process, hinders the generation of adhesive layer between steel plate and enamel.Affect enamel adhesion property when Si content is more than 0.10%, therefore limit Si≤0.10%.
(3) Main Function of Mn is the intensity improving steel.When Mn content is more than more than 1.0%, the Ac3 temperature of steel reduces amplitude comparatively greatly, causes part deformation excessive, so the content range of control Mn is 0.50 ~ 1.0% during enamel firing because of steel plate austenitizing.
(4) Ti/C is than being the important indicator ensureing enamel property.Ti/C >=1.5, make to occur having the precipitation particles such as the carbide of chemically active Ti, the carbonitride of Ti in a large number in the microtexture of steel plate, can provide enough storage hydrogen traps, after suppressing steel plate enamel firing, squama occur quick-fried.Slab quality problem when Ti too high levels can cause continuous casting.Therefore the span of control of Ti/C ratio is limited to 1.5 ~ 3.0.
(5) Ti is the important forming element of the precipitation particles as hydrogen trap.As previously mentioned, its content should be 1.5 ~ 3.0 times of C.Under this prerequisite, for ensureing the necessary surface-area of the hydrogen trap formed, Ti content should higher than 0.03%.But higher than 0.15% time can bring bad impact to sheet billet continuous casting.Therefore ensureing that Ti/C is than under the prerequisite between 1.5 ~ 3.0, determines that its content is 0.05 ~ 0.15%.
(6) in conventional steel plates, S and N is harmful element, and what therefore will control is as far as possible low.But in Glassed Steel, as the trap of storage hydrogen, there is squama after suppressing steel plate enamel firing quick-fried, therefore suitably can relax the content range of S and N in the second phase particles that appropriate S and N and Ti is formed.If but the too high levels of S and N, can form thick TiS and TiN particle in steel, the plasticity of grievous injury steel, thick TiS and TiN particle can not play it to the effect improving fish scaling resistance simultaneously.Therefore in steel of the present invention, the upper limit of S content controls 0.045%, the upper limit of N content controls 0.009%.If it is too low that the content of S and N controls, can not give full play to it to the effect improving fish scaling resistance, therefore in steel of the present invention, the lower limit of S and N controls respectively 0.01% and 0.003%.
(7) P does not have disadvantageous effect to enamel property.If but its too high levels, the welding property of steel can be reduced.Therefore controlling its upper content limit is 0.025%.
(8) Als is deoxidation products, for making steel clean, should carry out Al deoxidation, and Als is 0.005% ~ 0.050% time, and can be enough to the cleanliness factor ensureing steel, Als makes the cost of steel increase more than 0.050%.Therefore control Als content is between 0.005% ~ 0.050%.
(9) Cr is the element that can improve the condition of surface of rolling rear steel plate.The degree of roughness of surface of steel plate can be adjusted with it, improve enamel tack.Due to Cr lower than 0.05% time, the degree improving steel surface roughness is not obvious, and when reaching 0.20%, its effect is saturated.And higher than 0.20% time also make the production cost of steel plate increase.So determine that the scope of adding Cr is 0.05% ~ 0.20%.
The manufacture method of the hot-rolled double-side enamel steel of fish scaling resistance excellence, comprises smelting, continuous casting, strand heating, roughing, finish rolling, section cooling, batches:
Slab heating temperature 1180 ~ 1260
through high-pressure water descaling after soaking, roughing becomes intermediate blank.
Finish rolling within the scope of 820 ~ 1080 DEG C, through 5 ~ 7 passes to target thickness, wherein finish rolling start rolling temperature is 960 ~ 1080
final rolling temperature is too high, ferrite crystal grain coarsening, and grain boundary area reduces relatively, unfavorable to fish scaling resistance.Final rolling temperature is too low, increases mill load; Finishing temperature is 820 ~ 900, and too low can the induction of DEG C finishing temperature is first separated out, and make the uneven and precipitation particles coarsening of precipitation, thick particle is unfavorable to fish scaling resistance.Under the condition of cooling fast after rolling, 820
upper finish to gauge, the degree of this coarsening is also not remarkable.And 900
roll, the quantity that TiC particle is first separated out in induction is little.
Take Cooling Mode after rolling, in 8S, be chilled to coiling temperature 550 ~ 650 soon with>=40 DEG C/S cooling rate
under the condition of Slow cooling, the scope separated out due to Ti particle is very wide, and its precipitation particles is easy to coarsening, and the total surface area of precipitated phase is reduced; Ferrite grain size is thick on the other hand, ferrite grain boundaries area reduces relatively, the insufficient total amount of storage hydrogen trap, and therefore the present invention proposes to adopt high quick speed of cooling, make the precipitation particles small and dispersed more of the Ti again separated out, add the total surface area of precipitated phase; Ferritic structure simultaneously in steel obtains refinement, and ferrite crystal grain, more than 10 grades, makes ferrite grain boundaries area relatively increase, and the factor of two aspects makes to have enough storage hydrogen traps in steel, is conducive to the generation suppressing squama quick-fried.Take the leading portion type of cooling to be chilled to coiling temperature soon with>=40 DEG C/S cooling rate after rolling in 8S, the precipitation particles of thick Ti can be suppressed completely to be formed, be conducive to fetrite grain refinement, therefore determine that rolling rear cooling rate should be not less than 40
/ S
For steel of the present invention, coiling temperature is lower than 550
, suppressed as the precipitation of the precipitation particles of the titanium of storage hydrogen trap, storage hydrogen trap insufficient total amount, is not enough to the generation suppressing squama quick-fried.And coiling temperature is higher than 650
ferrite crystal grain there will be coarsening, and ferrite grain boundaries area reduces relatively, the insufficient total amount of storage hydrogen trap.Therefore the scope controlling coiling temperature is 550 ~ 650
Beneficial effect of the present invention is:
(1) steel of the present invention is controlled by reasonable component design and processes, makes to form enough storage hydrogen traps in steel, improves the fish scaling resistance of steel plate.Manufacture for large-scale enamel assembling component provides a kind of steel plate materials of fish scaling resistance excellence.
(2) the present invention is at control Ti/C than under the prerequisite being 1.5 ~ 3.0, is no more than 0.15% by control Ti content, enables steel plate by the method stably manufactured of continuous casting and hot rolling.
Accompanying drawing explanation
Fig. 1 is embodiment 1 metallographic structure photo.
Fig. 2 is the tiny precipitated phase of embodiment 1.
Embodiment
Below by embodiment, the present invention is further illustrated.
The embodiment of the present invention, according to the component proportion of technical scheme, is carried out smelting, the heating of continuous casting, strand, roughing, finish rolling, section cooling, to be batched.The smelting composition of embodiment of the present invention steel is in table 1.The main technologic parameters of embodiment of the present invention steel is in table 2.The performance of embodiment of the present invention steel is in table 3.
The smelting ingredient w t% of table 1 embodiment of the present invention steel
The main technologic parameters of table 2 embodiment of the present invention steel
The performance of table 3 embodiment of the present invention steel
Temperature is 850 ~ 890, DEG C enamel firing time 8 ~ 12min.The quick-fried situation of squama is the investigation result to placing 6 months after sample double-face spray painting enamel enamel firing.
Because the quick-fried defect of squama is easier to occur at hot-rolled double-side enamel steel, therefore reasonable component design and processes controls to be crucial.The present invention is by controlling N, S element content range appropriate in steel on the one hand, adds appropriate Ti element, makes can form enough second phase particles in steel, as the trap of storage hydrogen, improves the fish scaling resistance of steel plate.On the other hand adopt Controlled Rolling And Controlled Cooling, make in steel that ferrite crystal grain is more than 10 grades, crystal grain is more tiny, and grain boundary area increases relatively.Crystal boundary is also considered to a kind of trap of effective storage hydrogen, and namely grain boundary area is larger, and in steel plate enamel firing process, hydrogen storage ability is stronger, more favourable to the fish scaling resistance of steel plate.
Claims (2)
1. the hot-rolled double-side enamel steel of fish scaling resistance excellence, it is characterized in that, the composition of this steel plate is as follows by weight percentage: C:0.02 ~ 0.06%, Si≤0.10%, Mn:0.50 ~ 1.0%, P :≤0.025%, S:0.010 ~ 0.045%, N:0.003 ~ 0.009%, Ti:0.05 ~ 0.15%, Als:0.005 ~ 0.050%, Ti/C:1.5 ~ 3.0, Cr:0.05 ~ 0.20%, and all the other are iron and inevitable impurity.
2. the manufacture method of the hot-rolled double-side enamel steel of a fish scaling resistance excellence according to claim 1, comprise smelting, continuous casting, strand heating, roughing, finish rolling, section cooling, batch, it is characterized in that: slab heating temperature 1180 ~ 1260 DEG C, through high-pressure water descaling after soaking, roughing becomes intermediate blank; Finish rolling within the scope of 820 ~ 1080 DEG C, through 5 ~ 7 passes to target thickness, finish rolling start rolling temperature is 960 ~ 1080 DEG C, and finishing temperature is 820 ~ 900 DEG C, take Cooling Mode after rolling, in 8S, be chilled to coiling temperature 550 ~ 650 DEG C soon with >=40 DEG C/S cooling rate.
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Cited By (8)
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| CN105349884A (en) * | 2015-10-15 | 2016-02-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Ti-contained hot-rolled and acid-pickled enameled steel strip and production method thereof |
| CN106148855A (en) * | 2015-04-27 | 2016-11-23 | 鞍钢股份有限公司 | A kind of hot rolling glassed steel production method with excellent fish scaling resistance |
| CN106282846A (en) * | 2015-05-28 | 2017-01-04 | 鞍钢股份有限公司 | A kind of glassed steel with excellent fish scaling resistance and the manufacture method of steel plate thereof |
| CN106811705A (en) * | 2015-12-02 | 2017-06-09 | 鞍钢股份有限公司 | A kind of excellent enamel steel plate of fish scaling resistance and its manufacture method |
| CN108396236A (en) * | 2017-02-05 | 2018-08-14 | 鞍钢股份有限公司 | A kind of subway decoration hot rolling enamelled pressed steel and its manufacturing method |
| CN113684413A (en) * | 2020-05-18 | 2021-11-23 | 宝山钢铁股份有限公司 | Cold-rolled enamel steel for deep drawing liner and manufacturing method thereof |
| CN115161555A (en) * | 2022-07-01 | 2022-10-11 | 鞍钢股份有限公司 | Rare earth hot rolled steel plate for 410 MPa-grade double-sided enamel after enamel and manufacturing method thereof |
| CN115198183A (en) * | 2022-07-01 | 2022-10-18 | 鞍钢股份有限公司 | Rare earth hot rolled steel plate for 350 MPa-grade double-sided enamel after enamel and manufacturing method thereof |
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| CN106282846A (en) * | 2015-05-28 | 2017-01-04 | 鞍钢股份有限公司 | A kind of glassed steel with excellent fish scaling resistance and the manufacture method of steel plate thereof |
| CN105349884A (en) * | 2015-10-15 | 2016-02-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Ti-contained hot-rolled and acid-pickled enameled steel strip and production method thereof |
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