CN104250705A - Enamel steel with high-temperature baking hardenability and manufacturing method thereof - Google Patents
Enamel steel with high-temperature baking hardenability and manufacturing method thereof Download PDFInfo
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- CN104250705A CN104250705A CN201410483551.8A CN201410483551A CN104250705A CN 104250705 A CN104250705 A CN 104250705A CN 201410483551 A CN201410483551 A CN 201410483551A CN 104250705 A CN104250705 A CN 104250705A
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Abstract
The invention discloses enamel steel with high-temperature baking hardenability. The enamel steel comprises chemical elements in percentage by weight as follows: 0.008-0.020% of C, 0.05-0.50% of Mn, 0.021-0.035% of S, 0.005-0.050% of Alt or 0.003-0.045% of AlS, larger than 0 and less than 0.003% of N, larger than 0 and less than or equal to 0.010% of O and element Ti, wherein the weight percentage of element Ti meets the conditions N*Ti smaller than or equal to 3*10<-4>,S*Ti greater than or equal to 2*10<-3> and Ti greater than or equal to 3.43N+1.5S+0.02, and the balance is Fe and unavoidable impurity elements. The invention further discloses a manufacturing method of the enamel steel, which comprises the steps of pretreatment of hot metal, converter smelting, refining, continuous casting and hot rolling. The enamel steel with high-temperature baking hardenability has relatively good forming property, good welding property, excellent firing property and excellent enameling property.
Description
Technical field
The present invention relates to a kind of alloy steel products and manufacture method thereof, particularly relate to a kind of Steel for enamel and manufacture method thereof.
Background technology
For displacement type water heater, inner bag is its key part, which determines use safety and the work-ing life of water-heater.Be that the enamel inner container of end base has that solidity to corrosion is good, surface hardness is high, the smooth various features such as easy to clean with steel plate, such enamel inner container improves work-ing life and the over-all properties of water heater liner significantly.Adopt steel plate to be end base when making the enamel inner container of water-heater, first steel plate needs through blanking, shapes, welds laggard, then carries out the application of slip, finally burns till under the hot conditions of about 830 DEG C.But produce the requirement of high quality enamel inner container to meet, steel plate must meet plasticity, intensity, weldability, scaling resistance, anti-pin hole and high temperature resistantly many-sided performance requriements such as burn till.
Before, enamel inner container is welded by three parts usually, i.e. two end caps and a ladle body, and therefore an enamel inner container generally has three road weld seams, it comprise twice circumferential weld with together with vertical masonry joint, two requirements of end cap to plasticity are relatively low.But, a kind of novel internal bladder is there is in prior art, this novel internal bladder is welded by upper barrel, lower barrel two portions, three original road weld seams are reduced to middle one girth welding, therefore, novel internal bladder eliminates volume circle, reaming and twice weld seam in the course of processing, and manufacture craft is simplified widely.Meanwhile, the minimizing of weld seam can improve the voltage endurance capability of inner bag significantly.Meanwhile, because the punching press of novel internal bladder is comparatively dark, after punching press, carry out the processing such as reaming again, thus, the punching performance of steel plate and reaming performance requriements are significantly improved.
In order to meet the processing request of inner bag, mainly adopt cold-rolled steel sheet, its forming property is better than hot-rolled steel sheet.The steel plate being generally used for inner bag in prior art can meet punching press requirement, but its reaming performance is lower, and namely after deep-draw, reaming is easily ftractureed.Simultaneously, owing to lacking the suppression mechanism of ferrite crystal grain abnormal growth under high temperature in steel, the crystal grain severely subnormal of Seam and heat effected zone is grown up after welding, after high-temperature coating enamel firing becomes, crystal grain is also easily grown up, cause the yield strength of steel plate mother metal, Seam and heat effected zone etc. to decline, finally cause inner bag very easily ftracture around weld seam when suppressing and leak.In addition, owing to storing hydrogen trap deficiency in steel, even if under the one side application of slip condition of inner bag, also often can produce fish-scaling effect.
Publication number is CN1966753A, publication date is on February 23rd, 2007, name is called that the Chinese patent literature of " a kind of steel plate for hot-rolled double-side enamel and manufacture method thereof " relates to a kind of enamel sheet, and its each elemental composition (wt.%) is: C:0.02% ~ 0.06%, Si :≤0.50%, Mn:0.15% ~ 0.40%, P :≤0.15%, S :≤0.006%, N≤0.003%, Ti:0.08% ~ 0.20%, Al
s: 0.005% ~ 0.055%, Ti/C:2.2 ~ 5, surplus is Fe and inevitable impurity.Hot-rolled state undertissue be crystal grain diameter at the ferrite of 2 μm ~ 20 μm, be uniform-distribution with the TiC particle of diameter at below 20nm in the tissue.In the technical scheme disclosed in this patent documentation, enamel sheet has the higher Ti element of content and the lower S element of content.
Publication number is CN101684532A, publication date is on March 31st, 2010, name is called that the Chinese patent literature of " a kind of enamel steel for cold rolling water heater and production method " discloses a kind of Glassed Steel, its chemical element mass percentage is the composition composition of (wt.%): C:0.01% ~ 0.08%, Si≤0.03%, Mn:0.10% ~ 0.60%, P≤0.02%, S:0.003% ~ 0.02%, N:0.001% ~ 0.006%, Al
s≤ 0.04%, Ti:0.02% ~ 0.12%, all the other are iron and inevitable impurity, and the superfluous titanium content in steel meets relational expression: Ti-(4*C+3.43*N+1.5S)≤0.The yield strength of Glassed Steel disclosed in this Chinese patent literature after simulation enamel firing is lower than the yield strength before simulation enamel firing.
Publication number is CN101586210A, publication date is on November 25th, 2009, the Chinese patent literature that name is called " high strength enamel steel and production thereof and burning ward off technique " discloses a kind of for Steel for enamel, and the mass percentage of its each chemical element is: C:0.01 ~ 0.12, Si≤0.03, Mn:0.50 ~ 1.00, P≤0.070, S≤0.015, Nb:0.020 ~ 0.050, Mo:0.05 ~ 0.30, Al
s: 0.005 ~ 0.070, surplus is Fe and inevitable impurity.Meanwhile, this Steel for enamel also meets 10Nb >=Mo and 0.30≤10Nb+Mo≤0.50.
Summary of the invention
The object of the present invention is to provide one to have the indurative Steel for enamel of high bake, this Steel for enamel has excellent forming property, good welding property and excellent application of slip performance.In addition, Steel for enamel of the present invention also possesses excellent enamel firing performance, and its yield strength after high temperature enamel firing can significantly promote, and namely has high bake hardening.In addition, the alloy interpolation cost of Steel for enamel of the present invention is low.
To achieve these goals, the invention provides one and have the indurative Steel for enamel of high bake, its chemical element percent mass proportioning is:
C：0.008～0.020％；
Mn：0.05～0.50％；
S：0.021～0.035％；
Alt 0.005 ~ 0.050% or Al
s0.003 ~ 0.045wt.%;
0＜N＜0.003％；
0＜O≤0.010％；
And Ti element, and the mass percentage of Ti element meets N × Ti≤3 × 10
-4, S × Ti>=2 × 10
-3, Ti>=3.43N+1.5S+0.02; Surplus is Fe and inevitable impurity element.
In the technical program, inevitable impurity mainly refers to P element and Si element.P content is easy to segregation on the crystal boundary in steel time higher, thus, easily produce bubble and stain when enamel firing, thus affect the surface quality of enamel.Not only can damage the enamel property of steel when Si content is higher, but also the very poor oxide inclusion of ductility can be formed, thus the plasticity of infringement steel.For technical scheme of the present invention, P element and Si element are harmful elements, and it is more low better that their content in steel needs, and therefore, the content of Si element can be controlled as≤0.10wt.%, and are controlled by the content of P element as≤0.035wt.%.
The principle of design of each chemical element had in the indurative Steel for enamel of high bake of the present invention is:
C and Ti: first, in steel, carbon content has a significant impact the forming property of steel plate and intensity, and carbon content is higher, and plasticity is lower, and intensity is higher, and vice versa.Secondly, carbon except solid solution exists, also can form the microtexture such as cementite or perlite in steel.In addition, after interpolation titanium alloy, carbon can also form titanium carbide compound with titanium.
In the inventive solutions, by the content of titanium elements controlling carbon content and react with carbon, and in conjunction with follow-up technology controlling and process, make carbon can not form perlite microtexture, but exist with the carbide (such as, titanium carbide, cementite etc.) in disperse or a small amount of solution.Because cementite is assembled in a large number in perlite microtexture, a large amount of bubbles can be formed on the one hand in enamel process, in enamel firing process, be unfavorable for the intensity improving steel on the other hand.When carbon content is higher than 0.020wt.%, then carbon is easy to be formed comparatively thick cementite, even can produce perlite microtexture, otherwise, when carbon content is lower than 0.008wt.%, and not only in steel cementite content little, the titanium carbide formed with titanium is also little, cannot play strengthening effect, the intensity of steel reduces, and does not also reach the effect of high bake sclerosis.
For technical scheme of the present invention, the amount adding titanium alloy is very important.Calculate known according to the solubility product of the compound formation of titanium: titanium first and nitrogen react, secondly and sulphur react, finally and carbon react, thus, with such precipitation sequentially, must ensure after a part of titanium and carbon react and form titanium carbide.When the mass percentage of the titanium elements added meets relational expression: during Ti >=3.43N+1.5S+0.02, just can ensure a part of titanium and carbon reaction, and make cementite particle little than existing cementite particle by controlling hot rolling technology, and titanium carbide, titanium carbonitride exist with fine particle state, to realize the object of matrix strengthening.Simultaneously; in enamel high temperature sintering process; originally with the cementite of small and dispersed state existence and titanium carbide, carbon titanium nitride particle; in subsequent heat process, understand some dissolve; and separate out again in process of cooling subsequently; the particle of again separating out can more tiny, disperse, thus realizes the object reaching baking hardening through pyroprocess.On the contrary, if the mass percentage of titanium elements is too low, if lower than the content that relational expression limits, namely during Ti < 3.43N+1.5S+0.02, so just be difficult to the titanium carbide, the titanium carbonitride particle that ensure to there is some amount in steel, like this, the object of precipitation strength can not also just be played.For this reason, after burning till through high temperature, the intensity of steel cannot be improved further.Thus, should control to be 0.008 ~ 0.020wt.% at the content of the C element had in the indurative Steel for enamel of high bake of the present invention, and the content of Ti element should meet: Ti >=3.43N+1.5S+0.02.
In addition, more preferably, the content of C element is controlled between the scope of 0.015 ~ 0.020wt.%.
Mn: manganese is the deoxidant element in steel, adds the content that it can control oxygen in steel.Manganese can generate manganese sulfide with reaction of Salmon-Saxl.Add titanium elements in steel after, manganese also can form with it the inclusion of compound, such as manganese sulfide titanium etc.This type impurity is spherical, can reduce the impact of manganese sulfide on processing characteristics significantly.But, when Fe content is too high, the reaction at steel and enamel interface can be affected in enamel process, the adherence of infringement enamel, and easily produce the defects such as bubble.Given this, the Mn content had in the indurative Steel for enamel of high bake of the present invention is set as 0.05 ~ 0.50wt.%.
Preferably, the above-mentioned Mn content had in the indurative Steel for enamel of high bake is set as 0.1 ~ 0.3wt.% further.
S: in general, the sulphur in steel is harmful element, this is because sulphur and manganese can form manganese sulfide inclusion thing, manganese sulfide inclusion thing can damage the horizontal plastic property of steel plate.But S element is not harmful element in the inventive solutions, needs to control in Steel for enamel S content between 0.021 ~ 0.035wt.% scope, and will S × Ti>=2 × 10 be ensured
-3.Why controlling between 0.021 ~ 0.035wt.% scope by sulphur content, is that sulphur and titanium can form titanium sulfide, can form a large amount of storage hydrogen traps around titanium sulfide particle, not easily produce the quick-fried defect of squama in enamel process because on the basis adding titanium.Meanwhile, add titanium elements in steel after, the manganese sulfide that formed in steel can also be reduced to the disadvantageous effect of steel plasticity.But if sulphur content is higher than 0.035wt.%, then sulphur needs to consume more titanium and manganese to form sulfide, and the sulfide grain formed can be very large, like this, can damage the plasticity of steel.In addition, the sulfide of larger particles is also very limited to the effect improving fish scaling resistance.In addition, sulphur can form titanium sulfide with titanium or can form the manganese sulfide titanium of compound with titanium and manganese.Ensure S × Ti>=2 × 10 by the control of sulphur content
-3, titanium sulfide can be made to be formed prior to manganese sulfide.Its reason is that the product of S × Ti is larger, then the formation temperature of titanium sulfide is higher, and titanium sulfide particle shape presents spherical, like this, can be improved the shape and size of titanium sulfide in subsequent hot rolled process by control heating and milling step further.Similarly, for manganese element, manganese also can form the manganese sulfide titanium inclusion of compound with sulphur, titanium, and its particle shape is also rendered as spherical, for this reason, just avoids and form simple plasticity manganese sulfide inclusion in steel, thus improves the processing characteristics of steel.
In addition, being controlled to be 0.021 ~ 0.03wt.% by S content in Steel for enamel is the more preferred technical scheme of one.
Alt or Al
s: aluminium is also strong deoxidant element.Oxygen level when aluminium content is higher in steel will reduce, otherwise when aluminium content is too low, then the oxygen level in steel will promote.The oxygen remained in steel mainly exists with oxide inclusion form, and it seriously can damage the plasticity of steel.Appropriate aluminium can reduce the oxygen level in steel, and thus, aluminium is one of element that must add in steel.For this reason, for of the present invention, there is the indurative Steel for enamel of high bake, if Al limits with the form of Alt (total aluminium), then need Alt content to be controlled to be 0.005 ~ 0.050wt.%, if Al is with Al
sthe form of (dissolved aluminum) limits, then need control Al
sbe 0.003 ~ 0.045wt.%.
N: nitrogen is one of inevitable relict element in steel.Usual nitrogen is solid solution element, and add titanium in steel after, because nitrogen very easily forms metallic compound with titanium, therefore, in the steel after adding titanium, nitrogen can have precedence over sulphur and carbon more, forms titanium nitride with titanium.The formation of titanium nitride is successively relevant with the content of titanium, nitrogen, and this solubility product that can be formed according to titanium nitride calculates, i.e. lg [Ti] * [N]=5.4-15790/T, wherein, T is the solid solubility temperature of titanium nitride, and unit is the mass percentage that K, Ti and N are element.Nitrogen and/or titanium content higher, the amount of the titanium nitride of formation is also higher, and particle is also larger.Meanwhile, if desired fix the nitrogen of 0.001wt.%, then need the titanium consuming 0.00343wt.%, the quality that titanium consumes is about 3.43 times of the quality of nitrogen.Titanium nitride particles can form small hole in machining deformation around particle, and to be conducive to the storage hydrogen of steel plate in enamel process, but titanium nitride particles also can other mechanical properties such as the plasticity of grievous injury steel plate and reaming performance.In addition, titanium nitride particles can not improve intensity and the intensity of steel after enamel firing of steel.For this reason, in order to avoid forming titanium nitride inclusion thick in steel, and reduce the consumption of nitrogen to titanium, nitrogen in steel is low as best one can, is 0 < N < 0.003wt.%, and meets N × Ti≤3 × 10 by Control of Nitrogen Content
-4.
O: because molten steel mainly relies on reaction between carbon and oxygen in smelting process, therefore, oxygen is inevitable in steel.But, can oxide inclusion be formed when oxygen content in steel is too high and affect the processing characteristics of steel.Based on this, of the present invention have the indurative Steel for enamel of high bake must by O control be: 0 < O≤0.010wt.%.
In the inventive solutions, the restriction for the mass percentage of titanium is limited by following three constraint formulations: 1) N × Ti≤3 × 10
-4, 2) and S × Ti>=2 × 10
-3, and 3) Ti>=3.43N+1.5S+0.02.That is, the interpolation of Ti element receives the constrained of the mass percentage of N and S element.
Because the carbon content in Steel for enamel of the present invention is low, most of carbon can be fixed to form titanium carbide compound add titanium in steel after, this makes the carbon under free state or cementite content be all few, this greatly can suppress the generation of needle pore defect in application of slip process, thus improves the work-ing life of enamel inner container significantly.
Further, the C element had in the indurative Steel for enamel of high bake of the present invention exists with the carbide form of disperse.
Further, described carbide is titanium carbide, the titanium carbonitride that cementite and particle are tiny.
Further, the particle diameter of described titanium carbide, carbon titanium nitride particle is 10 ~ 30 μm.
Further, have in the indurative Steel for enamel of high bake of the present invention, also containing 0 < Cu≤0.10%, 0 < Cr≤0.10%, 0 < Ni≤0.10%, 0 < Mo≤0.10%, 0 < Nb≤0.010%, 0 < V≤0.020%, 0 < B≤0.0005% at least one of them, and 0.05%≤5 × Nb+Cu+V+Ni+Cr+Mo+10 × B≤0.20%.
The content fluctuation of the copper in steel, chromium, nickel and molybdenum all can affect the enamel property of steel plate, particularly can affect the adherence of steel, and can produce surface imperfection, also can affect intensity and the plasticity of steel plate.In order to ensure the reliable and stable of the application of slip performance of steel etc. further, by the control of these Addition ofelements be: 0 < Cu≤0.10wt.%, 0 < Cr≤0.10wt.%, 0 < Ni≤0.10wt.%, 0 < Mo≤0.10wt.%
Add the recrystallization temperature that niobium, vanadium and boron can improve steel.Once recrystallization temperature improves, then the hot-rolled temperature of steel plate also needs correspondingly to improve.For thin specification steel plate, such as, finished product thickness is at the steel plate of below 2.5mm, and too high finishing temperature is difficult to realize, and can cause the problem of the temperature inequality of steel band different sites, finally causes mixed crystal and the tissue abnormalities defect of steel plate.In addition, although the raising of recrystallization temperature has certain effect for the intensity before raising enamel sintering, for the effect that the intensity improved after enamel sintering is too not large.In order to reduce the disadvantageous effect of these Addition ofelements to microstructure after hot rolling, need them to control within limits, i.e. 0 < Nb≤0.010wt.%, 0 < V≤0.020wt.%, 0 < B≤0.0005wt.%.
Meanwhile, demand fulfillment is gone back when above-mentioned element adds: 0.05wt.%≤5 × Nb+Cu+V+Ni+Cr+Mo+10 × B≤0.20wt.%.
Correspondingly, present invention also offers and a kind ofly produce the manufacture method with the indurative Steel for enamel of high bake mentioned above, this manufacture method comprises step: hot metal pretreatment → converter smelting → refining → continuous casting → hot rolling.
Further, of the present invention there is the hot-rolled step of the manufacture method of the indurative Steel for enamel of high bake after also comprise successively: pickling → cold rolling → annealing → smooth.
Further, in described cold rolling step, control total reduction and be greater than 70%.Further preferably, cold rolling total reduction >=75% is controlled.In addition, steel surface roughness can also be controlled within the scope of 0.4 ~ 2.0 μm by the roughness changing roll surface at cold rolling step.
Further, in described annealing steps, annealing temperature is 650-800 DEG C.
Further, in above-mentioned hot-rolled step, Heating temperature is 1100 ~ 1250 DEG C, heat-up time >=thickness of slab × 1min/mm, wherein thickness of slab unit is mm, and wherein this thickness of slab refers to continuously cast bloom thickness of slab.
In order to ensure that the microtexture in steel forms uniform austenite, i.e. abundant austenitizing, and the cementite assembled in steel billet or perlite are dissolved, namely the particle making some high temperature be formed dissolves as titanium nitride etc. or is partly dissolved, and the Heating temperature of continuously cast bloom is set as 1100 ~ 1250 DEG C.Certainly, the concrete heat-up time within the scope of this can adjust according to steel billet thickness, and general steel billet is thinner, and its heat-up time is shorter, its heat-up time demand fulfillment t >=thickness of slab × 1min/mm.
Further, in above-mentioned hot-rolled step, hot rolling finishing temperature is 850 ~ 930 DEG C, and hot-rolling coiling temperature is 630 ~ 780 DEG C.
Due in hot-rolled step, the carbide before dissolved in casting process etc. can be separated out again with the form of compound, therefore, need the finishing temperature reasonably controlled in hot-rolled step, present small and dispersed distributions in ferritic matrix to make carbide.Given this, control Steel for enamel of the present invention and complete hot rolling finish to gauge in 850 ~ 930 DEG C of temperature ranges, to guarantee that hot rolling completes more than recrystallization temperature, avoid, in austenite+ferrite two-phase region rolling, preventing the defect causing steel plate mixed crystal and tissue abnormalities.
The manufacture method with the indurative Steel for enamel of high bake of the present invention makes cementite and titanium carbide exist with fine particle state, to reach the object of matrix strengthening by controlling processing parameter in hot-rolled step.In addition, the shape and size of titanium sulfide in steel are improved further by the finishing temperature in Heating temperature in control continuous casting step and hot-rolled step and coiling temperature.
Compare to existing Steel for enamel, of the present invention have the yield strength of the indurative Steel for enamel of high bake after high temperature enamel firing and significantly promote, thus improve the voltage endurance capability of Steel for enamel goods, extends its work-ing life.
Of the present invention have the indurative Steel for enamel of high bake and possess good processability, its unit elongation >=39%, hole expansibility >=60%, is particularly suitable for the water heater liner making various complicated shape.
Of the present invention have the indurative Steel for enamel of high bake and possess good welding property.
Of the present invention have the indurative Steel for enamel of high bake and possess excellent application of slip performance, and its hydrogen permeation time long (>=10min), higher than the hydrogen permeation time (>=8min) of counterenamel steel in prior art.
Owing to have employed the lower alloy Addition ofelements of price, the cost of alloy with the indurative Steel for enamel of high bake of the present invention is low, and manufacturing cost is relatively economical also.
The production technique with the manufacture method of the indurative Steel for enamel of high bake of the present invention is simple.
Accompanying drawing explanation
Fig. 1 be embodiment A 1 there is the indurative Steel for enamel of high bake under 830 DEG C of keeping warm modes along with the trend map of yield strength that soaking time is passed.
Fig. 2 is the micro-organization chart with the indurative Steel for enamel of high bake of embodiment A 1.
Fig. 3 is the shape appearance figure with the precipitated phase in the indurative Steel for enamel of high bake of embodiment A 1.
Embodiment
To have the indurative Steel for enamel of high bake and manufacture method thereof and make to of the present invention and further illustrating according to specific embodiment below, but specific embodiment and related description do not form the improper restriction for technical scheme of the present invention.
Embodiment A 1-A6 and comparative example B1
Manufacture the Steel for enamel in embodiment A 1-A5 and comparative example B1 according to following step (1)-(5), manufacture the Steel for enamel in embodiment A 6 according to following step (1)-(9):
1) hot metal pretreatment;
2) converter smelting: realize decarburization, dephosphorization by top and bottom combined blown converter, removes residual element and obnoxious flavour etc.;
3) refining: slough obnoxious flavour and residual element further, adds the alloying element such as titanium, in enter the deoxidations such as aluminium, realize the accurate control of chemical composition.The percent mass proportioning controlling each chemical element of embodiment A 1-A6 and comparative example B1 is as shown in table 1;
4) continuous casting: the continuously cast bloom that molten steel casting becomes 200,230mm is thick, after continuously cast bloom cooling, Surface Quality carries out hand inspection, and effects on surface defect carries out labor cleaning;
5) hot rolling: is heated by continuously cast bloom before hot rolling, Heating temperature is 1100 ~ 1250 DEG C, heat-up time t >=thickness of slab × 1min/mm, wherein thickness of slab unit is mm; The continuously cast bloom thick to 200mm, controls at 200 ~ 240min or longer its heat-up time, and the continuously cast bloom thick to 230mm controls at 230 ~ 260min or longer its heat-up time; As required, hot rolling end of a period thickness is 1.5 ~ 18mm, and hot rolling finishing temperature is 850 ~ 930 DEG C, batches after section cooling to coiling temperature, and hot-rolling coiling temperature is 630 ~ 780 DEG C;
6) pickling: the main hydrochloric acid of dilution that adopts carries out pickling, and alternate manner also can be taked to carry out pickling, and the object of pickling is the iron scale eliminating surface;
7) cold rolling: to control total reduction more than 70%;
8) anneal: 650 ~ 800 DEG C of annealing, object is the recrystallize and the grain growth that realize cold rolling rear steel plate tissue, to obtain good plasticity;
9) smooth: smooth unit elongation is 0.8 ~ 1.2%.
In each step, concrete technology parameter is in detail see table 2.
Table 1 lists the percent mass proportioning of each chemical element in the Steel for enamel of this case embodiment A 1-A6 and comparative example B1.
Table 1. (wt.%, surplus is Fe and other the inevitable impurity except P and Si)
| Sequence number | A1 | A2 | A3 | A4 | A5 | A6 | B1 |
| C | 0.013 | 0.018 | 0.02 | 0.008 | 0.01 | 0.013 | 0.031 |
| Mn | 0.25 | 0.2 | 0.1 | 0.3 | 0.25 | 0.15 | 0.22 |
| S | 0.029 | 0.025 | 0.035 | 0.025 | 0.03 | 0.021 | 0.007 |
| Al | 0.041 | 0.035 | 0.035 | 0.028 | 0.005 | 0.02 | 0.031 |
| N | 0.0018 | 0.002 | 0.0025 | 0.0015 | 0.002 | 0.002 | 0.0026 |
| O | 0.005 | 0.006 | 0.003 | 0.005 | 0.003 | 0.003 | -- |
| P | 0.011 | 0.015 | 0.009 | 0.01 | 0.008 | 0.011 | 0.01 |
| Si | 0.008 | 0.02 | 0.05 | 0.03 | 0.1 | 0.008 | 0.006 |
| Ti | 0.09 | 0.08 | 0.09 | 0.085 | 0.15 | 0.12 | 0.002 |
| Cu | 0.01 | 0.02 | 0.02 | 0.05 | 0.01 | 0.06 | -- |
| Cr | 0.02 | 0.05 | 0.02 | 0.015 | 0.05 | 0.06 | -- |
| Ni | 0.008 | 0.025 | 0.008 | 0.01 | 0.02 | 0.005 | -- |
| Mo | 0.005 | 0.005 | 0.015 | 0.008 | 0.02 | 0.01 | -- |
| Nb | 0.005 | 0.002 | 0.002 | -- | -- | 0.002 | -- |
| V | 0.015 | -- | -- | -- | 0.005 | 0.01 | -- |
| B | -- | 0.0002 | -- | -- | 0.0004 | -- | -- |
| Relational expression 1) | 0.00016 | 0.00016 | 0.00023 | 0.00013 | 0.0003 | 0.00024 | 5.2×10 -6 |
| Relational expression 2) | 0.0026 | 0.002 | 0.0032 | 0.0021 | 0.0045 | 0.0025 | 1.4×10 -5 |
| Relational expression 3) | 0.07 | 0.064 | 0.081 | 0.063 | 0.072 | 0.058 | 0.039 |
| Relational expression 4) | 0.02 | 0.016 | 0.009 | 0.022 | 0.078 | 0.062 | -0.037 |
| Relational expression 5) | 0.08 | 0.11 | 0.07 | 0.08 | 0.11 | 0.16 | 0 |
Note: relational expression 1) N × Ti, relational expression 2) S × Ti, relational expression 3) 3.43N+1.5S+0.02, relational expression 4) Ti-(3.43 × N+1.5 × S+0.02), relational expression 5) 5 × Nb+Cu+V+Ni+Cr+Mo+10 × B.
Table 2 lists the processing parameter of the manufacture method of the Steel for enamel of this case embodiment A 1-A6 and comparative example B1.
Table 2.
At room temperature, horizontal sampling is all adopted for embodiment A 1-A6 and comparative example B1, measure R
eL, R
m, A
80mmand hole expansibility.The hydrogen storage capacity weighing the Steel for enamel of embodiment A 1-A6 and comparative example B1 is then the hydrogen permeation time measuring steel plate according to the electrochemistry experiment method in standard EN 10209, and is all converted into the standard thickness of 1mm.
Under the keeping warm mode of 830 DEG C, heat-treat after laterally sampling is all adopted for embodiment A 1-A6 and comparative example B1, after being namely placed on the constant temperature oven inside holding 10min of 830 DEG C, take out air cooling to room temperature.Model after Overheating Treatment, measures R
eL, R
mand A
80mm.
Table 3 lists the mechanical property parameters of Steel for enamel respectively at room temperature and under the keeping warm mode of 830 DEG C in this case embodiment A 1-A6 and comparative example B1.
Table 3.
As can be seen from Table 3, at room temperature, the yield strength of embodiment A 1-A6 all>=197MPa, tensile strength all>=315MPa, unit elongation A
80>=39%, hole expansibility>=70%, the yield strength of hydrogen permeation time>=12min, and under 830 DEG C of keeping warm modes, embodiment A 1-A6 brings up to>=315MPa, tensile strength all>=412MPa, unit elongation A
80>=40%, it can be said that bright, Steel for enamel of the present invention not only has higher unit elongation, longer hydrogen permeation time, higher hole expansibility, and all embodiments all obtain improve significantly through the yield strengths after 830 DEG C of insulation 10min and tensile strength, this illustrates that the Glassed Steel that the technical program relates to has excellent high bake hardening, has this voltage endurance capability being beneficial to raising Steel for enamel goods significantly and work-ing life.
Hydrogen permeation time >=the 12min of Steel for enamel of the present invention.As a rule, as hydrogen permeation time >=8min, steel plate just can meet the quick-fried requirement of anti-squama during counterenamel, and that is, no matter adopt which kind of type glaze in actual production, namely this type of steel plate can meet the quick-fried requirement of anti-squama.Because counterenamel is more harsher than the quick-fried performance requriements of one side enamel antagonism squama, therefore, Steel for enamel of the present invention can meet the requirement of one side enamel completely.
What Fig. 1 showed embodiment A 1 has the indurative Steel for enamel of high bake under 830 DEG C of keeping warm modes along with the trend of the yield strength of time lapse.
As shown in Figure 1, under 830 DEG C of keeping warm modes, the Steel for enamel of embodiment A 1 is when not yet reaching soaking time (about the 10min) of regulation, the yield strength of the Steel for enamel of embodiment A 1 increases along with the passing of soaking time, but after reaching the soaking time of regulation, its yield strength reduces along with the passing of soaking time.But, even if the soaking time under 830 DEG C of keeping warm modes is long again, its yield strength compares to its yield strength under room temperature situation and still has raising by a relatively large margin.
Fig. 2 shows the microtexture of the Steel for enamel of embodiment A 1, and Fig. 3 then shows the shape appearance figure of the precipitated phase in this Steel for enamel.
As shown in Figures 2 and 3, the microtexture of the Steel for enamel of embodiment A 1 is uniform ferritic structure, and there are no the cementite particle of pearlitic structure and large-size, its precipitated phase is tiny, Dispersed precipitate, based on titanium carbide or titanium carbonitride.
It should be noted that above enumerate be only specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar changes thereupon.If all distortion that those skilled in the art directly derives from content disclosed by the invention or associates, protection scope of the present invention all should be belonged to.
Claims (14)
1. have the indurative Steel for enamel of high bake, its chemical element percent mass proportioning is: C:0.008 ~ 0.020%, Mn:0.05 ~ 0.50%, S:0.021 ~ 0.035%, Alt:0.005 ~ 0.050% or Al
s: 0.003 ~ 0.045%, 0 < N < 0.003%, 0 < O≤0.010% and Ti element, and the mass percentage of Ti element meets N × Ti≤3 × 10
-4, S × Ti>=2 × 10
-3, Ti>=3.43N+1.5S+0.02, surplus is Fe and inevitable impurity element.
2. have the indurative Steel for enamel of high bake as claimed in claim 1, it is characterized in that, described C element exists with the carbide form of disperse.
3. have the indurative Steel for enamel of high bake as claimed in claim 2, it is characterized in that, described carbide is titanium carbide, the titanium carbonitride that cementite and particle are tiny.
4. have the indurative Steel for enamel of high bake as claimed in claim 3, it is characterized in that, the particle diameter of described titanium carbide, carbon titanium nitride particle is 10 ~ 30 μm.
5. there is high bake indurative Steel for enamel as claimed in claim 1, it is characterized in that, also containing 0 < Cu≤0.10%, 0 < Cr≤0.10%, 0 < Ni≤0.10%, 0 < Mo≤0.10%, 0 < Nb≤0.010%, 0 < V≤0.020%, 0 < B≤0.0005% at least one of them, and 0.05%≤5 × Nb+Cu+V+Ni+Cr+Mo+10 × B≤0.20%.
6. have the indurative Steel for enamel of high bake as claimed in claim 1, it is characterized in that, described C element content is C:0.015 ~ 0.020%.
7. have the indurative Steel for enamel of high bake as claimed in claim 1, it is characterized in that, described S constituent content is 0.021 ~ 0.030%.
8. have the indurative Steel for enamel of high bake as claimed in claim 1, it is characterized in that, described Mn constituent content is 0.1 ~ 0.3%.
9. as the manufacture method with the indurative Steel for enamel of high bake in claim 1 ~ 8 as described in any one, it is characterized in that, comprise step: hot metal pretreatment → converter smelting → refining → continuous casting → hot rolling.
10. there is the manufacture method of the indurative Steel for enamel of high bake as claimed in claim 9, it is characterized in that, after described hot-rolled step, also comprise successively: pickling → cold rolling → annealing → smooth.
11. manufacture method as claimed in claim 10 with the indurative Steel for enamel of high bake, is characterized in that, in described cold rolling step, control total reduction and are greater than 70%.
12. manufacture method as claimed in claim 10 with the indurative Steel for enamel of high bake, it is characterized in that, in described annealing steps, annealing temperature is 650-800 DEG C.
13. manufacture method as claimed in claim 9 with the indurative Steel for enamel of high bake, it is characterized in that, in described hot-rolled step, Heating temperature is 1100-1250 DEG C, heat-up time >=thickness of slab × 1min/mm, wherein thickness of slab unit is mm.
14. manufacture method as claimed in claim 9 with the indurative Steel for enamel of high bake, it is characterized in that, in described hot-rolled step, hot rolling finishing temperature is 850-930 DEG C, and hot-rolling coiling temperature is 630-780 DEG C.
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| EP15841538.0A EP3196328B1 (en) | 2014-09-19 | 2015-09-16 | Enamel steel having high-temperature baking hardenability and manufacturing method therefor |
| PCT/CN2015/089695 WO2016041490A1 (en) | 2014-09-19 | 2015-09-16 | Enamel steel having high-temperature baking hardenability and manufacturing method therefor |
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| WO2016041490A1 (en) * | 2014-09-19 | 2016-03-24 | 宝山钢铁股份有限公司 | Enamel steel having high-temperature baking hardenability and manufacturing method therefor |
| CN104928577B (en) * | 2015-06-18 | 2017-08-25 | 宝山钢铁股份有限公司 | A kind of steel plate and its manufacture method with high hole expansibility and excellent application of slip performance |
| CN104928577A (en) * | 2015-06-18 | 2015-09-23 | 宝山钢铁股份有限公司 | Steel plate with high hole expansion rate and excellent enameling performance and manufacturing method thereof |
| CN107419183A (en) * | 2016-05-23 | 2017-12-01 | 上海梅山钢铁股份有限公司 | A kind of two-period form enamel internal container of water-heater hot rolled steel plate and its manufacture method |
| CN106222551A (en) * | 2016-08-16 | 2016-12-14 | 武汉钢铁股份有限公司 | A kind of flawless nitriding in surface iron ware substrate and production method |
| CN106222551B (en) * | 2016-08-16 | 2018-05-01 | 武汉钢铁有限公司 | A kind of flawless nitriding iron ware substrate in surface and production method |
| CN108796391A (en) * | 2017-04-26 | 2018-11-13 | 宝山钢铁股份有限公司 | A kind of enamel steel and its manufacturing method with excellent plasticity and toughness and scaling resistance |
| CN108796391B (en) * | 2017-04-26 | 2020-12-22 | 宝山钢铁股份有限公司 | Glass-lined steel with excellent plasticity and toughness and fish scaling resistance and manufacturing method thereof |
| CN107574375B (en) * | 2017-08-31 | 2019-06-07 | 武汉钢铁有限公司 | Counterenamel hot rolling acid-cleaning steel plate and its manufacturing method with excellent application of slip performance |
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| CN109554607A (en) * | 2017-09-25 | 2019-04-02 | 上海梅山钢铁股份有限公司 | Cold rolling enamelled pressed steel and its manufacturing method with excellent scaling resistance and deep drawing quality |
| CN110777301A (en) * | 2018-07-30 | 2020-02-11 | 宝山钢铁股份有限公司 | Cold-rolled enamel steel and manufacturing method thereof |
| CN110777301B (en) * | 2018-07-30 | 2021-05-14 | 宝山钢铁股份有限公司 | Cold-rolled enamel steel and manufacturing method thereof |
| CN109652739A (en) * | 2019-01-22 | 2019-04-19 | 山东钢铁股份有限公司 | A kind of enamel high intensity cold strip rolling and preparation method thereof |
| CN109943779A (en) * | 2019-04-30 | 2019-06-28 | 马鞍山钢铁股份有限公司 | A kind of enamel low-carbon cold rolling steel plate and its production method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3196328B1 (en) | 2019-08-14 |
| WO2016041490A1 (en) | 2016-03-24 |
| EP3196328A1 (en) | 2017-07-26 |
| CN104250705B (en) | 2017-01-18 |
| EP3196328A4 (en) | 2018-04-18 |
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