CN109423578A - Enamel cold-rolled steel sheet and its manufacturing method - Google Patents
Enamel cold-rolled steel sheet and its manufacturing method Download PDFInfo
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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
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
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- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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- 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
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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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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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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- 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
- C21D8/0236—Cold rolling
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- 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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- 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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- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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Abstract
The present invention relates to enamel cold-rolled steel sheet and its manufacturing methods, in terms of weight %, the cold-rolled steel sheet includes: C: more than 0 weight % and 0.0015 weight % or less, the weight of Mn:0.2~0.4 %, Al: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight % and 0.02 weight % or less, S: more than 0 weight % and 0.02 weight % or less, the weight of Cr:0.05~0.1 %, the weight of Nb:0.03~0.05 %, N: more than 0 weight % and 0.002 weight % or less, the weight of O:0.02~0.04 %, the Fe of surplus and other inevitable impurity, it and include Mn-Nb-Cr composite oxides, so as to improve mouldability and fishscale resistance.
Description
Technical field
The present invention relates to enamel cold-rolled steel sheet and its manufacturing methods, more specifically, relate to improve mouldability and
The enamel cold-rolled steel sheet and its manufacturing method of fishscale resistance.
Background technique
Enamelled pressed steel is the coated glass matter glaze on the cold-rolled steel sheet as basic steel plate, then fire at high temperature and
Improve a kind of Surface conditioning articles of corrosion resistance, weatherability, heat resistance etc..This enamelled pressed steel be mainly used for construction exterior,
Household electrical appliances, tableware etc..
Existing enamel sheet is prevented in enamelware by decarburizing annealing process or batch annealing process
Know the scale explosion for most serious defect or improves mouldability.But this method results in the rising of goods cost.
Recently, in order to reduce manufacturing cost, Ti is added, and manufacture enamel sheet using continuous annealing process.But
Recrystallization temperature for improving the steel of enamel is high, to need to be made annealing treatment at high temperature, therefore has productivity low
And the disadvantage that manufacturing cost is high.
In particular, TiN and intermetallic compound are generated in continuous casting working procedure due to addition Ti for Ti system glassed steel,
To which there is a phenomenon where spray nozzle cloggings, therefore continuous casting quantity is restricted, and the rising of production cost and production can be caused negative
Lotus.In addition, there is the problem of Ti can hinder the adhesiveness between enamelled pressed steel and the ceramic glaze bed of material when largely adding Ti.
In addition, as ensuring the scheme of fishscale resistance, it has been proposed that improve steel in oxygen content and artificially in steel
Middle generation oxide, and ensure using oxide the high-oxygen steel of hydrogen storage performance.But make resistance to since the oxygen content of high-oxygen steel is high
The melting loss of fiery object is extremely serious, to have the operational dangers such as molten steel leakage, and has continuous casting very low and steel
The high disadvantage of water manufacturing cost.
Existing technical literature
Patent document
(patent document 1) KR2013-0073424A
(patent document 2) KR2016-0041967A
Summary of the invention
Technical problems to be solved
The present invention provides the enamel cold-rolled steel sheet and its manufacturing method for being able to suppress surface defect and improving mouldability.
The present invention provide improve hydrogen storage performance and processing when will not crack defect enamel cold-rolled steel sheet and its
Manufacturing method.
Technical solution
Enamel cold-rolled steel sheet of the invention may include in terms of weight %: C: more than 0 weight % and 0.0015 weight
Measure % or less, weight %, Al of Mn:0.2~0.4: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight % and
0.02 weight % or less, S: more than 0 weight % and 0.02 weight % or less, weight %, Nb:0.03~0.05 Cr:0.05~0.1
Weight %, N: more than 0 weight % and 0.002 weight % or less, the weight of O:0.02~0.04 %, surplus Fe and other can not keep away
The impurity exempted from, and may include Mn-Nb-Cr composite oxides.
3 μm or more of size of the Mn-Nb-Cr composite oxides can be 100/mm2More than.
In the Mn-Nb-Cr composite oxides, the ratio between score (K2) of the score (K1) of Mn and Cr and Nb (K1/K2) can
Think 0.1~1.0.
The method of manufacture enamel cold-rolled steel sheet of the invention may comprise steps of: manufacture is compound comprising Mn-Nb-Cr
The molten steel of oxide；Slab is cast using the molten steel；The slab is rolled, to manufacture steel plate；And it will be described
Steel plate is annealed.
The step of manufacturing the molten steel is the following steps are included: carry out deoxidation for the molten steel for completing converter refining；And it is passing through
Investment Mn, Cr and Nb in the molten steel of deoxidation is crossed, to form Mn-Nb-Cr composite oxides；It is multiple to form the Mn-Nb-Cr
The step of closing oxide can be successively to put into described Mn, Cr and Nb.
It may include the step of feeding MnO to silk when putting into the Mn.
Following molten steel can be manufactured in the step of manufacturing the molten steel, in terms of weight %, includes: C: more than 0 weight %
And 0.0015 below weight %, weight %, Al of Mn:0.2~0.4: more than 0 weight % and 0.001 weight % or less, P: more than 0
Weight % and 0.02 weight % or less, S: more than 0 weight % and 0.02 weight % or less, weight %, Nb of Cr:0.05~0.1:
0.03~0.05 weight %, N: more than 0 weight % and 0.002 weight % or less, the weight of O:0.02~0.04 %, surplus Fe and
The molten steel of other inevitable impurity.
Before the step of manufacturing the steel plate, may include 1200~1300 DEG C at a temperature of, by the slab into
Row heat treatment 1 hour the step of.
The step of manufacturing the steel plate may comprise steps of: the slab be carried out hot rolling, and at 800~900 DEG C
At a temperature of carry out hot finishing；550~700 DEG C at a temperature of, the steel plate Jing Guo hot rolling is wound；And with 75
The steel plate Jing Guo hot rolling is carried out cold rolling by~80% reduction ratio.
The step of annealing, can implement 20 seconds or more at 800~900 DEG C.
Invention effect
According to the present invention, make solid solution carbon (C) in steel and solid solution nitrogen (N) with NbC, NbN by adding niobium (Nb)
Form solid solution, so as to improve the processability of enamel cold-rolled steel sheet.In addition, the carbon and nitrogen in steel are removed to the maximum extent,
To minimize for the obstruction that dislocation is mobile in base material, and the input amount of the niobium of high price is minimized, so that it is guaranteed that economy
It can be improved mouldability simultaneously.
In addition, the fine emptying aperture of hydrogen can largely be adsorbed to improve hydrogen storage performance, so as to anti-by being formed in base material
Only because of the generation of scale explosion caused by the dissolution of hydrogen.At this moment, Mn-Nb-Cr composite oxides are formed in base material to improve
Brokenness, so as to form a large amount of fine emptying aperture.
Detailed description of the invention
Fig. 1 is the chart for showing the relationship of input amount and steel mouldability of Nb.
Fig. 2 is the chart for showing the relationship of input amount and fishscale resistance of Nb.
Fig. 3 is the electron scanning micrograph of the Mn-Nb-Cr composite oxides of the embodiment of the present invention.
Fig. 4 is the broken of the Mn-Nb-Cr composite oxides contained in the enamel cold-rolled steel sheet for show the embodiment of the present invention
The optical microscope photograph of broken state.
Fig. 5 be show the embodiment of the present invention manufacture enamel cold-rolled steel sheet method in formation Mn-Nb-Cr it is compound
The flow chart of the method for oxide.
Specific embodiment
In the following, the embodiment of the present invention is described in more details with reference to attached drawing.But the present invention is not limited
It in embodiments disclosed below, but can be realized with different various ways, these embodiments have been used for the purpose of
Site preparation discloses the present invention, and is provided to more completely inform invention scope to the technical staff with usual knowledge
's.In explanation, identical reference symbol is imparted for identical composition, and in order to accurately illustrate implementation of the invention
Example, a part of attached drawing may exaggerate its size, and the identical symbol in attached drawing indicates identical element.
For enamelled pressed steel, in order to ensure mouldability, ultra-low-carbon steel system substantially considerably less using the carbon (C) in steel
The cold-rolled steel sheet of column is as material.Also, the major way of the existing enamelled pressed steel using precipitate is, in order to refine
Remaining carbon (C) and nitrogen (N) are solid-solubilized in base material with the carbon such as TiC and TiN/nitride and add a large amount of Ti in steel process, with
Ensure the processability of enamelled pressed steel.It, can be in enamelled pressed steel but when being mixed into the TiN in molten steel and being exposed to the surface of enamelled pressed steel
Surface induce bubble shape blistering (Blister) defect.In addition, the Ti largely added can hinder enamelled pressed steel and ceramic glaze
Adhesiveness between the bed of material.In order to improve the problem of this Ti causes and use the oxide without Ti glassed steel series and
Speech, due to containing a large amount of oxygen and poor in processability in material.
In addition, being the manufacture work of enamelled pressed steel for the scale explosion of one of the defect of most serious of enamelled pressed steel
In sequence, when the hydrogen being solid-solution in steel is reduced to room temperature with the temperature of steel plate, due to the solubility of internal hydrogen difference and discharge
It is generated to the surface of steel.Therefore, scale explosion in order to prevent, it is necessary to which being formed in the inside of steel plate can largely adsorb
The space for the hydrogen being dissolved in steel.In general, the existing enamel steel grade using precipitate uses FeP, TiS, TiN, BN, cementite
(Cementite) etc. as storage hydrogen source.But the storage hydrogen source of this precipitate series is the atomic arrangement in precipitate and base material
Temporarily with H around crystal boundary between non-uniform precipitate and base material+The fixed hydrogen of state of atom, therefore, because external
Factor, the very small hydrogen atom of atomic radius will lead to the deviation for generating hydrogen storage performance, so as to cause mass deviation.
In this regard, utilizing Nb in the present invention, by adding Nb, by the solid solution C in steel plate and N is dissolved in the form of NbC, NbN
While solid solution, Mn-Nb-Cr composite oxides are formed in steel plate, it is excellent so as to provide mouldability and fishscale resistance
Enamel cold-rolled steel sheet.
The enamel cold-rolled steel sheet of the embodiment of the present invention may include in terms of weight %: C: more than 0 weight % and
0.0015 weight % or less, weight %, Al of Mn:0.2~0.4: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight
Measure % and 0.02 weight % or less, S: more than 0 weight % and 0.02 weight % or less, weight %, Nb:0.03 of Cr:0.05~0.1
~0.05 weight %, N: more than 0 weight % and 0.002 weight % or less, the weight of O:0.02~0.04 %, surplus Fe and other
Inevitable impurity, and may include Mn-Nb-Cr composite oxides.
In the following, to one of main feature of the invention addition constitute steel composition each alloying component the reasons why and it
Content range appropriate be illustrated.Wherein, the content of each ingredient indicates weight %.
Fig. 1 is the chart for showing the relationship between the input amount of Nb and the mouldability of steel, and Fig. 2 is the input amount for showing Nb
The chart of relationship between the fishscale resistance of steel.
C: more than 0 weight % and 0.0015 weight % or less
When adding C more than 0.0015 weight %, the amount for being dissolved carbon in steel it is more and in annealing obstruction texture at
It is long, to make mouldability reduce and generate aging phenomenon, so that surface occur when being processed after long-time after manufacture
A possibility that defect (stretcher strain (stretcher strain) defect), is high, therefore the upper limit value of C is limited to 0.0015 weight
Measure %.In addition, when C is more than 0.0015 weight %, it is also necessary to increase the additive amount of high valence elements Nb and economy can be reduced, because
This, is set as 0.0015 weight % for the upper limit of C.
The weight of Mn:0.2~0.4 %
The intensity that Mn can be in order to ensure steel plate, and be precipitated in order to which sulphur will be dissolved in steel with manganese sulfide, to prevent
Red shortness (Hot shortness) and add.Therefore, when the content of manganese is less than 0.2 weight %, the possibility of red shortness occurs
Property it is high, therefore the lower limit value of Mn is set as 0.2 weight %, when the content of manganese is more than 0.4 weight %, mouldability can be greatly reduced,
To which defect can occur at the time of molding, therefore the upper limit value of Mn is set as 0.4 weight %.In addition, compound forming Mn-Nb-Cr
When oxide, Mn is the element for forming initial stage Mn oxide (MnO), when Mn is less than 0.2 weight %, forms Mn oxide when institute
The Mn needed is insufficient, to form Mn oxide with can not be successfully, therefore the lower limit of Mn is set as 0.2 weight %.
The weight of Nb:0.03~0.05 %
Nb is element mostly important in the present invention, is to ensure mouldability so that a large amount of NbC, NbN precipitate is precipitated
While formed Mn-Nb-Cr composite oxides purpose and add.At this point, in order to make the Mn- in Mn-Nb-Cr composite oxides
The difference of Cr and Nb is reduced, and at least may include the Nb of 0.03 weight %.
When Nb is less than 0.03 weight %, although may insure fishscale resistance, mouldability can be reduced, when Nb is more than 0.05
When weight %, although the addition of Nb can improve processability, the oxygen in steel can be reduced, so that fishscale resistance can be reduced.
As described above, the optimum range in order to obtain Nb, by investigation according to the mouldability and fishscale resistance of the additive amount of Nb
Result be shown in Fig. 1 and Fig. 2.
With reference to Fig. 1 it is recognised that with Nb content in steel increase, the mouldability of steel is improved.But Nb is
High valence elements put into least Nb in order to ensure economy to ensure that mouldability is extremely important in industrial aspect.
With reference to Fig. 2 it is recognised that with Nb additive amount increase, fishscale resistance can be deteriorated.This is because having with oxygen affine
The increase of the additive amount of the Nb of power and reduce the oxygen of steel, to reduce the forming amount of composite oxides, therefore reduce
Fine emptying aperture (Micro Void), causes fishscale resistance to be deteriorated.Therefore, the additive amount of Nb is limited to ensure to form simultaneously
0.03~0.05 weight % of the range of property and fishscale resistance.
The weight of Cr:0.05~0.1 %
In the present invention, Cr is the important element for being only second to Nb, is added with improving the purpose of fishscale resistance.Cr be with
Mn-Nb oxide in conjunction with and form the indispensable elements of a large amount of Mn-Nb-Cr composite oxides.In order to ensure fishscale resistance, need
The Cr of 0.05 weight % or more is added, but when Cr is more than 0.1 weight %, mouldability can be deteriorated.
P: more than 0 weight % and 0.02 weight % or less
P is the element for hindering the physical property of steel, when P is more than 0.02 weight %, mouldability can be greatly reduced, therefore will
The upper limit value of P is set as 0.02 weight %.But it is almost impossible, therefore the lower limit of P is specific for completely removing the P in steel
For more than 0 weight %.
S: more than 0 weight % and 0.02 weight % or less
It is known that, conventionally, S is to hinder the element of the physical property of steel that extension can be greatly reduced when S is more than 0.02 weight %
Property, and it is easy to produce red shortness caused by sulphur, therefore the upper limit value of S is limited to 0.02 weight %.In addition, being formed by S
Sulfide be attached together to be formed with composite oxides, to oxide after rolling can be hindered broken and the fine emptying aperture that is formed
(micro-void) formation, or established fine emptying aperture can be filled, therefore reduce the content of S preferably as far as possible.But
It is the S completely removed in steel is almost impossible, therefore by the lower limit of S specifically for more than 0 weight %.
Al: more than 0 weight % and 0.001 weight % or less
Al is used as the deoxidier of the strength of the oxygen in removal molten steel, therefore the additive amount of Al is limited to 0.001 weight %
Below.When the Al in steel is more than 0.001 weight %, will form Al-Nb composite oxides rather than formed Mn-Nb-Cr it is compound
Oxide to can substantially reduce the amount of fine emptying aperture (micro-void) and keep enamel poor, therefore limits the input amount of Al.
But it is almost impossible for completely removing the Al in steel, therefore by the lower limit of Al specifically for more than 0 weight %.
N: more than 0 weight % and 0.002 weight % or less
The amount of added N is more, then mouldability is poorer, and it also requires increase the input amount of high-priced alloying element Nb,
Therefore the upper limit value of N is limited to 0.002 weight %.But it is almost impossible for completely removing the N in steel, therefore by N's
Lower limit is specifically for more than 0 weight %.
The weight of O:0.02~0.04 %
The amount of O is more, then fishscale resistance is more excellent, but when O is more than 0.04 weight %, mouldability can be deteriorated, therefore by O
Upper limit value be limited to 0.04 weight %.Also, when O is less than 0.02 weight %, it is used to form the O of Mn-Nb-Cr composite oxides
The lower limit of O so that fishscale resistance be made to be deteriorated, therefore is set as 0.02 weight % by deficiency.
During hot rolling and cold rolling with the enamel sheet of the invention formed as described above, Mn-Nb-Cr composite oxygen
Compound is broken and forms a large amount of fine emptying aperture (micro-void), thus with the H of molecular state2Gaseous state storage of hydrogen and simultaneously
It is not with H+State of atom storage of hydrogen, therefore can permanently storage of hydrogen, so as to prevent scale explosion.
Further, since use the Mn-Nb-Cr composite oxides of high temperatures as storage hydrogen source, therefore hardly by
To the influence of the control condition of hot rolling and cold rolling, so as to reduce mass deviation.
In the present invention, the breaking capacity of composite oxides when in order to increase hot rolling and cold rolling, can be used in steel Mn,
Nb and Cr forms polynary system complex oxide.In general, under identical depressing force, it is more compared with the oxide of single component
The breaking capacity of the oxide of ingredient system composition is more excellent.This is because when forming multicomponent system, according to the affinity with oxygen
Difference, the group in oxide is shaped to unevenly.That is, it is due at a high temperature of 1600 DEG C or so, in a very short period of time
Polynary system oxide is formed by the reduction reaction of oxide, therefore the time that oxide is integrally homogenised is inadequate.Cause
This, according at being grouped as and according to position in the oxide, with the hardness for the oxide unevenly formed that polynary system is formed
Can be different, therefore, compared with the oxide being formed uniformly by single component, in hot rolling and cold rolling, be easy to happen it is broken, from
And a large amount of three-dimensional fine emptying aperture (Micro Void) can be formed inside steel.
For 3 μm or more of Mn-Nb-Cr composite oxides used in the present invention, due in complex inclusion at
The different substrate iron of intensity and Mn-Nb-Cr composite oxides are broken and are formed a large amount of fine when dividing difference, hot rolling and cold rolling
Emptying aperture (Micro-void), to be used as storage hydrogen source.
Fig. 3 is the electron scanning micrograph of the Mn-Nb-Cr composite oxides of the embodiment of the present invention, and Fig. 4 is to show
The optical microphotograph of the broken state of the Mn-Nb-Cr composite oxides contained in the enamel cold-rolled steel sheet of the embodiment of the present invention
Mirror photo.
Fig. 3 shows the Mn-Nb-Cr composite oxides formed in casting process, and Mn-Nb-Cr composite oxides are with block
Form is formed.This Mn-Nb-Cr composite oxides are crushed during rolling slab and form plate as illustrated in figure 4
Type.Mn-Nb-Cr composite oxides form fine emptying aperture when broken around it, and the fine emptying aperture being thusly-formed may be used as steel
The space of hydrogen is store in plate.
In addition, for the enamel cold-rolled steel sheet of the embodiment of the present invention, for being observed with scanning electron microscope
500mm2Area when detected particle diameter be 1 μm or more non-metallic inclusion, pass through spectrum analysis method (Energy
Dispersive Spectrometry, EDS) composition analysis is carried out, so as to calculate Mn-Nb-Cr combined oxidation field trash
Group becomes simultaneously containing the composite oxides of Mn, Nb and Cr, and the diameter of field trash is scaled bowlder, and particle diameter is 3 μ
The score of Mn and Cr and Nb in the field trash of m or more.Wherein, the score of Mn and Cr is set as K1, when the score of Nb is set as K2,
Mn and the ratio between Cr and Nb (K1/K2) be indicate Mn in the Mn-Nb-Cr composite oxides with 3 μm or more of size and Cr with
The value of the distribution of Nb, value can be 0.1~1.0.When K1/K2 is less than 0.1, the size of composite oxides is smaller, and multiple
The composition for closing Nb in oxide accounts for major part, causes to break between the interface and substrate iron of composite oxides in rolling
It is broken and fine emptying aperture is made to tail off, to be unable to ensure fishscale resistance.On the other hand, when K1/K2 is more than 1.0 or more, composite oxygen
The content of Nb reduces and reduces breaking capacity in compound, is unable to fully the problem of ensuring fine emptying aperture to have.
In addition, every 1mm2Mn-Nb-Cr composite oxides quantity can be 100 or more.As every 1mm2Mn-Nb-
When the quantity of Cr composite oxides is less than 100, it is unable to fully ensure fine emptying aperture, therefore there is asking for reduction fishscale resistance
Topic.
In the following, being illustrated to the method for the manufacture enamel rolled plate of the embodiment of the present invention.
Fig. 5 be show the embodiment of the present invention manufacture enamel cold-rolled steel sheet method in formation Mn-Nb-Cr it is compound
The flow chart of the method for oxide.
The method of the manufacture enamel rolled plate of the embodiment of the present invention may comprise steps of: manufacture includes Mn-
The molten steel of Nb-Cr composite oxides；Cast slab；Slab is rolled, to manufacture steel；And annealing.
The step of manufacturing molten steel may comprise steps of: using vacuum deaerator plant, the molten steel for completing refining being passed through
Decarburization and carry out deoxidation；And Mn, Cr, Nb are put into the molten steel Jing Guo deoxidation, to form Mn-Nb-Cr composite oxides.
With reference to Fig. 5, the method for forming Mn-Nb-Cr composite oxides, which can be, first puts into Mn in the molten steel Jing Guo deoxidation,
It reacts it with oxygen remaining in molten steel and forms MnO (S10).At this moment, MnO is fed to silk, so as to form a large amount of MnO's
Meanwhile, it is capable to be evenly dispersed in molten steel.Later, Cr is put into restore MnO, so as to form Mn-Cr-O (S20).It connects
Investment Nb, so as to form Mn-Nb-Cr (S30) polynary system complex oxide.Mn, Cr and Nb are successively put into as described above
The reason of be, put into since the low ingredient of oxygen affinity, to form a large amount of Mn-Nb-Cr composite oxides.
Compared with the oxide of commonly used single component system, the polynary system Mn-Nb-Cr composite oxygen that is formed as described above
Compound is heavier, therefore, even if being formed in molten steel step, floating upper separation will not occur, to oxide-based be mingled with common
Object is compared, and can be remained in molten steel in large quantities.Furthermore, which is characterized in that do not put into the very high Al of the affinity of oxygen, with
Form a large amount of Mn-Nb-Cr composite oxides.Further, since can be omitted the input amount of Ti, thus with existing disclosed Ti system
The problem that well-known technique of glassed steel is compared, and a large amount of investments due to Ti are able to solve.
The molten steel so manufactured may include in terms of weight %: C: more than 0 weight % and 0.0015 weight % or less,
Weight %, Al of Mn:0.2~0.4: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight % and 0.02 weight % with
Under, S: more than 0 weight % and 0.02 weight % or less, weight %, Nb:0.03 of Cr:0.05~0.1~0.05 weight %, N: super
Cross 0 weight % and 0.002 weight % or less, the weight of O:0.02~0.04 %, surplus Fe and other inevitable impurity.
After manufacturing molten steel, molten steel can be transferred in continuous casting equipment and be cast into slab.It is cast using the molten steel
Slab be of identical composition with molten steel.
Casting slab after is fitted into heating furnace, then 1200~1300 DEG C at a temperature of can carry out be heat-treated 1 hour
The step of.
After the heat treatment for completing slab, slab can be rolled to manufacture steel plate.
Hot rolling can be carried out to the slab in heating furnace by heating to manufacture steel plate.At this point, hot finishing temperature can be with
It is 800~900 DEG C or so.When final rolling temperature is lower than 800 DEG C, rolling resistance when rolling is excessive, to reduce productivity, separately
On the one hand, when final rolling temperature is more than 900 DEG C, the oxide layer undue growth of hot-finished material, to reduce yield.It is therefore preferable that
Implement finish rolling at 800~900 DEG C.
For slab is carried out hot rolling and the steel plate that manufactures, wound using winder, winding temperature can for 550~
700 DEG C or so.At this moment, when winding temperature is set below 550 DEG C, the size of the crystal grain formed in steel plate becomes smaller, to can drop
Poor-compactibility.On the other hand, when winding temperature is more than 700 DEG C, excessive hot rolling oxide layer can be generated.It is therefore preferable that will receive
Rolling up limit temperature is 550~700 DEG C.
Later, the steel plate Jing Guo hot rolling is subjected to pickling processes, so that removal is formed in the oxide film on surface, and with 75
The cold rolling reduction ratio of~80% range implements cold rolling.At this moment, when cold rolling reduction ratio is less than proposed range, it is brilliant to reduce recrystallization
The growth of body tissue reduces steel to have to reduce mouldability, and Mn-Nb-Cr composite oxides can not be crushed completely
The problem of fine emptying aperture in plate.On the other hand, when cold rolling reduction ratio is greater than proposed range, ductility, and Mn- are reduced
Nb-Cr composite oxides are formed by fine emptying aperture when broken and are compressed, so that the absolute quantity of fine emptying aperture can be reduced, therefore
It is preferred that being 80% by the ceiling restriction of cold rolling reduction ratio.
By the way that steel plate is fitted into annealing furnace after hot rolling and cold rolling manufacture steel plate, and in 800~900 DEG C or so of temperature
Under, implement continuous annealing 20 seconds or more.
Continuous annealing process is in order to assign ductility and mouldability to the steel plate Jing Guo cold rolling, at this point, by annealing temperature
It when being set below 800 DEG C, does not complete to recrystallize and be difficult to ensure ductility and mouldability, on the other hand, when annealing temperature is super
When crossing 900 DEG C, scene needs excessive heating equipment, to actually be difficult to be heated, and excessively high temperature can be damaged
The durability degree of roller.It is therefore preferable that the range at 800~900 DEG C implements continuous annealing.In addition, when the time for implementing annealing is too short,
Also without completing recrystallization, therefore, it is difficult to ensure ductility and mouldability.
In the following, carrying out more specific description to the present invention by embodiment.It is to be noted, however, that following embodiments
Just for the sake of illustrating the present invention by illustrating, and the interest field being not meant to limit the present invention.This is because this hair
Bright interest field is content by recording in patent claims and thus the content of reasonable analogies is determined.
Implement converter-double refining-continuous casting working procedure, so that casting has the slab of composition as described in Table 1.This
When, the deoxidation by decarburization is carried out using vacuum deaerator plant in double refining process, then successively puts into Mn, Cr and Nb,
Form Mn-Nb-Cr composite oxides.Later, slab is kept for 1 hour in 1250 DEG C of heating furnace, then implements hot rolling, this
When hot finishing temperature be set as 900 DEG C, winding temperature is set as 650 DEG C, and final thickness is set as 3.2mm.For slab is carried out hot rolling
And the hot rolled steel plate manufactured carries out pickling processes and then implements cold rolling to remove the oxide film on surface.At this moment, cold rolling
Lower rate is set as 78%, to manufacture the cold-rolled steel sheet of 0.8mm thickness.
[table 1]
Later, in order to investigate enamel characteristics and mechanical property, processing cold-rolled steel sheet manufacture enamel processing test piece and stretching are tried
Then piece implements continuous annealing.
Enamel processing test piece is that cold-rolled steel sheet is cut to the size of 70mm × 150mm, is then implemented at 830 DEG C continuous
Annealing.Complete degreasing is carried out after completing annealing, is then coated with ground coat enamel glaze, and dries 10 minutes and completely removes at 200 DEG C
Moisture.It will complete dry test piece and keep 7 minutes at 830 DEG C to be cooled to room temperature after implementing firing processing.Complete ground coat enamel
In the test piece of enamel processing, it is coated with overglaze glaze again, is then dried 10 minutes at 200 DEG C and completely removes moisture.It will be complete
Kept at 800 DEG C at dry test piece 7 minutes it is air-cooled to implement to carry out after firing processing.At this moment, with regard to the atmosphere item of baking furnace
For part, dew-point temperature is set as 30 DEG C, to apply the exacting terms for being easiest to that scale explosion occurs.Later, will
The test piece for completing enamel processing is kept for 20 hours in 200 DEG C of holding furnace, accelerates processing squama quick-fried.
Later, the quantity for the scale explosion formed in test piece that detects by an unaided eye, and R-bar value is measured, then by mouldability
It is determined as 5 very excellent, excellent, general, poor, excessively poor stages, and is shown in Table 2.
In addition, utilizing the 500mm of each test piece of electron microscope observation2Area when, according to EDS analyze particle diameter be 1 μ
The composition of the non-metallic inclusion of m or more becomes the composite oxides containing Mn, Nb and Cr simultaneously using the group of field trash and incites somebody to action
The diameter of field trash is scaled the field trash that the particle diameter of bowlder is 3 μm or more, the distribution to Mn-Nb-Cr composite oxides
It is analyzed.Also, electron microscope is utilized, point count is passed through with the image in 40 visuals field under 5000 times
(pointcounting) quantity for measuring Mn-Nb-Cr composite oxides, uses image analyzer (imageanalyzer) later
It is scaled every 1mm2Quantity calculate.
[table 2]
With reference to above-mentioned table 2, the quantity and size of the Mn-Nb-Cr composite oxides of Examples 1 to 6, which belong in the present invention, to be limited
The range of system, therefore that also there is no squamas under severe conditions is quick-fried, ensures that fishscale resistance, and mouldability is also very
It is excellent.
On the other hand, the Al content of embodiment 7 is high and form Al2O3Field trash, and a part is formd as in table 1
The microinclusions Al-Nb containing Nb recorded causes hydrogen storage performance very low, produces from without forming fine emptying aperture
93 or more a large amount of squamas are quick-fried.Although the quantity of the Mn-Nb-Cr composite oxides of embodiment 8 belongs to and limits in the present invention
Range, but the content of Nb is low, therefore indicates that the value of the K1/K2 of the distribution of Mn-Nb-Cr composite oxides was shown and be higher than this hair
Bright middle limited range.Thus mouldability is also excessively poor, and the squama for also producing 23 or more is quick-fried.
In addition, in embodiment 9, although the distribution of Mn-Nb-Cr composite oxides and quantity belong to the model limited in the present invention
It encloses, but the content of Nb is higher, causes not favorably accomplishing the broken of Mn-Nb-Cr composite oxides when rolling, so as to store hydrogen
Fine emptying aperture it is few, therefore the squama for producing 46 or more is quick-fried.In embodiment 10, though the Nb containing 0.032 weight %, but drop
The content of the C of poor-compactibility is high, is 0.0042 weight %, therefore insufficient formability.
The preferred embodiment of the present invention is shown and is illustrated above, but the present invention is not limited to above-mentioned implementations
Example, in not departing from claims in the case where claimed purport of the invention, can thus implement various deformation and
Same other embodiments, this is to be understood that for the technical staff in fields of the present invention with usual knowledge
's.Therefore, technical protection scope of the invention should be determined according to patent claims.
Claims (10)
1. enamel cold-rolled steel sheet, in terms of weight %, it includes: C: more than 0 weight % and 0.0015 weight % or less, Mn:0.2
~0.4 weight %, Al: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight % and 0.02 weight % or less, S:
More than 0 weight % and 0.02 weight % or less, weight %, Nb:0.03 of Cr:0.05~0.1~0.05 weight %, N: more than 0 weight
Measure % and 0.002 weight % or less, the weight of O:0.02~0.04 %, surplus Fe and other inevitable impurity,
It and include Mn-Nb-Cr composite oxides.
2. enamel cold-rolled steel sheet according to claim 1, wherein 3 μm or more of the Mn-Nb-Cr composite oxides
Size be 100/mm2More than.
3. enamel cold-rolled steel sheet according to claim 1 or 2, wherein in the Mn-Nb-Cr composite oxides, Mn and
The ratio between the score (K2) of the score (K1) of Cr and Nb (K1/K2) is 0.1~1.0.
4. the method for manufacturing enamel cold-rolled steel sheet comprising following steps:
Manufacture includes the molten steel of Mn-Nb-Cr composite oxides；
Slab is cast using the molten steel；
The slab is rolled, to manufacture steel plate；And
The steel plate is annealed.
5. the method for manufacture enamel cold-rolled steel sheet according to claim 4, wherein the step of manufacturing the molten steel include
Following steps:
The molten steel for completing converter refining is subjected to deoxidation；And
Mn, Cr and Nb are put into the molten steel Jing Guo deoxidation, to form Mn-Nb-Cr composite oxides；
The step of forming the Mn-Nb-Cr composite oxides is successively to put into described Mn, Cr and Nb.
6. the method for manufacture enamel cold-rolled steel sheet according to claim 5, wherein when putting into the Mn, including will
MnO feeds the step of silk.
7. the method for manufacture enamel cold-rolled steel sheet according to claim 5 or 6, wherein in the step for manufacturing the molten steel
The following molten steel of manufacture includes in terms of weight % in rapid: C: more than 0 weight % and 0.0015 weight % or less, Mn:0.2~0.4
Weight %, Al: more than 0 weight % and 0.001 weight % or less, P: more than 0 weight % and 0.02 weight % or less, S: more than 0
Weight % and 0.02 weight % or less, weight %, Nb:0.03 of Cr:0.05~0.1~0.05 weight %, N: more than 0 weight % and
0.002 weight % or less, the weight of O:0.02~0.04 %, the Fe of surplus and other inevitable impurity molten steel.
8. it is according to claim 7 manufacture enamel cold-rolled steel sheet method, wherein the step of manufacturing the steel plate it
Before, including 1200~1300 DEG C at a temperature of, by the slab carry out heat treatment 1 hour the step of.
9. the method for manufacture enamel cold-rolled steel sheet according to claim 8, wherein the step of manufacturing the steel plate include
Following steps:
By the slab carry out hot rolling, and 800~900 DEG C at a temperature of carry out hot finishing；
550~700 DEG C at a temperature of, the steel plate Jing Guo hot rolling is wound；And
With 75~80% reduction ratio, the steel plate Jing Guo hot rolling is subjected to cold rolling.
10. the method for manufacture enamel cold-rolled steel sheet according to claim 9, wherein the step of annealing is 800
Implement 20 seconds or more at~900 DEG C.
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| WO2021193953A1 (en) * | 2020-03-27 | 2021-09-30 | 日本製鉄株式会社 | Steel plate and enamel product |
| CN116200670A (en) * | 2023-02-28 | 2023-06-02 | 鞍钢股份有限公司 | Cold-rolled enamelled steel sheet with excellent adhesion performance and manufacturing method thereof |
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|---|---|---|---|---|
| CN101517115A (en) * | 2006-09-19 | 2009-08-26 | 新日本制铁株式会社 | Works for enameling and enameled products |
| CN101535517A (en) * | 2006-09-27 | 2009-09-16 | 新日本制铁株式会社 | Enameling steel sheet highly excellent in unsusceptibility to fishscaling and process for producing the same |
| CN104894472A (en) * | 2015-05-22 | 2015-09-09 | 武汉钢铁(集团)公司 | Steel with high oxygen content and smelting method thereof |
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| MXPA04003464A (en) * | 2001-10-29 | 2005-09-08 | Nippon Steel Corp | Steel sheet for vitreous enameling excellent in workability and fish scale resistance, and method for producing the same. |
| KR101019225B1 (en) * | 2005-11-09 | 2011-03-04 | 신닛뽄세이테쯔 카부시키카이샤 | Steel sheet for continuous cast enameling with highly excellent unsusceptibility to fishscaling and process for producing the same |
| KR101289415B1 (en) * | 2009-12-18 | 2013-07-24 | 주식회사 포스코 | Enameling steel sheet with surface defect free and manufacturing method thereof |
| KR101353643B1 (en) | 2011-12-23 | 2014-01-21 | 주식회사 포스코 | Method for manufacturing porcelain anamel steel sheet having superior adhesion and fishscale resistance |
| KR101723349B1 (en) | 2013-09-10 | 2017-04-05 | 신닛테츠스미킨 카부시키카이샤 | Cold-rolled steel sheet for enameling, method for producing same, and enamel product |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101517115A (en) * | 2006-09-19 | 2009-08-26 | 新日本制铁株式会社 | Works for enameling and enameled products |
| CN101535517A (en) * | 2006-09-27 | 2009-09-16 | 新日本制铁株式会社 | Enameling steel sheet highly excellent in unsusceptibility to fishscaling and process for producing the same |
| CN104894472A (en) * | 2015-05-22 | 2015-09-09 | 武汉钢铁(集团)公司 | Steel with high oxygen content and smelting method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021193953A1 (en) * | 2020-03-27 | 2021-09-30 | 日本製鉄株式会社 | Steel plate and enamel product |
| JPWO2021193953A1 (en) * | 2020-03-27 | 2021-09-30 | ||
| JP7115653B2 (en) | 2020-03-27 | 2022-08-09 | 日本製鉄株式会社 | Steel plate and enamel products |
| CN116200670A (en) * | 2023-02-28 | 2023-06-02 | 鞍钢股份有限公司 | Cold-rolled enamelled steel sheet with excellent adhesion performance and manufacturing method thereof |
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