CN101052736A - Magnetic shielding steel sheet for color cathode-ray tube - Google Patents

Magnetic shielding steel sheet for color cathode-ray tube Download PDF

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CN101052736A
CN101052736A CNA2005800378724A CN200580037872A CN101052736A CN 101052736 A CN101052736 A CN 101052736A CN A2005800378724 A CNA2005800378724 A CN A2005800378724A CN 200580037872 A CN200580037872 A CN 200580037872A CN 101052736 A CN101052736 A CN 101052736A
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crystal grain
steel
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steel sheet
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山中庆一
吉田勤
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Nippon Steel Coated Sheet Corp
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Nippon Steel and Sumikin Coated Sheet Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14708—Fe-Ni based alloys
    • H01F1/14716—Fe-Ni based alloys in the form of sheets
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/02—Hardening by precipitation
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • 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
    • 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
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/867—Means associated with the outside of the vessel for shielding, e.g. magnetic shields
    • 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
    • C21D8/0236—Cold rolling
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A magnetic shielding steel sheet which has a chemical composition, in mass %, that C: 0.002 to 0.01 %, Si: 0.5 % or less, Mn: 2.0 % or less, P: 0.4 % or less, S: 0.001 to 0.1 %, Al: 0.001 to 2 %, N: 0.01 % or less, Ti: 0.01 % or less, V: 0.01% or less, Nb: 0.01 % or less, Cu: 0.4 % or less, Sn: 0.2 % or less, Ni: 0.1 % or less, Cr: 0.1 % or less, Mo: 0.1 % or less and B: 0.001 % or less, wherein inclusions contained in the steel sheet satisfy (1) MnO/(Al<SUB>2</SUB>O<SUB>3</SUB> + SiO<SUB>2</SUB> + MnO + CaO) = 0.5, (2) Al<SUB>2</SUB>O<SUB>3</SUB>/(Al<SUB>2</SUB>O<SUB>3</SUB> + SiO<SUB>2</SUB>+ MnO + CaO) = 0.1, and (3) the total amount of inclusions in the steel = 0.01 mass %, and wherein crystal grains have an average oblateness in the range of 0.15 to 0.5 with respect to a steel sheet having a cold rolled structure, and have average grain diameter of 15 to 40 m with respect to a steel sheet having an annealed structure. The above magnetic shielding steel sheet exhibits high magnetic permeability with stability even when it contains impurity elements originated from a scrap.

Description

Magnetic shielding steel sheet for color cathode-ray tube
Technical field
The present invention relates to magnetic shielding steel sheet for color cathode-ray tube.In more detail, the present invention relates to the magnetic shielding cold-rolled steel sheet of cold rolling (full hard) type of a kind of high rigidity or annealing soft, even when system steel part of raw materials is used steel scrap, it also can be stablized and guarantees high permeability.
Background technology
The basic structure of color cathode ray tube is to be made of electron beam gun that electron beam takes place and the face that makes electron beam become reflection.The side that it is inner is by preventing that the magnetic shielding that electron beam is partial to because of the effect of earth magnetism (magnetic shield member) from covering.The magnetic shielding of being disposed in this cathode tube is called as inner magnetic screen (inner magnetic shield) or only is called inner shield.In addition, the situation that shields (also being called: " external shield ") in the outer setting external magnetic of cathode tube is also arranged.In the present invention, the shielding of this inner magnetic shield and external magnetic is referred to as magnetic shielding.
The former material of magnetic shielding generally is the steel plate as thin as a wafer of thick 0.1～0.4mm.In the makers' workshop of motor, behind this former material steel plate extrusion molding, implement to be called as the thermal treatment that melanism is handled with 500～650 ℃ temperature, form by Fe at surface of steel plate 3O 4Behind the oxide film that constitutes, the leonard's tube of packing into.Carry out purpose that melanism handles be antirust, improve the thermoemitting rate, prevent electronics diffuse-reflectance etc.
In recent years, the maximization of its picture of family expenses TV, broadization and complanation are pushed into.Consequently, the electronics line that is taken place by electron beam gun is because of its travel distance and scan distance and become big, so be subjected to from influence of geomagnetic easily.That is, cause the electron rays of being partial to arrive the place of face by earth magnetism, the skew in the place that should arrive during than earth magnetism never becomes big (being called as geomagnetic excursion).Therefore, wish that in magnetic shielding this geomagnetic excursion is controlled.In addition, in the leonard's tube that the watch-dog of PC etc. is used, require more high-precision still frame, therefore must do one's utmost to suppress the colour cast that geomagnetic excursion causes.
From such reason, can prevent the colour cast that causes by geomagnetic excursion, magnetic shielding steel sheet effectively with high performance magnetic shield property with regard to strong request.In order to make the steel plate of this high magnetic properties, always carry out high-precision composition adjustment in the system steel stage.But, from the pairing social desirability of environmental problem in recent years, make every effort to advance the resources effective utilization, can predict the increase of the usage quantity of the iron and steel scrap in the system steel.If so, amount and the kind that then is also referred to as the impurity element that captures element (trap element) (sneaking into element) in the steel must increase.Therefore, become the manufacturing of steel that high-performance magnetism shields the high permeability of the former material difficulty that becoming.
About this problem, the spy open flat 11-92886 communique (below, claim patent documentation 1) in, proposition have with the ratio from the element of sneaking into of iron and steel scrap as capturing element be suppressed to a certain degree following after, in being called as the steel of inclusion, make Al again among the oxide compound with respect to whole inclusiones 2O 3Mass ratio more than 0.1.Same motion also appears at the spy and opens (hereinafter referred to as patent documentation 2) in the 2002-180214 communique.
But, in above-mentioned patent documentation 1 and 2, not to the Al in the steel 2O 3The amount of the influence of inclusion in addition and whole inclusiones is studied, and wherein is difficult to obtain the having steel plate of stablizing excellent magnetic properties in the content of only record.Therefore, also may not be the steel plate of high permeability even steel is formed identical, the productivity and the productivity of goods are low.
In magnetic shielding, according to its shape, place, purposes etc. are set, the steel plate of the hard type of the steel plate of the soft of excellent in workability and excellent strength is used respectively.For example, the magnetic shielding of the cathode rays of big picture this from manufacturing process the aspect and when having rigidity to require, use the steel plate of hard type usually.On the other hand, needing flange (rib) to add the steel plate that uses soft man-hour usually.But, in above-mentioned patent documentation 1,2, only put down in writing as-annealed condition or implemented the steel plate of the soft of slight skin-pass thereafter, and the not research of steel plate that improved the cold rolling type of high rigidity of intensity about after annealing, carrying out cold rolling.
Summary of the invention
The present invention complies with these requirements of the times of a large amount of consumption of iron and steel scrap, even the amount and the kind of a kind of increase impurity element are provided, and magnetic shielding cold-rolled steel sheet that still can the stabilized presentation high permeability.
The present invention provides a kind of magnetic shielding cold-rolled steel sheet in addition, it is for each type of steel plate with the steel plate of the soft with annealed structure of the cold rolling type of high rigidity with cold rolling microstructure, decision becomes the condition processing of high permeability, thereby all demonstrates good magnetic properties in any type.
Magnetic shielding cold-rolled steel sheet of the present invention, it is formed in quality %, contain C:0.002～0.01%, below the Si:0.5, below the Mn:2.0%, below the P:0.4%, S:0.001～0.1%, Al:0.001～2%, below the N:0.01%, and according to circumstances from following element, select more than a kind or 2 kinds: below the Ti:0.01%, below the V:0.01%, below the Nb:0.01%, below the Cu:0.4%, below the Sn:0.2%, below the Ni:0.1%, below the Cr:0.1%, Mo:0.1% is following with below the B:0.001%, and inclusion satisfies following formula (1)～(3).
MnO/(Al 2O 3+SiO 2+MnO+CaO)≤0.5……(1)，
Al 2O 3/(Al 2O 3+SiO 2+MnO+CaO)≤0.1……(2)，
Inclusion total amount in the steel≤0.01 quality % ... (3).
The surplus that steel is formed is Fe and impurity.
Steel plate except the condition of above-mentioned steel composition and inclusion, also needs crystal grain to satisfy following condition in order to demonstrate high permeability.
(A) have the situation of steel plate of the cold rolling type of high rigidity of cold rolling microstructure:
The average flat ratio of crystal grain is 0.15～0.5.Here, the average flat ratio of so-called crystal grain is defined as, by the thickness of slab cross section on the rolling direction of observation by light microscope steel plate, try to achieve therefrom with rolling direction be the average length L of crystal grain that go up to measure of vertical direction (thickness of slab direction) 2The average length L of determined crystal grain on the rolling direction to steel plate 1Ratio (L 2/ L 1).
(B) have the steel plate situation of the soft of annealed structure:
The average crystal grain of crystal grain directly is 15～40 μ m.
According to the present invention, even contain the steel plate of multiple capture element owing to sneaking into of iron and steel scrap when the system steel, still can stablize positively provides a kind of permeability magnetic shielding cold-rolled steel sheet high, the magnetic properties excellence.In addition, in the present invention, the steel plate of the soft of the high-intensity steel plate of the cold rolling type of high rigidity and excellent in workability no matter, therefore all can access the cold-rolled steel sheet of high permeability, can make magnetic shielding according to purposes, the shape of this shielding, cold-rolled steel sheet that the suitable kind of employing such as place is set.
Description of drawings
Fig. 1 (a) and (b) be explanation in the thickness of slab direction cross section of steel plate, measure the mode chart of method of mean length of the crystal grain of rolling direction and thickness of slab direction (with the vertical direction of rolling direction).
Embodiment
Magnetic shielding cold-rolled steel sheet of the present invention is suitable for inner magnetic screen, promptly is in the inside of color cathode spool, with the magnetic shielding that the mode that covers from the side is configured, also goes for external magnetism shielding with respect to the direction of passage of electron rays.
(1) steel is formed
Magnetic shielding steel sheet of the present invention, because the steel plate that imagination is to use a large amount of steel scraps to make as part of raw materials, so as follows, also to stipulate to sneak into the content of certain impurity element the steel from steel scrap.In the following description, unless the % that forms about steel specifies all is quality %.
The C amount: 0.002～0.01%, be preferably 0.002～0.005%
C is if increase than 0.01%, then can hinder the growth of crystal grain in the annealing operation that the manufacturing process of cold-rolled steel sheet carries out cold rolling after, so the reduction of the magnetic properties of steel plate.On the other hand, if being measured, extremely reduces C, then the productivity variation of steel plate until being lower than 0.002%.
Si amount: below 0.5%, be preferably below 0.3%
Si is improving aspect the rigidity of steel plate effectively, and aspect such as the fracture of the steel plate when preventing to anneal and magnetic shielding material fractureing when processing is effective.But, if Si too much contains, then since when melanism is handled to SiO 2Selective oxidation causes the oxide film of Fe to be difficult to form and get rusty easily, and also can have problems at the aspects such as absorption of electron rays.The Si amount of this boundary is 0.5%.
Mn amount: below 2.0%, be preferably below 1.0%
Mn can improve the steel plate rigidity.If Mn becomes too much, then have the problem of adding cost, so the Mn amount is below 2.0%.
P amount: below 0.4%, be preferably below 0.2%
P is also effective aspect raising steel plate rigidity.But surpass 0.4% if P exists, then in the manufacturing of steel plate, be easy to generate crackle owing to segregation.
The S amount: 0.001～0.01%, be preferably 0.002～0.007%
If S excessively exists, then fine sulfide increases in steel, hinders the growth of crystal grain during annealing in the manufacturing process of former material and magnetic properties is reduced.On the other hand, if under suitable billet heating temperature, add the S amount of appropriateness, then become the growth that big sulfide can not hinder crystal grain.The proper content of considering above S is 0.001～0.01%.
The Al amount: 0.001～2.0%, be preferably 0.001～1.0%
The Al that is dissolved in the steel is effective on raising steel plate rigidity.But if Al is too much, the Al in the inclusion then 2O 3Ratio become many and the forfeiture high permeability.On the other hand,, then be difficult to carry out the control of the O amount in the steel, hinder productivity if excessively reduce the Al amount.Consider that above proper content is 0.001～2.0%.Also have, the Al amount during so-called steel is formed is meant acid-solubility Al (so-called sol.Al) content.
N amount: below 0.01%, be preferably below 0.007%
N then produces expansion bug at surface of steel plate if surpass 0.01%.
Following element is to sneak into element the steel from steel scrap.These elements need not contain in the steel of magnetic shielding steel sheet of the present invention is formed.Therefore, the following of the content of these each elements is limited to 0%, only stipulates the upper limit of element as follows.
Ti, V, Nb amount: respectively below 0.01%
Ti, V, Nb all form carbide and oxide compound and make the permeability deterioration, therefore respectively below 0.01%.
Cu amount: below 0.4%
Cu is that engine copper cash from the scraped car iron and steel of for example automobile etc. is blended into the element in the steel.At blase furnace cast iron is that the Cu amount generally is lower than 0.005% in the existing ordinary steel composition of main body.If Cu is too much, then in the surface of steel plate multiviscosisty, part evaporation among leonard's tube changes tone with the face reaction.The Cu amount of this boundary is 0.4%.
Sn amount: below 0.2%
The galvanized iron scurf that Sn uses from pot for cooking rice etc. is blended into the steel.The Sn amount generally is lower than 0.001% in existing ordinary steel is formed.If becoming at most, Sn also can make the anti-finger printing deterioration in the makers' steel plate of motor is handled in surface densification.The Sn amount of this boundary is 0.2%.
Ni, Cr amount: respectively below 0.1%
In existing ordinary steel was formed, the Ni amount was lower than 0.005%, and the Cr amount is lower than 0.004%.Ni, Cr sneak into from stainless steel scrap.Element becomes many quality problem that all do not manifest arbitrarily, but is located at below 0.1% separately from the aspect of adding cost.
Mo amount: below 0.1%
If Mo increases then permeability and Coercive Force reduction.The Mo amount of this boundary is 0.1%.
B amount: below 0.001%
B then makes recrystallization temperature rise if exceedingly add, and produces problems such as steel plate overvulcanization.The B amount of this boundary is 0.001%.Preferred B amount is below 0.0003%.
(2) steel inclusion
In magnetic shielding steel sheet of the present invention,, be not only Al about steel inclusion 2O 3, also carried out following regulation about MnO and inclusion total amount.
MnO/(Al 2O 3+SiO 2+MnO+CaO)≤0.5……(1)
Al 2O 3/(Al 2O 3+SiO 2+MnO+CaO)≤0.1……(2)
Inclusion total amount in the steel≤0.01 quality % ... (3).
Inclusion total amount in the steel (the inclusion total amount is for the mass ratio of steel) has a significant impact magnetic properties, if this mass ratio increase magnetic properties deterioration then.Therefore the steel inclusion total amount is 1 * 10 -2% following (below=0.01%).Be preferably 7 * 10 -3% following (below=0.007%).
Except that the total amount of inclusion, the composition of inclusion is also influential to magnetic properties.At first, MnO/ (Al 2O 3+ SiO 2+ MnO+CaO) ratio (below be also referred to as the MnO ratio) has a significant impact magnetic properties, if this ratio increase magnetic properties deterioration then.The MnO ratio of this boundary is 0.5.In addition, Al 2O 3/ (Al 2O 3+ SiO 2+ MnO+CaO) ratio (below be also referred to as Al 2O 3Ratio) increase, magnetic properties also can deterioration.In addition, Al 2O 3Ratio is also influential to surface quality, and worst condition is also to be created in porose such problem on the steel plate when cold rolling.From the viewpoint of magnetic properties and surface quality, Al 2O 3Ratio is below 0.1.
(3) crystal grain
In cold-rolled steel sheet, crystal grain is flat flat pattern in the rolling direction attenuation that is stretched.If at its after annealing, then crystal grain recrystallizes, and generate new crystal grain, so the shape of crystal grain is no longer flat.Cold rolling as if after annealing, carrying out again, then be stretched by the newly-generated crystal grain of annealing, become flat once again.Therefore being shaped as of the crystal grain of steel, the not flat annealed structure of the crystal grain that the cold rolling microstructure that crystal grain is flat forms with the recrystallize that is brought by annealing is greatly different.Become flat as if being stretched by cold rolling crystal grain, then steel plate hardening becomes high strength.In the present invention, for cold rolling microstructure and annealed structure separately, stipulate the shape of crystal grain as follows in order to ensure good magnetic properties.
(3-1) cold rolling microstructure
For example the steel plate of the cold rolling type of image height hardness like this, in having the steel plate of crystal grain by the rolling cold rolling microstructure that is stretched, the average flat ratio of crystal grain is in 0.15～0.5 scope.This is cold rolling owing to carrying out after annealing, and when tissue became cold rolling microstructure, the flat degree of crystal grain can have influence on the magnetic properties after melanism is handled.That is, the average flat ratio of crystal grain of steel plate with cold rolling microstructure is bigger than 0.5, or phase inverse ratio 0.15 is little, can distinguish that all the permeability of the steel plate after melanism is handled reduces.Average flat ratio is preferably more than 0.15, below 0.45.
The average flat ratio of crystal grain exists with ... cold rolling degree (draft).Therefore, in having the magnetic shielding steel sheet of the present invention of cold rolling microstructure, making the cold rolling average flat ratio with the crystal grain after cold rolling that carries out after the annealing is that 0.15～0.5 such condition is carried out.The cold rolling draft that is used to satisfy the average flat ratio of this crystal grain is formed also different according to steel, therefore cannot treat different things as the same, and the draft cold rolling as target is preferably more than 25%.
Carried out the annealed steel plate and generally carried out skin-pass for the Flatness that shows steel plate.This skin-pass also is cold rolling a kind of.But in common skin-pass, can not produce the cold rolling microstructure of the average flat ratio of crystal grain with the present invention's regulation.
The average flat ratio of crystal grain can be tried to achieve by the thickness of slab cross section of the rolling direction of observation by light microscope steel plate as Fig. 1 (a) and (b).
If observe the thickness of slab cross section of the rolling direction of steel plate with cold rolling microstructure, then shown in Fig. 1 (a), observation be the crystal grain of the flat pattern that on rolling direction, is stretched.In the microscopic examination visual field in this thickness of slab cross section, shown in Fig. 1 (b), draw and have certain-length a 1The line A of first rolling direction 1-1, at this line A 1-1On calculate the number of crystal grain.Line A 1-1Length a 1The length that exists thereon with the crystal grain more than 10 serves as suitable.Then move, draw identical length a in the thickness of slab direction 1The line A of second rolling direction 1-2(not shown) calculates the number of crystal grain equally.This operation repeats n the line A until last rolling direction 1-nThe suitable value of n is more than 3.Calculate the length a of rolling direction by n time measured value 1On the mean value n of number of crystal grain 1The average length L of the crystal grain of rolling direction 1For
L 1＝a 1/n 1
Here, as n 1=rolling direction length a 1On n time mensuration of crystal grain number under mean value calculated.
Secondly, in the same microscopic examination visual field, draw and have certain-length a 2The first line A of thickness of slab direction (with the vertical direction of rolling direction) 2-1, at this line A 2-1On calculate the number of crystal grain.In cold rolling microstructure, because the length of the crystal grain of thickness of slab direction is littler than the length of the crystal grain of rolling direction, so the line A of thickness of slab direction 2-1Length a 2Also can be than the A of rolling direction 1-1Length a 1Short, but be that length more than 3/4 is advisable with respect to the thickness of slab of steel plate.Move in rolling direction, draw identical length a 2The line A of the second thickness of slab direction 2-2(not shown) calculates the number of crystal grain equally.The line limit line A of n thickness of slab direction is to the last repeatedly moved in rolling direction in this operation limit 2-n, by the length a of n time measured value calculating thickness of slab direction 2On the mean value n of number of crystal grain 2The average length L of the crystal grain of thickness of slab direction 2For
L 2＝a 2/n 2
Here, as n 2=thickness of slab direction length a 2On n time mensuration of crystal grain number under mean value calculated.
According to the L that so tries to achieve 1And L 2Value, the average flat ratio conduct of crystal grain
Average flat ratio=L 2/ L 1Calculated.
Therefore, the value of this flat ratio is more little, and it is high more that the crystal grain flatness becomes.For example so-called flat ratio 0.5 means that crystal grain is 2 times of length of plate in the length of rolling direction, and so-called flat ratio 0.15 means that crystal grain is about 6.7 times of length of thickness of slab direction in the length of rolling direction.
The average flat ratio of the crystal grain of so trying to achieve in the present invention, is more than 0.15, below 0.5.If the average flat ratio of crystal grain is in this scope, then the median size of crystal grain is not limited especially, for example can be more than the 50 μ m.Therefore owing to can select annealing conditions before cold rolling from wide in range scope, so, for example can adopt a few hours～tens of hours the general annealing conditions of soaking time.The preferable range of average flat ratio is more than 0.16, below 0.35.
(3-2) annealed structure
In the present invention, the so-called annealed structure meaning is to have the tissue of the crystal grain that forms again by the recrystallize in the annealing, but is subjected to skin-pass or cold rolling thereafter, and it is flat that crystal grain becomes slightly, but also comprise this average flat ratio still than 0.5 big tissue.
In the present invention, the median size of the crystal grain of annealed structure is in the scope of 15～40 μ m.The big big more steel plate magnetic properties of the median size of crystal grain is good more.But if become excessive, then when handling steel plate, can fracture easily and be difficult to handle.From magnetic properties and easy to handle viewpoint, distinguish that the scope in suitable average crystal grain footpath is the scope of 15～40 μ m.
In other words, flat ratio with crystal grain carries out recrystallization annealing so that the average crystal grain of crystal grain directly is the scope of 15～40 μ m than under the steel plate of the 0.5 big annealed structure situation of (this comprises the steel plate under the as-annealed condition and has been subjected to skin-pass thereafter or cold rolling steel plate that draft is lower).Such average crystal grain footpath for example just can access by the high temperature annealing of short period of time.Also can after annealing, implement skin-pass.The preferred scope in average crystal grain footpath at 20～40 μ m.
Average flat ratio with crystal grain is than the steel plate of 0.5 big annealed structure, as above-mentioned, if average crystal grain directly becomes and then fractures easily greatly than 40 μ m.With respect to this, in that to have aforesaid average flat ratio be below 0.5 and have under the situation of steel plate of cold rolling microstructure of flat crystal grain, even it is bigger than 40 μ m that average crystal grain directly becomes, because crystal grain is overlapped, steel plate still is difficult to fracture and the high strength that becomes, so the average crystal grain footpath also can surpass 40 μ m.
The median size of crystal grain (average crystal grain footpath) D, it is by same try to achieve illustrated with the measuring method of average flat ratio, according to the average length L of crystal grain determined on rolling direction 1Mean number n with crystal grain 1And the average length L of determined crystal grain in the thickness of slab direction (with the vertical direction of rolling direction) 2Mean number n with crystal grain 2, follow following formula and calculate.
D＝(2/π 1/2)×[(L 1×L 2)/(n 1×n 2)] 1/2。
Following embodiment has not a particle of and limits the meaning of the present invention with the purpose that is illustrated as of the present invention.
Embodiment 1
Vacuum refinement has the molten steel of the chemical constitution of the steel shown in table 1 (example of the present invention) and the table 2 (comparative example), and casting becomes steel ingot, with 1000 ℃ it is carried out hot rolling, makes the thick hot rolling (hot coil) of 2.3mm.The Al of the steel inclusion of each steel 2O 3/ (Al 2O 3+ SiO 2+ MnO+CaO) mass ratio (Al 2O 3Ratio) and MnO/ (Al 2O 3+ SiO 2+ MnO+CaO) mass ratio (MnO ratio) and inclusion total amount, press the interpolation order of alloying element to molten steel, promptly, make be in the period of adding Al by Si and Mn carry out the preceding of deoxidation and after whenever, or further control free oxygen amount after the deoxidation, adjust to the value shown in table 1 and the table 2 thus.
The hot rolling that the process hot rolling is obtained carries out being cold-rolled to 0.5mm after the pickling.This steel plate is annealed in nitrogen atmosphere with 650 ℃ of conditions, carry out cold rolling after the annealing again until 0.15mm by soaking in 24 hours.The cold-rolled steel sheet that so obtains all has average flat ratio and is in 0.15～0.50 the interior cold rolling microstructure of scope.The median size of the crystal grain that forms by recrystallize under this annealing conditions is generally in the scope of 20～50 μ m.
In order to estimate the magnetic shielding magnetic properties of each cold-rolled steel sheet, measure its permeability as follows.
Downcut annular test portion (external diameter 45mm, internal diameter 33mm) from each for the examination steel plate, implement to handle suitable thermal treatment (N with melanism 2In the atmosphere, 590 ℃ kept 15 minutes down) after, measure dc magnetizing characteristic, be to measure BH hysteresis curve (magnetzation curve) specifically.As an index of magnetic properties, in the BH hysteresis curve that external magnetic field strength Hm=28A/m is measured in test portion in outer, the value of the external magnetic field strength cutting peakflux density that adds thus as the relative permeability merge record in table.This value equals the value of relative permeability in cgs unit system.
[table 1] example of the present invention
Figure A20058003787200121
[table 2] comparative example
What be with underscore is outside the scope of the invention
As shown in table 1, concerning steel plate with cold rolling microstructure, the example of the present invention in the composition of the chemical constitution of steel and inclusion is in the scope of the present invention's regulation for the examination steel plate in, can access relative permeability 28A/m under above the magnetic properties of 1000 excellence.But if the content of B is than more than 0.003%, perhaps the inclusion total amount is above 7 * 10 -3%, then magnetic properties slightly reduces, and relative permeability is also low slightly than 1000.
With respect to this, as shown in table 2, in the confession examination steel plate that consists of extraneous comparative example of the present invention of steel composition or inclusion, though the average flat ratio of crystal grain within the scope of the invention, the remarkable step-down of relative permeability can not get excellent magnetic properties.
Embodiment 2
In the hot rolling of the thick 2.3mm that in embodiment 1, makes, use has the hot rolling of example of the present invention of the composition of the chemical constitution of the steel shown in the steel grade No.14 of table 1 and inclusion, for pickling, cold rolling, annealing, for the second time cold rolling for the first time, obtain the thick cold-rolled steel sheet of 0.15mm successively.Carry out under the identical conditions of annealing with soaking in 650 ℃, 24 hours.By cold rolling change thickness of slab for the first time, the flatness of the crystal grain after for the second time cold rolling is changed.Try to achieve resulting average flat ratio for the crystal grain that tries steel plate by above-mentioned method, its result is in being presented at table 3.
Press the method for embodiment 1 record, chemical constitution and the inclusion composition of measuring the steel that so obtains are identical within the scope of the invention, and the different relative permeability for the examination steel plate of the average flat ratio of crystal grain.Its result also merge record in table 3.
The chemical constitution of [table 3] steel is formed identical with the steel grade No.14 of table 1 with inclusion
Test No. The average flat ratio of crystal grain Specific permeability under the 28A/m Reference
1 0.49 1050 Example of the present invention
2 0.33 1230
3 0.27 1311
4 0.18 1215
5 0.55* 720 Comparative example
6 0.67* 670
7 0.12* 770
8 0.07* 752
* outside the scope of the present invention
As shown in Table 3, even the chemical constitution of steel and inclusion are organized all within the scope of the invention, but littler or bigger than 0.5 than 0.15 as if the average flat ratio of crystal grain, then relative permeability still significantly reduces.Promptly, in having the steel plate of cold rolling microstructure, in order to ensure the magnetic properties of excellence, only control the chemical constitution of steel plate and inclusion and form in the scope that makes it to be in the present invention's regulation still insufficiently, also need to carry out cold rolling and make the average flat ratio of crystal grain be in 0.15～0.5 scope.
Embodiment 3
Vacuum refinement has the molten steel of the chemical constitution of the steel shown in table 4 (example of the present invention) and the table 5 (comparative example), and casting becomes steel ingot, with 1000 ℃ it is carried out hot rolling, makes the thick hot rolling (hot coil) of 2.3mm.The Al of the steel inclusion of each steel 2O 3/ (Al 2O 3+ SiO 2+ MnO+CaO) mass ratio (Al 2O 3Ratio) and MnO/ (Al 2O 3+ SiO 2+ MnO+CaO) mass ratio (MnO ratio) and the inclusion total amount to the mass ratio of steel, press the interpolation order of alloying element to molten steel, promptly, make be in the period of adding Al by Si and Mn carry out the preceding of deoxidation and after whenever, or further control free oxygen amount after the deoxidation, thus it is adjusted to the value shown in table 4 and the table 5.
After the hot rolling that obtains through hot rolling carried out pickling, be cold-rolled to 0.15mm, under the condition of soaking in 20 seconds, in nitrogen atmosphere, carry out continuous annealing with 750 ℃, obtain having the recrystallization annealing tissue for the examination steel plate.Certainly, the crystal grain of each steel plate is non-flat, and the average flat ratio of its crystal grain substantially exceeds 0.50.Under the such annealing conditions of soaking in 750 ℃, 20 seconds, each steel grade of the median size of crystal grain satisfies among the present invention the condition for the average crystal grain footpath of annealed structure regulation all in the scope of 20～35 μ m.
Measure each for the relative permeability of examination steel plate under 28A/m according to the method for embodiment 1 record.Its as a result merge record in table 4 and table 5.
[table 4] example of the present invention
Steel grade No The chemical constitution of steel (quality %) The MnO ratio Al 2O 3Ratio Inclusion total amount mass% Specific permeability under the 28A/m
C Si Mn P S sol.Al N Ti V Nb Cu Sn Ni Cr Mo B
1 0.0073 0.02 0.38 0.36 0.010 0.005 0.004 0.004 0.007 0.005 0.08 0.03 0.03 0.04 0.023 0.0003 0.46 0.09 0.0043 1257
2 0.0054 0.21 0.24 0.22 0.010 0.004 0.003 0.007 0.006 0.002 0.09 0.03 0.07 0.10 0.050 0.0003 0.26 0.06 0.0062 1235
3 0.0063 0.27 0.31 0.02 0.001 0.006 0.009 0.002 0.003 0.002 0.07 0.02 0.02 0.03 0.051 0.0002 0.10 0.07 0.0039 1257
4 0.0057 0.25 0.46 0.25 0.006 0.009 0.010 0.009 0.004 0.005 0.06 0.03 0.04 0.04 0.016 0.0002 0.07 0.09 0.0012 1296
5 0.0025 0.46 0.41 0.02 0.009 0.008 0.010 0.001 0.002 0.009 0.08 0.02 0.05 0.04 0.004 0.0002 0.08 0.09 0.0026 1214
6 0.0040 0.32 0.26 0.35 0.009 0.005 0.003 0.008 0.007 0.004 0.03 0.07 0.07 0.06 0.047 0.0002 0.25 0.07 0.0022 1288
7 0.0090 0.03 0.43 0.31 0.010 0.005 0.001 0.002 0.003 0.008 0.08 0.01 0.09 0.09 0.027 0.0002 0.38 0.04 0.0024 1226
8 0.0067 0.05 0.11 0.03 0.003 0.008 0.003 0.010 0.010 0.004 0.02 0.07 0.07 0.04 0.053 0.0002 0.05 0.09 0.0068 1245
9 0.0084 0.35 0.18 0.12 0.002 0.001 0.003 0.004 0.004 0.002 0.06 0.05 0.08 0.08 0.044 0.0002 0.17 0.01 0.0053 1226
10 0.0045 0.07 0.11 0.14 0.008 0.008 0.003 0.003 0.001 0.006 0.04 0.09 0.04 0.08 0.049 0.0002 0.46 0.07 0.0052 1306
11 0.0028 0.11 0.38 0.06 0.007 0.003 0.005 0.002 0.004 0.006 0.05 0.07 0.07 0.05 0.050 0.0002 0.39 0.10 0.0068 1228
12 0.0096 0.29 0.19 0.28 0.008 0.007 0.009 0.010 0.001 0.001 0.04 0.04 0.06 0.08 0.012 0.0001 0.44 0.08 0.0069 1248
13 0.0075 0.42 0.32 0.38 0.008 0.001 0.002 0.003 0.007 0.003 0.06 0.01 0.08 0.10 0.043 0.0002 0.09 0.04 0.0050 1266
14 0.0053 0.44 0.38 0.02 0.009 0.001 0.009 0.002 0.002 0.009 0.09 0.02 0.08 0.03 0.027 0.0001 0.17 0.08 0.0031 1288
15 0.0076 0.38 0.13 0.07 0.010 0.006 0.003 0.008 0.005 0.003 0.10 0.03 0.02 0.03 0.046 0.0003 0.46 0.02 0.0061 1304
16 0.0025 0.05 0.22 0.07 0.004 0.009 0.003 0.002 0.002 0.007 0.03 0.04 0.04 0.05 0.036 0.0001 0.48 0.03 0.0053 1230
17 0.0094 0.44 0.25 0.37 0.007 0.009 0.007 0.009 0.007 0.002 0.10 0.07 0.01 0.05 0.014 0.0001 0.21 0.04 0.0082 951
18 0.0022 0.24 0.17 0.10 0.007 0.008 0.003 0.002 0.010 0.010 0.02 0.02 0.10 0.05 0.044 0.0002 0.44 0.07 0.0098 968
19 0.0047 0.19 0.42 0.23 0.002 0.004 0.006 0.003 0.006 0.005 0.02 0.09 0.02 0.06 0.009 0.0005 0.49 0.03 0.0060 983
20 0.0098 0.29 0.47 0.29 0.004 0.001 0.002 0.004 0.009 0.010 0.02 0.06 0.06 0.03 0.028 0.0010 0.37 0.08 0.0068 963
[table 5] comparative example
Steel grade No The chemical constitution of steel (quality %) The MnO ratio Al 2O 3Ratio Inclusion total amount mass% Specific permeability under the 28A/m
C Si Mn P S so.Al N Ti V Nb Cu Sn Ni Cr Mo B
21 0.0142 0.41 0.30 0.16 0.003 0.004 0.009 0.005 0.001 0.002 0.07 0.05 0.05 0.05 0.030 0.0002 0.03 0.05 0.0041 596
22 0.0137 0.05 0.48 0.34 0.007 0.001 0.010 0.006 0.008 0.010 0.04 0.06 0.02 0.05 0.051 0.0002 0.22 0.07 0.0037 624
23 0.0095 0.13 0.43 0.35 0.0007 0.010 0.004 0.010 0.002 0.003 0.02 0.04 0.03 0.07 0.034 0.0002 0.32 0.05 0.0011 681
24 0.0089 0.43 0.22 0.33 0.0003 0.006 0.007 0.009 0.008 0.008 0.06 0.09 0.04 0.05 0.004 0.0003 0.38 0.07 0.0048 624
25 0.0036 0.35 0.31 0.19 0.005 3.7 0.007 0.009 0.004 0.005 0.08 0.07 0.09 0.03 0.027 0.0002 0.05 0.02 0.0018 635
26 0.0028 0.38 0.46 0.03 0.005 2.5 0.004 0.006 0.008 0.006 0.01 0.07 0.03 0.04 0.026 0.0002 0.29 0.05 0.0062 690
27 0.0053 0.22 0.14 0.12 0.003 0.007 0.010 0.018 0.002 0.003 0.04 0.06 0.03 0.04 0.027 0.0002 0.30 0.09 0.0038 669
28 0.0093 0.18 0.35 0.07 0.009 0.008 0.002 0.033 0.005 0.007 0.06 0.02 0.09 0.07 0.016 0.0001 0.06 0.09 0.0039 654
29 0.0091 0.24 0.19 0.26 0.010 0.009 0.009 0.009 0.021 0.002 0.02 0.03 0.09 0.04 0.010 0.0001 0.19 0.10 0.0065 608
30 0.0074 0.03 0.18 0.34 0.003 0.008 0.005 0.002 0.015 0.004 0.10 0.01 0.02 0.06 0.051 0.0001 0.07 0.05 0.0052 631
31 0.0026 0.18 0.49 0.12 0.005 0.009 0.007 0.003 0.010 0.017 0.08 0.01 0.01 0.03 0.056 0.0003 0.09 0.03 0.0063 645
32 0.0048 0.30 0.47 0.17 0.007 0.008 0.006 0.003 0.006 0.027 0.07 0.02 0.04 0.02 0.035 0.0002 0.04 0.07 0.0020 674
33 0.0053 0.46 0.38 0.09 0.005 0.004 0.008 0.007 0.008 0.002 0.03 0.07 0.10 0.05 0.27 0.0001 0.34 0.04 0.0023 629
34 0.0037 0.14 0.11 0.39 0.006 0.010 0.007 0.009 0.009 0.004 0.03 0.09 0.03 0.06 0.22 0.0002 0.04 0.01 0.0038 694
35 0.0042 0.31 0.35 0.37 0.003 0.008 0.002 0.003 0.007 0.010 0.06 0.09 0.09 0.03 0.029 0.0030 0.26 0.09 0.0037 626
36 0.0081 0.11 0.20 0.38 0.002 0.004 0.003 0.009 0.002 0.009 0.02 0.07 0.03 0.05 0.029 0.0017 0.11 0.10 0.0027 584
37 0.0062 0.31 0.49 0.01 0.003 0.008 0.008 0.007 0.005 0.003 0.07 0.01 0.09 0.09 0.021 0.0001 0.77 0.01 0.0018 614
38 0.0044 0.48 0.30 0.27 0.006 0.002 0.003 0.007 0.004 0.001 0.04 0.03 0.03 0.09 0.015 0.0002 0.62 0.04 0.0054 648
39 0.0009 0.12 0.35 0.32 0.002 0.006 0.001 0.009 0.001 0.009 0.10 0.02 0.03 0.05 0.023 0.0001 0.35 0.22 0.0030 655
40 0.0096 0.34 0.25 0.20 0.009 0.009 0.002 0.006 0.007 0.006 0.02 0.03 0.02 0.02 0.014 0.0001 0.36 0.34 0.0024 593
41 0.0057 0.32 0.17 0.21 0.004 0.008 0.005 0.008 0.009 0.009 0.05 0.04 0.07 0.04 0.020 0.0001 0.12 0.01 0.0209 701
42 0.0048 0.07 0.11 0.03 0.009 0.002 0.002 0.004 0.010 0.004 0.05 0.01 0.01 0.06 0.003 0.0002 0.12 0.01 0.0114 620
The numerical value of band underscore is outside the scope of the invention
As shown in table 4, even have crystal grain and be under the situation of steel plate of non-flat recrystallization annealing tissue, the chemical constitution of steel and the composition of the inclusion example of the present invention in the scope of the present invention regulation in the examination steel plate, still can access relative permeability 28A/m under above the magnetic properties of 1000 excellence.But, if the content of B than more than 0.003% or the inclusion total amount above 7 * 10 -3%, then magnetic properties slightly reduces, and relative permeability is also low slightly than 1000.
With respect to this, as shown in Figure 5, steel form or the composition of inclusion be in extraneous comparative example of the present invention for the examination steel plate in, though the median size of crystal grain is within the scope of the invention, the remarkable step-down of relative permeability can not get excellent magnetic properties.
Embodiment 4
In the hot rolling of the thick 2.3mm that in embodiment 3, makes, use has the hot rolling of example of the present invention of the composition of the chemical constitution of the steel shown in the steel grade No.10 of table 4 and inclusion, carry out cold rollingly after the pickling, implement continuous annealing in the nitrogen of soaking in 20 seconds with the different temperature shown in the table 6 afterwards up to 0.15mm.Try to achieve each median size of crystal grain by above-mentioned method for the examination steel plate, its result at merge record in table 6.
Press the method for embodiment 1 record, chemical constitution and the inclusion composition of measuring the steel that so obtains are identical within the scope of the invention, and the different relative permeability for the examination steel plate of the median size of crystal grain.Its result also merge record in table 6.
The chemical constitution of [table 6] steel is formed identical with the steel grade No.10 of table 4 with inclusion
Test Mo Annealing temperature (℃) Average crystal grain footpath (μ m) Specific permeability under the 28A/m Reference
1 660 15 970 Example of the present invention
2 700 18 1112
3 720 20 1190
4 750 27 1306
5 800 34 1750
6 900 39 2190
7 650 12* 780 Comparative example
8 630 10* 630
* outside the scope of the invention
As shown in Table 6, even the chemical constitution of steel and inclusion are organized all within the scope of the invention, but littler than 15 μ m as if the median size of crystal grain, then relative permeability still significantly reduces.Promptly, under the situation of the average flat ratio with crystal grain than the steel plate of 0.5 big, the tissue that constitutes by non-crystal grain flat or that flatness is little, magnetic properties in order to ensure excellence, only control the chemical constitution of steel plate and inclusion and form in the scope that makes it to be in the present invention's regulation still insufficiently, also need to anneal and average crystal grain directly is in more than the 15 μ m.

Claims (4)

1. color cathode spool magnetic shielding cold-rolled steel sheet, it is characterized in that, it is formed in quality %, contain C:0.002～0.01%, below the Si:0.5%, below the Mn:2.0%, below the P:0.4%, S:0.001～0.1%, Al:0.001～2%, below the N:0.01%, Ti:0～0.01%, V:0～0.01%, Nb:0～0.01%, Cu:0～0.4%, Sn:0～0.2%, Ni:0～0.1%, Cr:0～0.1%, Mo:0～0.1%, and B:0～0.001%
And the inclusion in the steel satisfies following formula (1)～(3):
MnO/(Al 2O 3+SiO 2+MnO+CaO)≤0.5……(1)，
Al 2O 3/(Al 2O 3+SiO 2+MnO+CaO)≤0.1……(2)，
Inclusion total amount in the steel≤0.01 quality % ... (3),
And, have from any tissue: (a) the average flat ratio L of crystal grain as selecting the undertissue 2/ L 1Be the cold rolling microstructure in 0.15～0.5 the scope, wherein, L 2Be the average crystal grain length with the vertical direction of rolling direction, L 1Be the average crystal grain length on the rolling direction of steel plate; Reaching (b), average crystal grain directly is the interior annealed structure of scope of 15～40 μ m.
2. magnetic shielding cold-rolled steel sheet according to claim 1 is characterized in that B content is below 0.0003%.
3. magnetic shielding cold-rolled steel sheet according to claim 1 and 2 is characterized in that, the inclusion total amount in the steel is below 0.007 quality %.
4. magnetic shielding cold-rolled steel sheet according to claim 1 and 2 is characterized in that the value of the relative permeability under the 28A/m is bigger than 1000.
CNA2005800378724A 2004-11-11 2005-11-08 Magnetic shielding steel sheet for color cathode-ray tube Pending CN101052736A (en)

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