CN1325665C - Coating composition, and method for manufacturing high silicon electrical steel sheet using thereof - Google Patents

Coating composition, and method for manufacturing high silicon electrical steel sheet using thereof Download PDF

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CN1325665C
CN1325665C CNB2003801005093A CN200380100509A CN1325665C CN 1325665 C CN1325665 C CN 1325665C CN B2003801005093 A CNB2003801005093 A CN B2003801005093A CN 200380100509 A CN200380100509 A CN 200380100509A CN 1325665 C CN1325665 C CN 1325665C
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steel plate
coating composition
annealing
steel sheet
sheet
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CN1692165A (en
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崔圭升
禹宗秀
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Posco Holdings Inc
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Posco Co Ltd
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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
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1255—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

There are provided a coating composition for siliconizing, and a method for manufacturing a high silicon electrical steel sheet using the same. The coating composition includes: a Fe-Si-based composite compound sintered powder having a grain size of - 325 mesh and containing 20 - 70 % silicon by weight; and a colloidal silica solution containing 15 - 30 part by weight of silica solid matter with respect to 100 part by weight of the sintered powder.

Description

Coating composition and this coating composition of use are made the method for high silicon electrical steel sheet
Technical field
The present invention relates to be used for the coating composition that electrical sheet is handled in silication (siliconizing), with the method for using described coating composition manufacturing electrical sheet, more specifically, the present invention relates to a kind of be used for by diffusion annealing process effectively the siliconizing electrical sheet coating composition and by using this coating composition manufacturing to have the method for the high silicon electrical steel sheet of outstanding high-gradient magnetism and outstanding power frequency characteristic.
Background technology
Usually electrical sheet is divided into grain-oriented electrical steel sheet and non-oriented electromagnetic steel sheet.Grain-oriented electrical steel sheet contains 3% silicon (Si) and has the crystallographic texture of grain orientation for { (110) [001] }.Its excellent magnetic along rolling direction can make the core material of above-mentioned grain-oriented electrical sheet as transformer, engine, generator and other electronics.Non-oriented electromagnetic steel sheet is characterised in that grain orientation is irregular alignment, and the magnetic deflection of direction of magnetization is little.Because these features, non-oriented electromagnetic steel sheet is mainly used in the iron core of rotating machine such as generator or engine, and wherein magnetic flux direction changes.
Recently, the kind of electrical equipment increases, and the requirement in the high frequency band operation improves to equipment simultaneously, thereby for the increase in demand of the core material with good high-gradient magnetism.
Meanwhile, in the Fe-Si alloy, because higher silicone content can cause hysteresis loss, magnetostriction, coercive force and magneticanisotropy in the core loss property to reduce and the maximum permeability raising, therefore high silicon steel product is considered to good soft magnetic material.The raising of silicone content can't cause the unlimited raising of magnetostrictive unlimited reduction and maximum permeability, but shows maximum value in 6.5% silicon steel.And well-known, the magnetic of 6.5% silicon steel reaches maximum value at high frequency and high power frequency wave band.Because its excellent magnetic at high frequency band, high silicon steel is mainly used in the high frequency reactor of gas turbo-generator, box power supply (tank power supply), inductance heating installation, uninterruption power source etc. and electroplates the high-frequency transformer of power supply, electroplating equipment wielding machine, the power supply of X-ray etc., and just is used as the equivalent material of silicon crystal grain oriented steel.In addition, high silicon steel can be used for reducing the energy consumption of engine and the efficient of raising engine.
Yet,, therefore may surpass 3.5% silicon steel sheet by cold rolling manufacturing silicone content hardly because the elongation of silicon steel sheet can sharply reduce along with the increase of silicone content in the Fe-Si steel.Although higher silicone content helps to obtain good magnetic, make above-mentioned high silicon steel sheet and be subjected to cold rolling restriction.Therefore, long ago people have just attempted overcoming the research of the novel substitute technology of cold rolling restriction.
Prior art as high silicon steel sheet manufacture method, Japanese Patent prospectus No.S56-3625 etc. discloses the direct casting of the high silicon steel sheet that uses single roller or two rollers, Japanese Patent prospectus No.S62-103321 etc. discloses the hot rolling method of carrying out under the heated condition of proper temperature, Japanese Patent prospectus No.H5-171281 etc. disclose at high silicon steel be in inside, low-silicon steel is in compound the rolling (cladrolling) of carrying out under the outside state.Yet above-mentioned prior art does not all also have commercialization.
For producing the high silicon steel product such as 3% non orientating silicon steel product in batches, in the prior art of Japanese Patent prospectus No.S62-227078, U.S. Patent No. 3,423,253 grades, already known processes may further comprise the steps: use SiCl 4With the surface of siliceous deposits, make the silicon homogenization by chemical vapor deposition method then at material.Yet because the difficulty of CVD technology, above-mentioned product manufactured price must be higher 5 times than 3% common silicon steel product.Although the product of above-mentioned manufacturing has good magnetic, the said products is difficult to promote and commercialization.
Equally, EP1052043A2, JP2000192204, JP2000144248, JP200045025 etc. disclose and have used powder metallurgy to make the technology of high silicon steel sheet.Yet, the shortcoming of these prior aries be high silicone content can not make have the expectation thickness steel plate.
In addition, United States Patent (USP) 3,634,148, United States Patent (USP) 4,073,668 grade proposes long term annealing technology, wherein prepares independent Fe-Si powdered alloy, or the mix powder of Fe-Si powder and tackiness agent, mix powder is rolling with the shrinkage less than 5%, long term annealing then.Yet, with powder coated to body material and the technology that applies the operation of rolling then be difficult to carry out cold rolling, be not suitable for manufacturing system in batches equally.Equally, consider productivity, low-temperature annealing is not suitable for making in batches for a long time.
In the electrical sheet of current circulation, has only siliceous 6.5% non-oriented electromagnetic steel sheet as high silicon steel production and sale.Because the irregular alignment of its crystal grain can produce magnetic biasing with the orientation of direction of magnetization when siliceous 6.5% non-oriented electromagnetic steel sheet is used for rotor.But the high silicon grain-oriented electrical steel sheet that has excellent properties when being used for transformer does not also have commercialization, wherein only uses the magnetic of steel plate along rolling direction.Therefore, people have carried out various manufacturings and have had the trial of the grain-oriented electrical steel sheet of excellent magnetic because of high silicon content, but also do not have this product that produces of success.
Disclosure of the Invention
Therefore, the present invention is exactly in order to make great efforts to solve the above-mentioned problems in the prior art.
The purpose of this invention is to provide by the diffusion annealing process coating composition of siliconizing electrical sheet effectively.
Another object of the present invention provides the method for making the high silicon electrical steel sheet with outstanding high-gradient magnetism, and it is by carrying out diffusion annealing on the surface that coating composition is coated in electrical sheet and to the coating steel plate, thereby electrical sheet is carried out siliconizing.
As the detailed description of the invention and general introduction, for achieving the above object with other advantage and purpose according to the invention, the invention provides coating composition, it comprises: Fe-Si is the complex chemical compound sintered powder, the silicon that it has-325 purpose granularities and comprises 20-70wt%; And colloidal-silica solution, it comprises the silica solid material of counting the 15-30 weight part with the sintered powder of 100 weight parts.
In one aspect of the invention, provide the method for making high silicon electrical steel sheet, it may further comprise the steps: the coating composition of above-mentioned preparation is coated on the surface of the steel plate that comprises 2.0-3.3wt%Si and dry; The exsiccant steel plate is carried out diffusion annealing at least in 1000-1200 ℃ temperature range in the nitrogen atmosphere that comprises 20% hydrogen.
In the present invention is aspect another, the method for making high silicon grain-oriented electrical steel sheet is provided, it may further comprise the steps: heat and hot rolling steel billet are made hot-rolled steel sheet again; To through hot rolled steel plate annealing and cold rolling, regulate the thickness of steel plate to carrying out through the annealed steel plate; To described steel plate decarburizing annealing; With described steel plate is carried out secondary recrystallization annealing, improved method further may further comprise the steps: the surface of the grain-oriented electrical steel sheet that secondary recrystallization handles is wherein finished in pickling, removes oxide layer; Be coated on the electrical sheet surface of pickling above-mentioned coating composition and drying; With in the nitrogen atmosphere that contains at least 20% hydrogen, in 1000-1200 ℃ temperature range, the exsiccant electrical sheet is carried out diffusion annealing.
In another aspect of the present invention, the method for making high silicon non-oriented electrical steel plate is provided, comprising following steps: heat and hot rolling steel billet are made hot-rolled steel sheet again; Hot-rolled steel sheet is annealed and the annealed steel plate carried out the thickness of cold rolling adjusting steel plate; To carrying out recrystallization annealing through cold rolling steel plate, improved method further may further comprise the steps: be coated on cold rolling surface of steel plate above-mentioned coating composition and drying; In the nitrogen atmosphere that comprises at least 20% hydrogen, in 1000-1200 ℃ temperature range, the exsiccant electrical sheet is carried out diffusion annealing.
Preferred embodiment
The present invention is described hereinafter.
Siliceous (Si) metal contacts with ferrous metal in surpassing 950 ℃ high-temperature hydrogen or nitrogen, and inter-diffusion reaction will take place, inter-diffusion reaction takes place, wherein Siliciumatom diffuses into ferrous metal, and iron atom diffuses into siliceous metal, thereby the concentration of both sides iron and silicon is equated.Therefore, when the silicon metal-powder contacted with the surface of electrical sheet and subsequently this electrical sheet carried out high temperature annealing, the silicon concentration difference caused inter-diffusion reaction, and wherein Siliciumatom diffuses into ferrous metal, and the iron atom of steel plate diffuses in the powder.
When comparing the inter-diffusion reaction of iron atom and Siliciumatom, because in the rate of diffusion of 1000-1200 ℃ of Siliciumatom than the rate of diffusion of iron atom fast 2 times approximately, therefore the phenomenon of Ke Kendaer effect (Kirkendall) effect will take place to be referred to as accordingly with non-homogeneous diffusion attitude.This non-homogeneous diffusion attitude causes the heterogeneous state defective or produces the various compounds that make the magnetic variation in reaction interface, such as FeSi 2, FeSi, Fe 5Si 3And Fe 3Si.Therefore, by contain Si powder and during in high temperature diffusion annealing, can not make high silicon grain-oriented electrical steel sheet applying on the electrical sheet with even composition.
For addressing the above problem, the inventor uses silica flour and iron powder that diffusion principle etc. has been carried out research repeatedly, find that at last the defective in the diffusion reaction part can remove effectively, its be not include only silica flour by use coating composition as the silication agent, be that the coating composition of complex chemical compound is as the silication agent and be to use Fe-Si.Therefore the inventor has proposed the present invention.
In other words, silication coating composition provided by the invention and use it to make the method for electrical sheet.The composition of coating composition allows to carry out such diffusion, Si atom and the equivalent replacement each other of Fe atom when promptly wherein also annealing then on the surface that applies electrical sheet with coating composition, formation causes the complex chemical compound of the Fe-Si bonding of steel surface diffusion reactive moieties generation surface imperfection hardly.
The following specifically describes the monotechnics of the control Si atomic diffusion amount that adopts among the present invention.
The first, for the rate of diffusion of the Si component that further slows down, do not use the powder that only comprises the Si metal, and use the main composition of the Fe-Si based compound of Si metal and Fe metal link, described Fe-Si based compound such as FeSi as the silication coating-forming agent 2, FeSi, Fe 5Si 3And Fe 3Si.For this purpose, that is, be that sintered powder exists as compound in order to make Fe-Si, the Si content that the present invention limits powder is at most 70wt%.
Second, in order to suppress the diffusion of Si atom, making Fe-Si is that the granularity of sintered powder is very thin, is that the sintering fine powder is coated on the surface of steel plate with Fe-Si, thereby reduce the surperficial contact area between body material and the metal-powder, the area that promptly interacts is at most 30% to contacting to compare with plate.Particularly, to limit Fe-Si be that the granularity of sintered powder is for-324 orders in the present invention.
The 3rd, Fe-Si in order to ensure as above preparation is the bonding of annealing powder and substrate material surface, with the coating property of the powder of guaranteeing to anneal, add the tackiness agent of white rouge particle as coating composition, its size is equivalent to colloidal particle and has very excellent dispersiveness in water.
At last, as Fe-Si when to be sintered powder be coated on the surface of steel plate then at high temperature annealing with pulpous state, pilot-gas of the present invention makes to form thin oxide film on surface of steel plate.This surface film oxide plays the effect of the barrier film of inter-diffusion reaction, spreads to body material to suppress the Si atom.
At first, specifically describe siliconizing coating composition of the present invention.
As the Fe-Si of silication coating composition main component of the present invention is that the manufacturing of powder is as follows: iron powder and silica flour are mixed with each other, and with mixed powder in the mixed-gas atmosphere of hydrogen and nitrogen in 1000-1200 ℃ temperature range sintering 3-5 hour, but must not be limited to this, can be by the several different methods manufacturing.At this moment, the component ratio of sintered powder compound changes along with the change of the amount of blended iron powder and silica flour.In theory, when the blended amount is 50%Si+50%Fe, produce compound F 17-hydroxy-corticosterone eSi 2When the blended amount is 34%Si+66%Fe, produce compound F 17-hydroxy-corticosterone eSi; When the blended amount is 25%Si+75%Fe, produce compound F 17-hydroxy-corticosterone e 5Si 3With when the blended amount is 14%Si+86%Fe, produce compound F 17-hydroxy-corticosterone e 3Si.Yet, in the sintering of reality, may have a spot of several compound according to initial mixed state.Particularly, when the mixing of sintering reaction by iron powder and silica flour produced, reaction was in this way carried out, promptly Si atom and Fe atom mutually mutual diffusion invade.Therefore, though the amount of Si is big slightly, sintered powder becomes wherein most of FeSi that is 2The state of compound or FeSi compound is equivalent on the surface that the Fe atom has been diffused into sintered powder, and pure Si atom is present in sintered powder inside.Therefore, there is the Fe-Si based compound on the surface of most of sintered powders.
In the present invention, the Fe-Si that more than obtains is that the silicone content in the sintered powder is limited in 20-70wt%.If silicone content is less than 20wt%, it is too little, makes rate of diffusion very slow.Simultaneously, the high-density of sintered powder may cause that the dispersiveness when manufacturing location carries out coating processes descends.Because it is FeSi that silicone content makes the main component of existence when surpassing 70wt% 2With extra metal Si mixture mutually, metal Si component contact substance surface to increase the possibility that produces defective in the siliconizing technological process from the teeth outwards, may be difficult to control silicone content when making silication.In other words, Fe-Si is that silicone content is the scope of 20-70wt% in the sintered powder by restriction, and might make Fe-Si is the complex chemical compound sintered powder, and it has FeSi 2, FeSi, Fe 5Si 3Or Fe 3Si is as main component.Be FeSi in the complex chemical compound more preferably at Fe-Si 2+ FeSi content is at least 90wt% in the annealing total weight of powder.
Equally, when preparation the invention described above Fe-Si is sintered powder, preferably in sintering and process for cooling process, form thin oxide film on the surface at sintered powder.Be somebody's turn to do the rate of diffusion of thin oxide film control silicon in diffusion annealing reaction subsequently, thereby suppress generation of defects in the substrate material surface, and can obtain having the product of excellent magnetism energy.
More preferably, oxygen level is limited in being at most 2.0% in the surface oxide film that forms.This is to cause the rate of diffusion of silicon too slow because oxygen level surpasses 2.0%.
Simultaneously, for coating property and the surface shape of improving body material among the present invention, preferably in the coating composition of above preparation, add ultra-fine SiO 2Powder, alumina powder and alumina sol.
More preferably, adding is selected from thin SiO 2At least a amount in powder, alumina powder and the alumina sol is that sintered powder is counted the 0.2-3.5 weight part with the Fe-Si of above-mentioned granularity of having of 100 weight parts and composition.If less than 0.2 weight part, making, add-on adds improving a little less than the effect of causing.If add-on surpasses 3.5 weight parts, because too much coated weight may make the surface properties variation.
When the Fe-Si that as above makes is a sintered powder when being used as the coating-forming agent of electrical sheet, this powder is made into pulpous state, and by using roller coating machine to be coated on the surface of steel plate, it is most economical in the manufacturing stage then.Fe-Si as the silication agent is that sintered powder should be thin as far as possible, and it increases the coating processibility in manufacturing stage, and is favourable to the surface shape of control diffusion reaction.Yet, since sintering reaction when finishing Fe-Si be that sintered powder is the frit state by high temperature and long-time reaction, the granularity that is necessary to control powder is thin as far as possible.
Therefore, under the circumstances, the invention enables Fe-Si is that the granularity of sintered powder is thin.Thinner crystal grain helps coating property.Preferably, consider the productivity and the cost that form fine powder, notice that granularity should be limited to-325 orders.
Simultaneously, the Fe-Si that considers as above preparation is the practical coating performance of sintered powder and to the control of the diffusing capacity of the Si that applies, and powder dissolution is made slurries in solvent, then with the slurries of preparation as coating composition.
For solvent, use colloidal-silica solution.At this moment, silicon components is the ultra-fine SiO with colloidal state size 2Particle.Because these ultra-fine SiO 2Particle is dispersed in the water, when they mix use with other solids, can increase the processibility of viscosity to guarantee to apply of slurries.
In the present invention, be to add the silicon dioxde solution of forming by 15-30 weight part silica solid material in the powder preferably to per 100 weight part Fe-Si.If add-on is less than 15 weight parts, because the Tension Difference between coating composition and the body material fracture surface, coating composition shows serious surface and splits, and it is poor to make with the adhesion of substrate material surface.If amount surpasses 30 weight parts, coating property is poor, and the rate of diffusion of silicon is too slow in the technology that homogenizes subsequently, needs long term annealing, and this is undesirable.
The method of using coating composition to make electrical sheet is described below.
The present invention makes high silicon electrical steel sheet, and it is by being coated to above-mentioned coating composition by the ordinary method manufacturing and comprising on the electrical sheet of silicon (silicon that preferably comprises 2.0-3.3wt%) of predetermined content.In other words, above-mentioned coating composition is coated in non-oriented electromagnetic steel sheet surface and the surface of the grain-oriented electrical steel sheet made by ordinary method on, high temperature annealing then, thus make high silicon electrical steel sheet.
[oriented electrical steel]
The manufacture method of grain-oriented electrical steel sheet may be with manufacturers's difference slightly.Yet this method generally includes following steps: regulate the component in the system steel; Make steel billet from molten steel; The heat again of steel billet; Hot rolling is through hot again steel billet; To hot-rolled steel sheet annealing with the annealed steel plate is carried out cold rolling, regulate the thickness of steel plate; To steel plate decarburizing annealing; Steel plate is carried out the high temperature annealing of secondary recrystallization; With final coating insulating film.Yet, the invention is not restricted to above-mentioned concrete manufacture method and process.For example, method of the present invention can be omitted the hot-roll annealing step, or can be used for comprising the manufacture method of decarburizing annealing with the electrical sheet of nitriding step.
The product of aforesaid method manufacturing has by glassy membrane (formal name used at school forsterite, 2MgOSiO 2) and the double membrane structure formed of the insulating film that in high-temperature annealing process, forms.Equally, the product that does not contain glass coating is arranged, wherein in high-temperature annealing process, add special additive, the formation of glass coating is suppressed, and on base layer, forms insulating film to form base layer.
In the present invention, the coating composition with above-mentioned composition can be coated on the surface of the conventional grain-oriented electrical steel sheet of having finished secondary recrystallization, and obtain basic magnetic property thus.In other words, purpose of the present invention can comprise that all that finished the grain-oriented electrical steel sheet product of secondary recrystallization, as the high temperature annealing steel plate, do not contain the steel sheet product of glass coating and be formed with the steel sheet product of duplicature on it.
Though the grain-oriented electrical steel sheet as parent material of the present invention comprises the Si component basically, but can comprise in addition necessary metal or non-metallic element as Mn, Al, S, N etc. as described in the auxiliary agent of manufacture method, but described additive is not only limited to above-mentioned concrete component.The oriented electrical steel that is coated with coating composition more preferably comprises the Si that counts 2.9-3.3wt% with the weight of steel plate itself.
In the present invention, remove by cleanup acid treatment at the surface film that carries out forming on the secondary recrystallization annealed steel plate, the coating composition that will have an above-mentioned composition by roller coating machine is coated on the steel plate then.At this moment, the coated weight that is coated in the coating composition on the steel plate preferably passes through following formula 1 and 2 decisions:
Y-5≤coated weight≤Y+5--------formula 1
Y (g/m 2)=7650t (x1-x2)/(A-14.4)---Shi 2
Wherein " t " is body material thickness, and A is the silicone content (%) in the Fe-Si system annealing powder, and x1 is the target silicone content (%) of body material, and x2 is the initial Si content of body material.
Therefore, the steel plate that scribbles coating composition is preferably at 200-700 ℃ temperature range inner drying.If drying temperature is lower than 200 ℃, then time of drying oversize, productivity is reduced.If drying temperature surpasses 700 ℃, may on surface of steel plate, produce oxide compound.
Then, the steel plate that drying is crossed joins in the annealing furnace and diffusion annealing.At this moment, the restriction annealing temperature is 1000-1200 ℃ of scope.If annealing temperature is less than 1000 ℃, then siliconizing speed is too slow, makes diffusion time long and the surface shape silicification reaction border is coarse, and makes the magnetic property variation thus.If annealing temperature surpasses 1200 ℃, then speed of reaction is too fast, makes the surface adhering of coiling steel coil strip, makes to separate the processibility variation.
Therefore, consider the surface shape and the processibility on border, preferably limiting the diffusion annealing temperature is 1050-1200 ℃.
Equally, in the present invention, need control shielding gas in the diffusion annealing step process is the nitrogen atmosphere that comprises at least 20% hydrogen.This is because if hydrogen richness less than 20%, forms thin and fine and close SiO on body material 2Be oxide compound, hinder silicification reaction, if partly there is the Al component, thereby AlN is precipitated out and makes the rapid variation of core loss in the cooling then after annealing.
The preferred restriction diffusion annealing time is 1-10 hour, if the diffusion annealing time less than 1 hour, then silication amount is little, if the diffusion annealing time was above 10 hours, then silication amount is too much, is difficult to implement suitable control, and undue reaction for a long time may make the surface shape variation of body material.
Simultaneously, can on the surface of silication steel plate, form insulating coating again.
This insulating coating forms by ordinary method; wherein in mixed phosphate by a small amount of chromic acid (chroicacid) being mixed into magnesium (Mg), aluminium (Al) and calcium (Ca) and the colloidal silica component and apply and form insulating coating; or forming insulating coating by applying the organic/inorganic composite coating-forming agent, described organic/inorganic composite coating-forming agent has chromic salt and acryl resin as the drawability main ingredient.Yet the present invention is not only limited to the concrete composition of above-mentioned insulating coating agent.
[non-oriented electromagnetic steel sheet]
The manufacture method of non-oriented electromagnetic steel sheet can be slightly different with manufacturers, basic manufacture method or purposes.Yet this method generally includes following steps: regulate the component in the system steel; Make steel billet from molten steel; The heat again of steel billet; Hot rolling is through hot again steel billet; To hot-rolled steel sheet annealing with the annealed steel plate is carried out cold rolling, regulate the thickness of steel plate; To carrying out recrystallization annealing through cold rolling steel plate; With final coating insulating film.Depend on manufacture method, Si content or magnetic property level, the manufactured and sale of product of multiple non-oriented electromagnetic steel sheet is arranged at present.
In the present invention, the body material that applies above-mentioned coating composition in the above is for by the cold rolling cold-rolled steel sheet that obtains in the non-oriented electromagnetic steel sheet manufacturing step.Apply cold-rolled steel sheet with coating composition, then at high temperature annealing, to have high silicon content.At this moment, preferred cold-rolled steel sheet comprises the Si that counts 2.0-3.3wt% with the weight of steel plate itself.This is that this is uneconomic because if it is that silicification reaction time of powder is long that Si content, uses Fe-Si as the silication agent less than 2.0%, if Si content above 3.3%, then steel plate becomes fragile, and makes the non-constant of cold rolling ability.
In the present invention, the coating composition that will have an above-mentioned composition by roller coating machine is coated on the surface of preparation steel plate.
So, before the applying coating composition, it is ideal that cold-rolled steel sheet is carried out process annealing.But by implement to heat up and in the process annealing stove of continuous operation to the cold-rolled steel sheet thermal treatment that homogenizes, the texture of body material is improved, thereby induces the optimization of initial magnetic property.Equally, by suitably controlling the annealing atmosphere condition in the process annealing, formation has fayalite (Fe in siliconizing step process subsequently 2SiO 4) as the thin and fine and close oxide film of main component, and as Fe-Si being the Si diffusion of components of sintered powder inhibition Fe in body material the time 3Si is the barrier layer of intermediate phase compound formation, and therefore, surface shape is that surfaceness improves, and thus, compares with using the silication of identical Si component, and magnetic property improves.
At this moment, to be 950-1100 ℃ be ideal to restriction process annealing temperature.If the process annealing temperature is lower than 950 ℃, then to texture to improve effect insufficient, if temperature surpasses 1100 ℃, be difficult to operating device.
Equally, preferred process annealing the nitrogen atmosphere that comprises at least 50% hydrogen carry out and regulate humid atmosphere with dew point oxidation capacity (PH as a reference 2O/PH 2) in the 0.06-0.30 scope.In comprising the atmosphere that is lower than 50% hydrogen, be difficult to controlled oxidation ability and the total oxygen content that is included in the oxide compound.Equally, if PH 2O/PH 2Surpass the 0.06-0.30 scope, then hydrogen atmosphere can not form fayalite.
In the present invention, the total oxygen content that is contained in the oxide layer of process annealing steel plate of expectation controlling packet is 210-420ppm.If total oxygen content less than 210ppm, then suppresses Fe 3The generation of the promptly middle defective phase of Si might be insufficient, if oxygen level surpasses 420ppm, then forms lot of F eO oxide film on fayalite.
In the present invention, when the coating composition that will have above-mentioned composition by roller coating machine is coated on the surface of cold-rolled steel sheet or on the surface of process annealing steel plate the time, the coated weight of preferred coatings composition is by following formula 1 and 2 decisions:
Y-5≤coated weight≤Y+5--------formula 1
Y (g/m 2)=7650t (x1-x2)/(A-14.4)---Shi 2
Wherein " t " is the thickness of body material, and A is that Fe-Si is the Si content (%) in the powder, and x1 is the target Si content (%) of body material, and x2 is the initial Si content of body material.
Thus, the steel plate that is coated with coating composition is preferably at 200-700 ℃ temperature range inner drying.If drying temperature is lower than 200 ℃, then time of drying oversize, productivity is reduced.If drying temperature surpasses 700 ℃, may on surface of steel plate, produce oxide compound.
Then, the steel plate that drying is crossed joins in the annealing furnace and diffusion annealing (homogenizing).At this moment, the restriction annealing temperature is 1000-1200 ℃.If annealing temperature is lower than 1000 ℃, then siliconizing speed is too slow, makes diffusion time surface shape long and the silicification reaction border coarse, thereby makes the magnetic property variation.If annealing temperature surpasses 1200 ℃, then speed of reaction is too fast, coils the surface adhering of steel coil strip, makes to separate the processibility variation.
Therefore, consider the surface shape and the processibility on border, preferably limit the diffusion annealing temperature in 1050-1200 ℃ of scope.
Equally, in the present invention, the gas that is necessary to control in the diffusion annealing step process is the nitrogen atmosphere that comprises at least 20% hydrogen.This is because if hydrogen richness is lower than 20%, forms thin and fine and close SiO on body material 2Be oxide compound, silicification reaction is hindered, if partly there is the Al component, then in the cooling after annealing, AlN precipitates, thereby makes the rapid variation of core loss.
The preferred restriction diffusion annealing time is 1-10 hour.If the diffusion annealing time, then silication amount was little less than 1 hour, if the diffusion annealing time surpasses 10 hours, then the siliconizing amount is too much, is difficult to carry out suitable control, and undue reaction for a long time may make the surface shape variation of body material.
Then, on the surface of silication steel plate, form insulating coating, thereby make final non-oriented electromagnetic steel sheet product.In other words, remove the not reactive material that remains on the silication surface of steel plate and last the coating has chromic salt and the acryl resin organic/inorganic composite coating-forming agent as main ingredient, thereby make final high silicon non-oriented electrical steel panel products.Yet, the invention is not restricted to the concrete composition of insulating coating agent.
Simultaneously, in the present invention, as above the coating composition of Zu Chenging can be applied to final non-oriented electromagnetic steel sheet product and above-mentioned cold-rolled steel sheet under these conditions naturally.Yet,, need independent annealing process if when coating composition is used to the finished product.Therefore, aspect the omission manufacturing step, it more preferably uses the cold-rolled steel sheet conduct matrix steel plate of applying coating composition in the above.
Hereinafter, by embodiment the present invention is described more specifically.Very natural, following embodiment should not be understood that it is restriction to the technology of the present invention scope.
Embodiment 1
The manufacture method of the grain-oriented electrical steel sheet by routine, preparation grain-oriented electrical steel sheet product, each product has thickness separately to be 0.23mm and to comprise Si:3.05wt%, Mn:0.12wt%, Cu:0.025wt%, Cr:0.13wt%, P:0.013wt%, and remaining is Fe and the impurity that comprises inevitably.Remove on the surface of steel plate of as above preparation and after the insulation layer that forms, use the slurries coated steel plates, described slurries are that sintered powder is dispersed in the colloidal-silica solution and forms by the Fe-Si that will have different grain size as shown in table 1 and composition.
Simultaneously, the solvent colloidal-silica solution of using is 30% colloidal-silica solution product of public offering.At this moment, the Fe-Si with 100 weight parts is that powder mixes with the colloidal-silica solution of 20 weight parts (with solid matter as a reference).
Being coated with Fe-Si is steel plate drying under 400 ℃ temperature of powder, and rolls into large-scale steel coil strip after visual observation applies state.Rolling steel plate homogenized 4 hours in 1125 ℃ of nitrogen atmospheres that comprising 50% hydrogen.Then, remove and remain on the unreacting substance on the steel plate when silicification reaction is finished and observe condition of surface.After this, the insulating coating agent that will be wherein a small amount of chromic acid be joined in the mixture of the phosphoric acid salt of magnesium (Mg), aluminium (Al) and calcium (Ca) and colloidal silica component is coated on the steel plate, form the insulating coating film, thereby make the grain-oriented electrical steel sheet that is formed with insulating coating on it.
Detect the Si content and the magnetic property of the product of as above making.Detect magnetic property by the monolithic measuring apparatus, i.e. core loss and magneticflux-density (B8), the result is as shown in following table 1.In this article, W10/50 represents that frequency is the core loss that 50Hz and magnetic strength should be 1.0 teslas, respectively, W10/400 represents that frequency is the core loss that 400Hz and magnetic strength should be 1.0 teslas, and W5/1000 represents that frequency is the core loss that 1000Hz and magnetic strength should be 0.5 tesla.Magneticflux-density B8 represents the magnetic flux that per unit area produces when being subjected to the magnetizing force of 800A commentaries on classics/m, and body material Si content is the end value of wet-way analysis.
Table 1
Numbering The Fe-Si powder The coating state Magnetic property Condition of surface Body material Si (%)
Si(％) Granularity (order) B8 (tesla) W10/50 (W/Kg) W10/400 (W/Kg) W5/100 0(W/Kg)
1 12 -325 Well 1.88 0.32 7.3 8.7 Well 3.7
2 25 -325 Well 1.79 0.30 6.7 7.4 Well 4.3
3 45 -325 Well 1.71 0.27 6.0 6.7 Well 5.8
4 62.5 -325 Well 1.69 0.26 5.8 6.4 Well 6.2
5 75 -325 Well 1.57 0.35 7.9 8.6 Aperture 7.4
6 85 -325 Well 1.55 0.36 8.2 9.4 The hole 7.9
7 100 -325 Well 1.52 0.38 8.8 10.9 The hole 8.5
8 50 -150～ +150 Thin 1.73 0.32 7.1 7.9 Defective 4.9
9 50 -250～ +250 Inhomogeneous 1.71 0.32 6.9 7.5 Defective 5.2
10 50 -325 Well 1.70 0.27 6.1 6.4 Well 5.9
11 50 -450 Well 1.70 0.26 6.0 6.4 Well 6.0
As seen from Table 1, control Fe-Si has the electrical sheet 2 to 4,10 of suitable silicone content and 11 silicone content increase in the sintered powder, and shows excellent core loss character at high frequency band and power frequency wave band band thus.Equally, they show excellent coating state.
Therefore by contrast, silicone content is too little after Fe-Si is electrical sheet 1 silication that silicone content is little in the sintered powder, to the weak effect that improves of magnetic property.In the situation that comprises the electrical sheet 5 to 7 that is at least 70%Si,, produce defective such as hole, so the magnetic property of steel plate dies down because silicone content is big.
In the situation of electrical sheet 8 and 9, when applying as pulpous state, it is not in size range of the present invention, they are thin and in uneven thickness, therefore the silicone content in the steel plate is little, and observe many defectives on the surface of steel plate, its expression quality is low relatively, the very little and magnetic property variation to the improvement of magnetic property.
Embodiment 2
Steel billet is warm again under 1220 ℃ temperature, each steel billet comprises Si:2.9wt%, Mn:0.022wt%, Al:0.3wt%, Sn:0.025wt%, P:0.003wt%, C:0.0025wt%, S:0.0011wt%, N 0.0003wt%, all the other are Fe and unavoidable impurities, and hot-rolled steel sheet is made in hot rolling then.Make hot-rolled steel sheet in 1000 ℃ of annealing five minutes and pickling.Be after final thickness is 0.20mm with the hot rolled cold-rolling of steel plate, removing and be coated in its lip-deep rolling oil.
Fe-Si with composition as shown in table 2 is sintered powder disperses formation in colloidal-silica solution the molten coated steel plates of slurries.Colloidal-silica solution used herein is 30% a colloidal-silica solution product of public offering.At this moment, to the Fe-Si of 100 weight parts be the colloidal-silica solution of mixed 20 weight parts (as a reference) in the powder with solid matter.
Being coated with Fe-Si is steel plate drying under 400 ℃ temperature of powder, and visual observation applies state.Then, the exsiccant steel plate is rolled into large-scale steel coil strip.The diffusion annealing 4 hours in 1125 ℃ of nitrogen atmospheres that comprising 50% hydrogen of rolling steel plate.Then, remove the unreacting substance that remains on when silicification reaction is finished on the steel plate, and observe condition of surface.After this, apply and to have chromic salt and acryl resin organic/inorganic composite coating-forming agent, thereby make the non-oriented electromagnetic steel sheet that is formed with insulating coating in the above as main ingredient.
In the product of as above making, detect Si content and magnetic property, and as shown in the following Table 2.The judgement criteria of specific nature is with embodiment 1.
Table 2
Numbering The Fe-Si powder The coating state Magnetic property Condition of surface Body material Si (%)
Si(％) Granularity (order) B8 (tesla) W10/50 (W/Kg) W10/40 0(W/Kg) W5/100 0(W/Kg)
1 12 -325 Well 1.46 0.80 11.45 11.06 Well 3.5
2 25 -325 Well 1.38 0.72 10.24 10.01 Well 4.2
3 50 -325 Well 1.32 0.64 9.14 8.98 Well 5.6
4 62.5 -325 Well 1.28 0.62 8.52 8.43 Well 6.0
5 75 -325 Well 1.23 0.71 11.02 11.23 The hole 6.8
6 85 -325 Well 1.21 0.73 11.11 11.52 The hole 7.1
7 100 -325 Well 1.20 0.74 11.36 12.02 The hole 7.7
8 50 -150～ +250 Thin 1.36 0.70 10.12 9.96 Defective 4.5
9 50 -250～ +325 Inhomogeneous 1.35 0.68 9.88 9.75 Defective 4.8
10 50 -325 Well 1.31 0.64 9.03 8.82 Well 5.7
11 50 -450 Well 1.26 0.61 8.50 8.41 Well 6.1
As seen from Table 2, control Fe-Si has the electrical sheet 2 to 4,10 of optimum size and composition and 11 silicone content increase in the sintered powder, and shows excellent core loss character at high frequency band and power frequency wave band band thus.Equally, they show good coating state.
By contrast, the silicone content that has after 1 silication of the very little electrical sheet of silicone content is too little, therefore to the weak effect that improves of magnetic property.In the situation that comprises the electrical sheet 5 to 7 that is at least 70%Si, so silicone content is big, produce defective such as hole, so the magnetic property of steel plate dies down.
Simultaneously, in the situation of electrical sheet 8 and 9, it is not in size range of the present invention, they are thin and in uneven thickness, therefore the silicone content in the steel plate is little, and observe many defectives on the surface of steel plate, its expression quality is low relatively, the very little and magnetic property variation to the improvement of magnetic property.
Embodiment 3
By using the AlN component as main inhibitor, making thickness from steel billet is the grain-oriented electrical steel sheet product of 0.23mm, and each steel billet comprises C:0.0020wt%, Si:3.15wt%, Mn:0.014wt%, P:0.025wt%, N:0.0002wt%S:0.0003wt%, remaining is Fe and unavoidable impurities.Then, in acidic solution, handle surface of steel plate to remove surface insulation layer fully.
Then, with pulpous state silication coating composition coated steel plates, described silication coating composition is that sintered powder is dispersed in the colloidal-silica solution and forms by the Fe-Si with composition as shown in table 3.
Simultaneously, by silica flour and iron powder are mixed with the different mixing proportion of 9-75% and at 1100-1175 ℃ sintering temperature five hours, to make granularity used herein then be sintered powder less than 325 purpose Fe-Si.Equally, colloidal-silica solution used herein is 30% a colloidal-silica solution product of public offering, and control silica solid material uses in the scope shown in the table 3 then.
The steel plate that is coated with coating composition is dry under 400 ℃ temperature, and visual observation applies state.Then, with the large-scale steel coil strip of exsiccant steel plate coiled.Coil steel plate diffusion annealing 4 hours in 1125 ℃ of nitrogen atmospheres that comprising 50% hydrogen.Then; remove the unreacting substance that remains on when silicification reaction is finished on the steel plate; then; to have chromic salt and acryl resin and be coated to as the organic/inorganic composite coating-forming agent of main ingredient and form the insulating coating film on the steel plate, thereby make the final high silicon grain-oriented electrical steel sheet that is formed with insulating coating in the above.
In the product of as above making, detect Si content and magnetic property, and as shown in the following Table 3.The judgement criteria of specific nature is with embodiment 1.
Table 3
Numbering The Fe-Si powder Colloidal state SiO 2Add-on (g) The coating state Magnetic property Body material Si (%)
Si(％) Add-on (g) B8 (tesla) W10/50 (W/Kg) W10/40 0(W/Kg) W5/100 0(W/Kg)
1 - 1.92 0.31 7.6 9.2 3.1
2 9 100 25 Thin 1.90 0.31 7.4 9.1 3.4
3 20 100 25 Well 1.85 0.28 6.8 7.5 4.0
4 50 100 25 Well 1.69 0.25 5.6 6.2 6.3
5 75 100 25 Thick 1.54 0.36 8.4 10.7 7.5
6 40 100 10 Leafing 1.48 0.33 7.9 9.9 6.9
7 40 100 25 Well 1.71 0.26 5.8 6.3 5.8
8 40 100 40 Thin 1.87 0.29 7.3 8.8 3.5
As seen from Table 3, compare with the electrical sheet 1 that is equivalent to conventional material, control Fe-Si is that powder has the electrical sheet 3,4 of suitable composition and 7 silicone content increases greatly, and shows excellent core loss character at high frequency band and power frequency wave band band thus.
By contrast, the coated weight and the silicone content after the silication of electrical sheet 2 with very little silicone content is too little, makes the weak effect that improves of magnetic property.In the situation of the electrical sheet 5 that comprises too many Si, silicone content is big, but condition of surface is coarse, so the core loss feature is on duty mutually.
Equally, in the situation of the relatively little electrical sheet 6 of silicone content, the leafing of coated membrane is serious, and the core loss feature is on duty mutually.In the situation of electrical sheet 8, the add-on of colloidal silica is too many, and the silicone content after the little and silication of the coated weight of coating composition is little, thus magnetic property to improve effect little.
Embodiment 4
With each self-contained C:0.0015wt%, Si:2.95wt%, Mn:0.022wt%, P:0.003wt%, Ni:0.012wt%, N:0.0006wt%, S:0.0011wt%, remaining is the steel billet of Fe and unavoidable impurities heat again under 1220 ℃ temperature, hot-roll annealing then, making thickness is the hot-rolled steel sheet of 2.5mm.Hot-rolled steel sheet is in 1000 ℃ of annealing five minutes and pickling.Be after final thickness is 0.20mm with the hot rolled cold-rolling of steel plate, removing and be coated in its lip-deep rolling oil.
At first, with the recrystallization annealing 2 minutes (as the conventional manufacture method of non-oriented electromagnetic steel sheet) in 1020 ℃ of nitrogen atmospheres that comprising 25% hydrogen of one of cold-rolled steel sheet of as above obtaining.In order to compare, on the surface of a plurality of cold-rolled steel sheets that as above obtain, apply coating composition as shown in table 4 with the steel plate of routine.
Simultaneously, by silica flour and iron powder are mixed with the different mixing proportion in the 10-80% scope and at 1100-1175 ℃ sintering temperature mix powder five hours, to make granularity used herein then be powder less than 325 purpose Fe-Si.Equally, colloidal-silica solution used herein is 30% a colloidal-silica solution product of public offering, and control silica solid material uses in the scope shown in the table 4 then.
The steel plate that is coated with coating composition is dry under 400 ℃ temperature, and visual observation applies state.Then, with the large-scale steel coil strip of exsiccant steel plate coiled.The steel plate of coiling homogenized 5 hours in 1150 ℃ of nitrogen atmospheres that comprising 75% hydrogen.Then, remove and remain on the unreacting substance on the steel plate when silicification reaction is finished and observe condition of surface.After this, apply and to have chromic salt and acryl resin organic/inorganic composite coating-forming agent, thereby make the non-oriented electromagnetic steel sheet that forms insulating coating in the above as main ingredient.
In the product of as above making, detect Si content and magnetic property, and as shown in the following Table 4.The judgement criteria of specific nature is with embodiment 1.
Table 4
Numbering The Fe-Si powder Colloidal state SiO 2Add-on (g) The coating state Magnetic property Body material Si (%)
Si(％ ) Add-on (g) B8 (tesla) W10/50 (W/Kg) W10/400( W/Kg) W5/1000( W/Kg)
1 - 1.46 0.85 11.95 11.61 2.9
2 10 100 20 Thin 1.49 0.85 11.72 11.53 3.0
3 25 100 20 Well 1.38 0.71 10.05 9.78 4.3
4 55 100 20 Well 1.27 0.59 8.47 8.26 6.4
5 80 100 20 Thick 1.23 0.73 12.03 12.35 7.1
6 40 100 10 Leafing 1.24 0.72 11.89 12.03 6.9
7 40 100 25 Well 1.33 0.64 9.24 8.96 5.5
8 40 100 40 Thin 1.45 0.82 11.35 11.22 3.4
As seen from Table 4, compare with the electrical sheet 1 that is equivalent to conventional material, control Fe-Si is that powder has the electrical sheet 3,4 of suitable composition and 7 silicone content increases greatly, and shows the core loss character in the excellence of the high frequency band of 400Hz and 1000Hz and power frequency wave band band thus.
By contrast, the coated weight and the silicone content after the silication of the electrical sheet 2 that silicone content is very little are too little, make the weak effect that improves of magnetic property.In the situation of the electrical sheet 5 that comprises too many Si, silicone content is big, but condition of surface is coarse, and the core loss feature is on duty mutually.
Equally, in the situation of the relatively little electrical sheet 6 of silicone content, the leafing of coated membrane is serious, and the core loss feature is on duty mutually.In the situation of electrical sheet 8, the add-on of colloidal silica is too many, and the silicone content after the little and silication of the coated weight of coating composition is little, make magnetic property to improve effect little.
Embodiment 5
Grain-oriented electrical steel sheet described in the preparation embodiment 3 is as body material.Equally, be preparation silication coating composition in the fine powder by the Fe-Si that comprises 50w%Si that colloidal-silica solution is mixed into 100 weight parts, the weight that consists of in solid matter of colloidal-silica solution has 25 weight part silicon-dioxide.Use roller coating machine that the coating composition of preparation is coated on the surface of body material steel plate.The coating steel plate is the dry and large-scale steel coil strip of coiled under 400 ℃ temperature.
The steel plate of coiling homogenizes under the different annealing conditions shown in the table 5, thereby removes the unreacting substance that remains on the surface of steel plate.Then, the mixed phosphate and the insulating coating agent in the colloidal silica component that will wherein a small amount of chromic acid be joined magnesium (Mg), aluminium (Al) and calcium (Ca) are coated in formation insulating coating film on the steel plate, thereby make the final high silicon grain-oriented electrical steel sheet that is formed with insulating coating in the above.
In the product of as above making, detect Si content and magnetic property.The judgement criteria of specific nature is with embodiment 1.
Table 5
Numbering The diffusion annealing condition Magnetic property Body material Si content (%)
Hydrogen ratio (%) Temperature (℃) B8 (tesla) W10/50 (W/Kg) W10/400 (W/Kg) W5/1000 (W/Kg)
1 0 1125 1.89 0.30 7.5 9.3 3.3
2 10 1125 1.84 0.29 7.3 8.8 3.6
3 25 1125 1.73 0.26 6.0 6.3 5.4
4 90 1125 1.72 0.25 5.8 6.2 5.7
5 50 950 1.92 0.34 7.9 9.6 3.1
6 50 1100 1.74 0.27 5.9 6.2 5.4
7 50 1225 1.56 0.36 6.8 7.3 6.1
8 75 1125 1.70 0.24 5.7 6.3 5.9
As seen from Table 5, controlling the electrical sheet 3,4,6 of the suitable condition that homogenizes and 8 body material silicone content increases, and shows the excellent core loss feature at high frequency band and power frequency wave band band thus.
By contrast, at 100% nitrogen atmosphere and the body material Si content increase that is comprising the electrical sheet 1 that homogenizes in the nitrogen atmosphere of 10% hydrogen and 2 seldom, make the improvement of core loss feature insufficient.
Equally, in having the electrical sheet 5 of low temperature thermal oxidation too, Si content does not almost change in the body material, can not obtain high silicon electrical steel sheet.In the situation of the electrical sheet 7 of 1225 ℃ of high temperature annealings, produce surface imperfection, make core loss feature variation at the power frequency wave band.
Embodiment 6
Grain-oriented electrical steel sheet is as body material described in the preparation embodiment 4.Equally, be preparation silication coating composition in the fine powder by colloidal-silica solution being mixed into the Fe-Si that 100 weight parts comprise 50%Si, the weight that consists of in solid matter of colloidal-silica solution has 25 weight part silicon-dioxide.Use roller coating machine that the coating composition of preparation is coated on the surface of body material steel plate.The coating steel plate is the dry and large-scale steel coil strip of coiled under 400 ℃ temperature.
The steel plate of coiling carries out diffusion annealing under the different annealing conditions shown in the table 6, thereby removes the unreacting substance that remains on the surface of steel plate.Then, apply and to have chromic salt and acryl resin organic/inorganic composite coating-forming agent, thereby make the final non-oriented electromagnetic steel sheet that is formed with insulating coating in the above as main ingredient.
In the product of as above making, detect Si content and magnetic property.The judgement criteria of specific nature is with embodiment 1.
Table 6
Numbering The diffusion annealing condition Magnetic property Body material Si content (%)
Hydrogen ratio (%) Temperature (℃) B8 (tesla) W10/50 (W/Kg) W10/400 (W/Kg) W5/1000 (W/Kg)
1 0 1150 1.49 0.84 11.68 11.48 3.0
2 10 1150 1.46 0.81 10.98 10.88 3.4
3 25 1150 1.35 0.68 9.48 9.13 5.0
4 90 1150 1.34 0.67 9.41 9.07 5.3
5 50 950 1.48 0.85 11.70 11.34 3.0
6 50 1100 1.35 0.71 9.55 9.31 4.9
7 50 1225 1.23 0.86 11.34 11.01 5.8
8 75 1150 1.33 0.63 9.18 8.88 5.7
As seen from Table 6, controlling the electrical sheet 3,4,6 of suitable diffusion annealing condition and 8 body material silicone content increases, and shows the excellent core loss feature at high frequency band and power frequency wave band band thus.
By contrast, in 100% nitrogen atmosphere and comprising the electrical sheet 1 of diffusion annealing in the nitrogen atmosphere of 10% hydrogen and 2 body material Si content increase seldom, make the improvement of core loss feature insufficient.
Equally, in having 950 ℃ the electrical sheet 5 of too low temperature thermal oxidation, Si content does not almost change in the body material, can not obtain high silicon electrical steel sheet.In the situation of the electrical sheet 7 of 1225 ℃ of high temperature annealings, produce surface imperfection, make core loss feature variation at the power frequency wave band.
Embodiment 7
With each self-contained C:0.0018wt%, Si:3.02wt%, Mn:0.020wt%, P:0.003wt%, Ni:0.010wt%, N:0.0005wt%, S:0.0010wt%, remaining is the steel billet of Fe and unavoidable impurities heat again under 1220 ℃ temperature, hot rolling is the hot-rolled steel sheet of 2.5mm to make thickness then.Hot-rolled steel sheet is in 1000 ℃ of annealing five minutes and pickling.At the hot rolled cold-rolling of steel plate is after final thickness is 0.20mm, removes to be coated in its lip-deep rolling oil.
The cold-rolled steel sheet of as above making is carried out process annealing under condition shown in the table 7.Apply the steel plate of process annealing with the pulpous state coating composition, described coating composition is for forming in the sintered powder by colloidal-silica solution being mixed into the Fe-Si that 100 weight parts comprise 45wt%Si, colloidal-silica solution to consist of in 100 weight part Fe-Si be that sintered powder has 25 weight part silica solid materials.Make the coating steel plate dry under 400 ℃ temperature, and the large-scale steel coil strip of coiled.Then, in the nitrogen atmosphere that is comprising 50% hydrogen under 1125 ℃, the exsiccant steel plate was homogenized 5 hours.Then, remove the unreacting substance that remains in the silicification reaction on the steel plate.After this apply and have chromic salt and acryl resin organic/inorganic composite coating-forming agent, thereby make the final high silicon non-oriented electrical steel plate that is formed with insulating coating in the above as main ingredient.
In the product of as above making, detect Si content and magnetic property.Identical in the judgement criteria of specific nature and the embodiment 1.But, it should be noted that matrix Si content is the end value of wet-way analysis.
Table 7
Numbering The process annealing condition Magnetic property Body material Si content (%)
Temperature (℃) H 2 (％) PH 2O /PH2 Oxygen level (ppm) B8 (tesla) W10/50 (W/Kg) W5/1000 (W/Kg)
1 1050 75 0.09 240 1.27 0.57 8.22 6.3
2 1050 75 0.28 380 1.27 0.59 8.24 6.3
3 1075 75 0.25 350 1.27 0.58 8.22 6.2
4 1000 75 0.25 350 1.26 0.58 8.24 6.3
5 1050 50 0.25 380 1.27 0.58 8.21 6.3
6 1050 90 0.25 375 1.27 0.57 8.20 6.4
As seen from Table 7, cold-rolled steel sheet is through process annealing, applying coating composition, then at high temperature annealing, thereby makes non-oriented electromagnetic steel sheet.
Though the above-mentioned preferred embodiment of reference shows and has described the present invention, can not think that the present invention is limited.By contrast, for those skilled in the art, obviously can carry out multiple modification and change therein, and not break away from defined the spirit and scope of the present invention in the additional claim.
Industrial applicibility
As mentioned above, it is that sintered powder is as the silication coating agent that the present invention uses the Fe-Si with best adjusting composition and granularity, so that final electric steel plate has high silicon content, and therefore might effectively produce power frequency wave band band and high frequency band have excellent magnetic can high silicon electrical steel sheet.

Claims (20)

1. silication coating composition, it comprises:
Fe-Si is the complex chemical compound sintered powder, and the silicon that it has-325 purpose granularities and comprises 20-70wt%, described Fe-Si are that the complex chemical compound sintered powder comprises FeSi 2, FeSi, Fe 5Si 3, and Fe 3At least a among the Si; With
Colloidal-silica solution, it comprises the silica solid material of counting the 15-30 weight part with the described sintered powder of 100 weight parts.
2. the coating composition of claim 1, wherein said Fe-Si are that the complex chemical compound sintered powder has the oxide layer that forms in its surface and this layer and comprises and be lower than 2.0% oxygen.
3. the coating composition of claim 1, it further comprises with the described Fe-Si of 100 weight parts is that the complex chemical compound sintered powder is counted following at least a of being selected from of 0.2-3.5 weight part: thin SiO 2Powder, alumina powder and alumina sol.
4. the coating composition of claim 1, wherein said Fe-Si is that the complex chemical compound sintered powder comprises that in described Fe-Si be the FeSi of the weight of sintered powder above 90wt% 2+ FeSi sintered powder.
5. make the method for high silicon electrical steel sheet, it may further comprise the steps:
Be coated on the surface of steel plate that comprises 2.0-3.3wt%Si each coating composition in the claim 1 to 4 and drying;
The exsiccant steel plate is carried out diffusion annealing at least in 1000-1200 ℃ temperature range in the nitrogen atmosphere that comprises 20% hydrogen.
6. the method for claim 5, wherein said drying step carries out under 200-700 ℃ temperature.
7. the method for claim 5, wherein said diffusion annealing step is carried out under 1050-1200 ℃ temperature.
8. make the method for high silicon grain-oriented electrical steel sheet, it may further comprise the steps: hot again and hot rolling steel billet, make hot-rolled steel sheet; To hot-rolled steel sheet annealing and this steel plate is carried out cold rolling, regulate the thickness of steel plate; Steel plate is carried out decarburizing annealing; With described steel plate is carried out secondary recrystallization annealing,
This is improved one's methods and further may further comprise the steps:
Pickling is carried out on surface to the grain-oriented electrical steel sheet of having finished secondary recrystallization, removes oxide layer;
Be coated on the electrical sheet surface of overpickling each coating composition in the claim 1 to 4 and drying; With
The exsiccant electrical sheet is carried out diffusion annealing at least in 1000-1200 ℃ temperature range in the nitrogen atmosphere that comprises 20% hydrogen.
9. the method for claim 8, wherein the steel plate of described coating composition to be coated comprises the Si that counts 2.9-3.3wt% with described steel plate weight.
10. the method for claim 8, the wherein said steel plate that has applied coating composition is dry under 200-700 ℃ temperature.
11. the method for claim 8, the wherein said steel plate diffusion annealing under 1050-1200 ℃ temperature that has applied coating composition.
12. the method for claim 8 wherein is coated in described coating composition on the described surface of steel plate, to satisfy following formula 1 and 2:
Y-5≤coated weight≤Y+5---------formula 1 and
Y (g/m 2)=7650t (x1-x2)/(A-14.4)-----Shi 2,
Wherein ' t ' is the thickness of body material, and A is that described Fe-Si is the Si content (%) in the sintered powder, and x1 is the target Si content (%) of body material and the initial Si content that x2 is body material.
13. make the method for high silicon non-oriented electrical steel plate, it may further comprise the steps: hot again and hot rolling steel billet, make hot-rolled steel sheet; To hot-rolled steel sheet annealing and annealed sheet steel is carried out cold rolling, regulate the thickness of steel plate; Cold-rolled steel sheet is carried out recrystallization annealing,
This is improved one's methods and further may further comprise the steps:
Each coating composition in the claim 1 to 4 is coated on the surface of described cold-rolled steel sheet and dry; With
The exsiccant electrical sheet is carried out diffusion annealing at least in 1000-1200 ℃ temperature range in the nitrogen atmosphere that comprises 20% hydrogen.
14. the method for claim 13, wherein the steel plate of described coating composition to be coated comprises the Si of 2.9-3.3wt%.
15. the method for claim 13, the wherein said steel plate drying under 200-700 ℃ temperature that has applied coating composition.
16. the method for claim 13, the wherein said steel plate that has applied coating composition homogenizes under 1050-1200 ℃ temperature.
17. the method for claim 13 wherein before applying described coating composition, is carried out process annealing to described cold-rolled steel sheet, makes that the total oxygen content in the oxide layer of described steel plate is 210-420ppm.
18. the method for claim 17, wherein said cold-rolled steel sheet are carried out process annealing in 950-1100 ℃ temperature range.
19. the method for claim 17, wherein said cold-rolled steel sheet is at nitrogen atmosphere that comprises at least 50% hydrogen and dew point (PH 2O/PH 2) carry out process annealing in the humid atmosphere of 0.06-0.30.
20. the method for claim 13 wherein is coated in described coating composition on the described surface of steel plate, to satisfy following formula 1 and 2:
Y-5≤coated weight≤Y+5---------formula 1 and
Y (g/m 2)=7650t (x1-x2)/(A-14.4)-----Shi 2,
Wherein ' t ' is the thickness of body material, and A is that described Fe-Si is the Si content (%) in the sintered powder, and x1 is the target Si content (%) of body material and the initial Si content that x2 is body material.
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