CN1054885C - Method for producing grain-oriented electrical steel sheet having mirror surface and improved core loss - Google Patents
Method for producing grain-oriented electrical steel sheet having mirror surface and improved core loss Download PDFInfo
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Abstract
The present invention discloses a method for producing grain-oriented electrical steel plates with mirror surfaces. The steel plates are of a strip type, contain 0.8 to 4.8% of Si, and are treated by a series of conventional procedures. The method comprises hot rolling with or without annealing, one time or at least two times of cold rolling with intermediate annealing to obtain final thickness, and decarburizing annealing with or without nitrogen treatment; annealing insulators which mainly comprise non-hydrated oxide are coated, and then final annealing is carried out. The improvement of the method comprises that the improvement of the method meets a relational expression [A] is larger than 0.2*[O], wherein [A] is total concentration (weight %) of alkali metal impurities in the annealing insulators, and [O] is the amount of oxygen (g/m<2>) contained in steel plates just before the final annealing.
Description
The present invention relates to the method for a kind of production as the grain-oriented electrical steel sheet of transformer or other electrical equipment iron cores.More properly be, the present invention relates to a kind of method of producing grain-oriented electrical steel sheet, with this method, by making steel plate produce minute surface and making it not have precipitate to reduce iron loss at surf zone.
Be used for dissimilar electrical equipments, mainly be the grain-oriented electrical steel sheet material of transformer contain the Si of 0.8-4.8% and have with 110}＜001〉crystalline structure arranged according to qualifications of orientation.The desired characteristic of grain-oriented electrical steel sheet is high magnetic flux density and low iron loss, and they are respectively with B
8And W
17/50Expression.A kind of core material that shows low electric energy loss, the grain-oriented electrical steel sheet that promptly has low iron loss is from the viewpoint of environment protection and energy saving, by tight demand.
Iron loss can be subdivided into eddy-current loss and Narrow Hystersis loss.The direct ratio that is reduced to of the former and steel plate magnetic domain width reduces, and the latter can be lowered by the obstacle of eliminating magnetic domain wall movement.The major cause of described obstacle is to have precipitate near the inhomogeneous or uneven surface of steel plate and the surface of steel plate.
Have in the low iron loss grain orientation electrical sheet in industrial production, the exploitation to magnetic domain improvement technology has given right of priority.For example, in patent disclosure (disclosing) No.55-18566 of Japanese unexamined, disclose under the situation that is being used for the laminated core material, part or straight line microstrain have been applied on the whole annealed steel plate by bombardment with laser beams.Also have, under the situation that in patent disclosure (disclose) No.61-117218 of Japanese unexamined, discloses the core material that is being used to wind the line, stress relieving is applied in makes on the core of getting well and do not produce the improved effect of magnetic domain.According to the method described above, because eddy-current loss reduces in a large number, total iron loss is lowered.
On the other hand, the various different methods that have the grain-oriented electrical steel sheet of low Narrow Hystersis loss with low cost production have been released.These methods are a kind of all even smooth at obtaining, or the steel surface of mirror-like (being referred to as " minute surface steel surface " in the literary composition of back).Yet, use the industrial production of these methods still to be unrealized.
Below be set fourth as the various conventional scheme that reduces the Narrow Hystersis loss and explain how these schemes can not commercializations.
On the surface of the grain-oriented electrical steel sheet that makes by existing production technique, have one mainly by SiO
2The inner oxide layer of forming is a kind of mainly by forsterite (Mg
2SiO
2) glassy membrane formed.Described inner oxide layer forms on the steel surface by decarburizing annealing.In addition, above-mentioned glassy membrane is forming on above-mentioned inner oxide layer during the annealing eventually, and is adhering to each other to avoid coil winding, and annealing makes SiO eventually
2React with MgO.
Owing to this glassy membrane forms based on above-mentioned inner oxide layer, so the interface between glassy membrane and steel plate is rough, because there is precipitate to exist.As a result, these precipitates have become the obstacle of domain motion.According to various report, for example by S.D.Washko, T.H.Shen and W.G.Morris be at Journal of AppliedPhysics., vol.53, and the report of being done among the pp8296-8298, this phenomenon is known.Thus, the various different methods of this phenomenon have been advised dealing with.For example, a kind of in these methods is the formation that prevents glassy membrane during final annealing, and another kind is after removing glassy membrane, and the polishing by chemistry and machinery obtains all even slick surface.During annealing spacer when using to non-hydrated oxide compound thick with high purity aluminium oxide, on the steel surface of resulting product, do not form any glassy membrane as final annealing.This method is disclosed in U.S. Patent No. 3785882.
Yet owing to just have residual settling and residual uneven surface in the steel lower face behind final annealing, shown iron loss is improved has only 2% at most.
Use a kind of passing through to handle in order to form minute surface by eliminating the residue settling that exists under the steel surface, to be known that as disclosed chemistry or electropolishing among Japanese Unexamined Patent Publication No.49-96920 and the 60-39123.Above-mentioned these methods are suitable for handling small sample in the laboratory, and do not obtain actual use as yet in industrial-scale production.This is because the control chemistry is spissated very difficult, and needs waste treatment device.
With regard to producing a kind of grain-oriented electrical steel sheet that does not have a precipitate with specular light knot degree steel surface, the inventor has proposed a kind of described as Japanese Unexamined Patent Publication No.6-256848 previously, prevent under the steel surface, to form the method for precipitate, this method is to eliminate behind formed oxide skin on the steel plate that has taken off carbon by pickling, by means of applying a kind of annealing spacer of mainly being made up of aluminum oxide.According to this method, with compare iron loss under the situation that oxide skin is not eliminated can be at W
17/50At present reduce 0.1w/kg.Although can technical scale implement pickling according to the method described above, thereby this method need the extra investment in pickler increase production cost.Thereby, a kind of by easy technology and to obtain having with lower production cost serve as that the grain-oriented electrical steel sheet that reduces the minute surface of iron loss exists the intensive demand for exploitation.
Main purpose of the present invention has minute surface and has reduced iron loss, the grain-oriented electrical steel sheet of no precipitate under the surface in order to provide a kind of.Another object of the present invention provides a kind of easy processing method, and this method reduces production cost by the cancellation acid pickling step.
The inventor has carried out a series of tests of overcoming the routine techniques shortcoming and achieving the above object of being intended to, to develop a kind of more effective production method for the minute surface steel surface that obtains no precipitate under the grain-oriented electrical steel sheet product surface.
In this research, the inventor has found, the amount of impurities in as the oxide compound of annealing spacer, particularly alkali-metal concentration, according to contained oxygen amount in the steel plate when the decarburizing annealing and controlled, the precipitate that increases iron loss forms and can be prevented from the beginning, and in addition, the formation of minute surface can obtain promoting in the final annealing step.
According to the present invention, for reach reduce iron loss by use a kind of annealing spacer of mainly forming by the non-hydrated oxide compound and the concentration that is controlled at alkali metal impurity in this annealing spacer and exactly the oxygen amount in the steel plate before final annealing a kind of grain-oriented electrical steel sheet with low iron loss minute surface is provided.More particularly, according to the present invention, obtain minute surface by satisfying following relational expression:
[A]＞0.2×[O]，
Wherein [A] is the total concn (weight %) of alkali metal impurity in the annealing spacer,
And [O] is just before final annealing the time, the oxygen level (g/m in this steel plate
2).
In addition, the invention provides and a kind ofly mainly forms, be contained in the non-hydrated oxide compound in the annealing spacer, so that obtain the iron loss of mirror steel surface and reduction by aluminum oxide.
In addition, above-mentioned alkali metal impurity is at least by a kind of composition the among Li, Na and the K.This annealing spacer also contains at least a in oxyhydroxide, nitrate, vitriol, muriate or the acetate of Li, Na or K in addition.
Thereby, can easily obtain the mirror steel surface of no precipitate under the surface by a kind of easy method, so that reduce iron loss, particularly Narrow Hystersis loss.
Fig. 1 shows coating alumina as the annealing spacer, and the result who carries out X-ray diffraction (CuK α) microscopy of the grain-oriented electrical steel sheet of final annealing subsequently.(a) show at an example that uses X-ray diffraction analysis (CuK α) result under the high purity aluminium oxide situation.(b) show use contain 0.2 (weight %) Na as the aluminum oxide situation of impurity under X-ray diffraction analysis (CuK α) result's a example.
Fig. 2 is explanation oxygen level and curve of just concerning between the formation of steel lower face precipitate in the steel plate when sodium amount and decarburizing annealing in as the isolated aluminum oxide of annealing.There is not precipitate in " 0 " representative, and there is precipitate in " " representative.
Fig. 3 shows the aluminum oxide that has applied as the annealing spacer, makes the Photomicrograph of the grain-oriented electrical steel sheet sectional view of final annealing then.(a) show at an example that uses under the situation of high purity aluminium oxide.(b) show to use and contain 0.2 (weight %) Na and be an example under the aluminum oxide situation of impurity.
The inventor has used the oxide compound as the annealing spacer of various different types of aluminum oxide-normally, and finds, influences the formation of precipitate and the minute surface situation on steel surface as the sodium of impurities in the aluminum oxide.This is because when having a large amount of Na, even there is oxide film, also can obtain minute surface.In addition, when the steel surface demonstrates the minute surface situation, just do not observe any settling in the steel lower face.The inventor does not also find out the reason of this situation.It is believed that, so because the SiO that exists Na in the time may impelling during the final annealing step, to form in decarburizing annealing
2Reduce.If in the final annealing step, be easy to take place SiO
2Minimizing, what then once forming just just reduces and disappears at the subsurface precipitate of steel.Otherwise they do not form from the beginning.As a result, can easily obtain mirror steel surface.
In producing grain-oriented electrical steel sheet, carbon is a kind of for to obtain the fundamental element of required crystalline structure in the intermediate product, so that promote according to qualifications in the finished product 110}＜001 crystalline orientation.Although the production phase must comprise carbon with required amount in early days, the carbon that remains in the finished product increases iron loss.Therefore, in wet hydrogen/nitrogen mixed gas atmosphere, carry out a full annealed so that decarburization.A this full annealed is commonly referred to decarburizing annealing.The concentration of residue carbon must be limit to less than 30ppm in the finished product.
Usually, the speed of decarburizing reaction depends on the reaction potentiality of oxygen in the decarburizing atmosphere.When the reaction potentiality step-down of oxygen, decarburizing reaction slows down.Fan Ying oxygen potentiality can be increased on the other hand, forms mainly by SiO on the electrical sheet surface
2The inner oxide layer of forming.At present, also do not find, can finish decarburization between carbon period simultaneously and form the inner oxide layer, do not reduce the condition of productivity in addition.
Therefore, the decarburizing annealing steel plate of handling under normal operation comprises that inevitably one deck is mainly by SiO
2The inner oxide layer of forming.As mentioned above, if, carry out final annealing then, then can there be the grain-oriented electrical steel sheet of oxide film from the teeth outwards with thick overlaying on the decarburization steel plate with inner oxide layer with the high-purity mangesium oxide aluminum coating.Yet the steel plate that obtains so not only shows appearance steel surface, but also just has precipitate under the steel surface.In being shown in the surface of steel plate microscopic cross-section figure of Fig. 3 (a), clearly observe these precipitates.
These chemical structures that just are being formed at the precipitate under the steel surface depend on whether containing sour molten Al before the final annealing in steel plate.When containing sour molten aluminium in the steel plate before final annealing, to observe by X-ray diffraction (CuK α) microscopy, formed precipitate is mainly by mullite (3Al
2O
32SiO
2) form.On the other hand, when not containing sour molten Al in the steel plate before final annealing, observe resistates by infrared spectra and show that formed precipitate is mainly by SiO
2Form.
Because the rising of dew point increased contained SiO among these precipitates when just the amount of the precipitate that forms was with decarburizing annealing under the steel surface
2Origin form when being considered to be in decarburizing annealing contain SiO
2The inner oxide layer.On the other hand, contained Al in precipitate
2O
3Origin is inferred the sour molten Al for the control secondary recrystallization contained in the steel plate, and is the aluminum oxide as the annealing spacer.This is because these precipitates are not to be exposed to the steel surface.Set out by the above-mentioned fact, will be understood that, the SiO that during decarburizing annealing, forms
2The inner oxide layer just stay the steel surface under, so this SiO
2Reducing atmosphere in the time of can not be by final annealing reduces.Particularly, when containing sour molten Al in the steel plate, this sour molten Al can and SiO
2Reaction also just forms mullite under the steel surface.Because these precipitates are present within the steel plate, they can not be reduced under the reducing atmosphere condition under back half high temperature of final annealing.If these precipitates are not to exist on the steel surface, then atomic diffusion is promoted powerfully, therefore quickens the formation of mirror-finishing.On the other hand, if these precipitates just are present under the steel surface, then the promoter action of atomic diffusion is prevented from, and therefore the formation of mirror-finishing also is prevented from when final annealing.
Consider the relevant above-mentioned mechanism that when final annealing, just under the steel surface, forms precipitate, produce under the following conditions in the grain-oriented electrical steel sheet and always can have problems: when (1) contains suction Si when steel, (2) in the time must carrying out decarburizing annealing, and (3) are not when forming the glassy membrane that contains forsterite when form minute surface during final annealing.Thereby, can apply the present invention to produce the grain-oriented electrical steel sheet of all kinds basically according to above-mentioned condition (1)-(3).
The inventor has used various different types of aluminum oxide, this oxide compound is usually as the annealing spacer, described aluminum oxide contains the impurity of different amounts, as Na, K or Li and/or other compounds, and find, when containing Na in the aluminum oxide and be impurity, even there is oxide film, it also can influence the formation of precipitate and the situation of specular brightness.In addition, this phenomenon depends on the Na amount.Therefore, the aluminum oxide that contains a large amount of Na when use is during as the annealing spacer, just finding less than any precipitate under the steel surface and obtains mirrored surface.In the microscope figure of Fig. 3 (a) and Fig. 1 (b), clearly observe this phenomenon.The inventor it be unclear that the reason of this phenomenon so far.People's hypothesis is because exist Na, so the SiO that forms when decarburizing annealing
2Minimizing can in the final annealing step, be accelerated.If SiO takes place in the final annealing step easily
2Minimizing, the precipitate that forms under positive steel surface then reduces and disappears, or does not just form originally.As a result, if use the aluminum oxide that contains a large amount of Na as the annealing spacer.Then can easily obtain minute surface.
According to discovering further that for what stop the Na concentration that just under the steel surface, forms in the required aluminum oxide of precipitate the oxygen level in the decarburizing annealing is depended in the existence of precipitate.Fig. 2 shows the Na concentration and the precipitation state of the precipitate under the steel surface just in the aluminum oxide.When oxygen level in the decarburization steel plate after a little while, required Na amount is also few.This has derived following relational expression:
[A]＞0.2 * [O] wherein [A] is the Na concentration (weight %) in the aluminum oxide that is used as the annealing spacer, and [O] is each surperficial oxygen level (g/m of decarburization steel plate
2).Therefore, when the decarburization steel plate satisfied the above-mentioned relation formula with the annealing spacer, the product that finally obtains not had precipitate and has minute surface.
In order to satisfy above-mentioned relation, preferably reduce the dew point of decarburizing annealing atmosphere, or after decarburizing annealing, eliminate oxide film by slight pickling as contained Na in the aluminum oxide of annealing spacer.In addition, in order to satisfy above-mentioned relation under the oxygen level of decarburization steel plate, preferably select to contain the aluminum oxide that appropriate amount Na is an impurity, or with any different sodium compound of aequum, in the adding aluminum oxide such as oxide compound, oxyhydroxide, muriate, vitriol or nitrate as sodium.Under above-mentioned every kind of situation, all can obtain minute surface.As for the impurity except that Na that is contained in the aluminum oxide, basic metal as Li and K etc., demonstrates the effect identical with Na.Therefore, lithium compound or potassium compound can be added in the aluminum oxide.
In the time can using actual production grain-oriented electrical steel sheet of the present invention, can use typical common process method.These methods are included in U.S. Patent No. 1,965, disclosed use MnS is as the people's such as N.P.Goss of main inhibitor method, in US Patent No 3 in 559,287, disclosed use AlN and MnS are as the Taguchi of main inhibitor in 183, (Al, Si) N is as the people's such as Komatsu of main inhibitor method for people's such as Sakakura method and disclosed use in the clear 60-45285 of Japanese patent laid-open publication gazette No. (bulletin).The component and the employed amount of steel of the present invention below are described.
Carbon be a kind of for form γ mutually required and for recrystallization structure of control before final annealing to guarantee the necessary element of suitable secondary recrystallization.Therefore, contained carbon must be in the 0.02-0.1% scope in cold-rolled steel sheet.If carbon content is greater than 0.1%, recrystallization structure period of worsening and need grow for decarburization then.
Silicon is the important element that improves resistance and reduce iron loss.If silicone content is less than 0.8%, transformation and infringement crystalline structure and the orientation of α to γ then takes place when final annealing, and if silicone content greater than 4.8%, then because crackle makes the cold rolling difficulty that becomes.Preferable silicone content is 0.8%-4.8%.
Manganese and sulphur form the inhibitor that suppresses a crystal grain generation.In order to guarantee stable secondary recrystallization, the content of manganese and sulphur must respectively be limited in the scope of 0.02-0.3% and 0.005-0.40%.
Acid molten aluminium be a kind of fundamental element, it combine with nitrogen formation AlN or (Al, Si) N as inhibitor to obtain high magnetic flux density.The content of preferable sour molten aluminium is 0.012-0.05%.
Nitrogen also is a kind of fundamental element, and it combines with solubility in acid aluminium and forms a kind of inhibitor.If greater than 0.01%, then undesirably forming in the finished product, nitrogen content scabs.Preferable nitrogen content is for being not more than 0.01%.
Deacidify outside the molten aluminium, other elements also can be used to form inhibitor as B, Bi, Pb, S, Se, Sn or Ti.
Be transferred to the directly cold rolling or hot rolled band annealing in short-term of hot rolled strip in the mentioned component scope with currently known methods.Described hot rolled band annealing is effectively to the magnetic energy that improves the finished product, and carries out under the temperature between 750 ℃ and 1200 ℃ 30 seconds to 30 minutes.According to required quality product or cost determination annealing conditions.
Using AlN or (Al Si) under the situation of N as inhibitor, is used in disclosed known cold rolling process among the clear 40-15644 of Japanese patent laid-open publication gazette (bulletin) No., is carrying out under greater than 8% condition cold rolling with the compression ratio of final thickness.Certainly, cold rolling condition can be variable according to used inhibitor.
In wet atmosphere, under the temperature between 750 ℃ and 900 ℃, cold-rolled steel strip is carried out decarburizing annealing then, to carry out a recrystallization and from cold-rolled steel strip, to remove carbon elimination.(Al Si) under the situation of N as main inhibitor, carries out nitriding treatment after decarburizing annealing using.Described nitriding treatment is containing the NH with nitrogenize ability
3Carry out in the atmosphere gas.The nitrogenize amount is more than 0.005% of nitrogenous total amount in the steel plate, preferably greater than the equivalent thickness of aluminium of steel plate.
Subsequently, a kind of spacer of annealing is coated on the steel band of decarburization or nitrogenize so that when final annealing, form glassy membrane and prevent bonding.Spendable in the present invention annealing spacer is a kind of oxide compound that is difficult to hydration.If use a kind of oxide compound that is easy to hydration, like MgO then forms one deck oxide skin in steel surface generation peroxidation or owing to be reflected at the steel surface with the oxide film that is formed by decarburization, thereby can not get minute surface when final annealing.
If the annealing spacer is a kind of steady oxide with non-hydrated characteristic, then be not limited to specific oxide compound.Can use as ZrO
2Or Y
2O
3Such oxide compound.
Aluminum oxide is owing to its non-hydrated characteristic and low cost, so be a kind of appropriate oxide of the present invention.Suitable be to use the aluminum oxide that the charge is small, because it contains a large amount of sodium.Use this annealing spacer with ordinary method or by electrostatic coating with pulpous state.When this annealing spacer when being suspended in the water, what meet the requirements is to add resist steel surface oxidisation when preventing to apply to this suspension.Under using the thicker oxide particle situation that is suspended in the water, add binding agent, as methylcellulose gum to improve coating ability and adhesive capacity.
For the requirement of the regulation that obtains minute surface of the present invention is in decarburizing annealing and must satisfies the condition of following defined when applying the annealing spacer.Described condition is a relational expression: [A]＞0.2 * [O], wherein [O] is the oxygen amount (g/m in the steel plate just before final annealing the time
2), and [A] is the total concn (weight %) of alkali metal impurity in the annealing spacer.
Above-mentioned condition can reach by following means.The oxide compound that contains the low concentration alkali metallic impurity when use can be by the oxygen level in the slight cleanup acid treatment reduction steel plate after decarburizing annealing during as the annealing spacer.But, occurring from the production cost viewpoint, this method can not be recommended, because this needs extra step.In the decarburizing annealing operation, can according to when decarburization is almost finished in steel plate the oxygen amount of contained generation, use contains the non-hydrated oxide compound of alkali metal impurity as the annealing spacer, and selects to avoid a kind of suitable atmosphere and the annealing cycle of steel plate oxidation.
Can adopt following means to guarantee necessary concentration as alkali metal impurity in the non-hydrated oxide compound of annealing spacer.Normally used cheap commercial alumina owing to its production method, contains the amount of impurity Na about 0.2% natively.Therefore, this commercial alumina at a low price is very useful as the annealing spacer to reaching purpose of the present invention.When the quantity not sufficient of contained Na impurity in the aluminum oxide with the amount of oxidation coupling of steel plate the time, or use the non-hydrated oxide compound do not have alkali metal impurity during as the annealing spacer, a kind of alkali metal chloride (or salt) is added this oxide powder or a kind of alkali metal chloride (or salt) is dissolved in the slurry of preparation annealing spacer with necessary amount.For this alkali metal chloride (or salt), feasible be to use a kind of water-soluble salt, this salt is selected from the thing group that is made of the oxyhydroxide of Na, K or Li etc., nitrate, vitriol, muriate or acetate etc.
At last, after applying the annealing spacer, be secondary recrystallization and purification, carry out final annealing.No.2-258929 is disclosed as Japanese Unexamined Patent Publication (disclosing), and keeping steady temperature in heating steps is effective with the regulation heating period that promotes secondary recrystallization to improving magneticflux-density.
Finish secondary recrystallization in final annealing after, in temperature during greater than 100 ℃, insulation is to purify nitride and the minute surface adjustment is done on the steel surface in 100% nitrogen atmosphere with the steel band after the heating.
One insulating coating applied be added on the steel band to produce tension effect and to reduce iron loss.In addition, can use magnetic domain by laser radiation improves and handles with further reduction iron loss.
Explain the present invention now with reference to following embodiment, but this and do not mean that the scope of the present invention that limits.The present invention will can be applicable to disclosed so far, independent or other steel that meet the following conditions that combine are formed or other producing and manufacturing technique: (1) steel contains Si, (2) essential decarburizing annealing, and (3) form minute surface during final annealing and do not contain the glassy membrane of forsterite in producing grain-oriented electrical steel sheet.Embodiment 1
With a kind of 0.05% (weight) C, 3.3% (weight) Si, 0.1% (weight) Mn, 0.007% (weight) S, the sour molten Al of 0.03% (weight), 0.008% (weight) N and 0.05% (weight) Sn of containing, its surplus comprises that the grain oriented electrical steel material of Fe and inevitable impurity handles, used method is common production stage, promptly be hot-rolled down to 2.3mm thickness, 1100 ℃ of following hot rolled band annealing of temperature 2 minutes, then be cold-rolled to the pickling simultaneously of 0.23mm final thickness.Then, the cold-strip that obtains is like this handled by decarburizing annealing through different annealing times in different atmosphere.Oxygen level in the steel plate is shown in table 1.Then, at NH
3Carry out nitriding treatment in the atmosphere gas, make in the steel plate nitrogen content reach 0.025% to strengthen inhibitor.Subsequently, a kind of spacer of annealing is coated on the steel plate of nitrogenize.The MgO of routine is coated on some steel plates, and will contain different sorts basic metal is that the aluminum oxide with different concns pulpous state impurity is coated on the steel plate that is stayed.Then, carry out final annealing, method therefor be in 100% nitrogen with 10 ℃/time constant heating rate steel plate is heated to 1200 ℃, and it was kept 20 hours down in 1200 ℃ of temperature in 100% hydrogen.In the time of 1200 ℃, convert atmosphere gas to hydrogen by nitrogen.At last, handle the steel plate of forcing at final annealing with insulating coating with by the magnetic domain improvement that laser radiation is carried out.The product that obtains has the magnetic property that is shown in Table 1.
Table 1
Embodiment 2
| Oxygen amount/per surface (g/m 2) | The kind of annealing spacer | Impurity Na concentration (weight %) in the annealing spacer | The basic metal amount (weight %) that adds the annealing spacer | The method that basic metal adds | The situation on steel surface | Have or not precipitate under the surface | Magnetic property | ||
| B 8 (T) | W 17/50 (w/kg) | ||||||||
| Comparative example 1 | 0.7 | MgO | - | - | - | Glassy membrane | - | 1.91 | 0.80 |
| Comparative example 2 | 0.7 | Al 2O 3 | 0.12 | - | - | Nonspecular surface | Have | 1.92 | 0.81 |
| The present invention 1 | 0.7 | Al 2O 3 | 0.20 | - | - | Minute surface | Do not have | 1.94 | 0.63 |
| The present invention 2 | 0.5 | Al 2O 3 | 0.05 | 0.10 | Add NaOH | Minute surface | Do not have | 1.94 | 0.63 |
| Comparative example 3 | 0.3 | Al 2O 3 | 0.03 | - | - | Nonspecular surface | Have | 1.95 | 0.79 |
| The present invention 3 | 0.3 | Al 2O 3 | 0.03 | - | - | Minute surface | Do not have | 1.95 | 0.62 |
| The present invention 4 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add KOH | Minute surface | Do not have | 1.96 | 0.61 |
| The present invention 5 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add LiOH | Minute surface | Do not have | 1.96 | 0.62 |
| Comparative example 4 | 0.2 | Al 2O 3 | 0.015 | - | - | Nonspecular surface | Have | 1.94 | 0.80 |
| The present invention 6 | 0.2 | Al 2O 3 | 0.08 | - | - | Minute surface | Do not have | 1.97 | 0.58 |
| The present invention 7 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaCl | The border face | Do not have | 1.96 | 0.61 |
| The present invention 8 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaNH 3 | Minute surface | Do not have | 1.96 | 0.60 |
| The present invention 9 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add potassium acetate | The border face | Do not have | 1.95 | 0.62 |
To contain 0.07% (weight) C, 3.3% (weight) Si, 0.07% (weight) Mn, 0.025% (weight) S, the sour molten Al of 0.026% (weight), 0.008% (weight) N and 0.1% (weight) Sn, surplus comprises that the grain-oriented electrical steel sheet material of Fe and inevitable impurity handles, used method is common production stage, promptly be hot-rolled down to 2.3mm thickness, the band of hot rolling was unannealed 2 minutes of 1100 ℃ of temperature, be cold-rolled to final thickness 0.23mm then, pickling simultaneously.Then, by in different atmosphere through different annealing times through decarburizing annealing, handle the cold-strip obtain like this.Oxygen level in the steel plate is shown in table 2.
Subsequently, a kind of spacer of annealing is coated on the steel band after the decarburization.The MgO of routine is coated on some steel plates, and will contain different types of, as the slurry coating of the alkali-metal aluminum oxide of impurity and different concns on remaining steel plate.Then, carry out final annealing, used method is in the mixed atmosphere that contains 15% nitrogen and 85% hydrogen, with 15 ℃/time constant heating rate steel plate is heated to 1200 ℃, further under 1200 ℃ of temperature, this steel was kept 20 hours in 100% hydrogen then.Finally be converted to hydrogen by nitrogen at 1200 ℃ of gases with atmosphere.At last, with insulating coating with inject capable magnetic domain by the laser width of cloth and improve to handle and be applied on the band of final annealing.The product that obtains has magnetic property as shown in table 2.
Table 2
Embodiment 3
| Oxygen amount/per surface (g/m 2) | The kind of annealing spacer | Impurity Na concentration (weight %) in the annealing spacer | The basic metal amount (weight %) that adds the annealing spacer | The method that basic metal adds | The situation on steel surface | Have or not precipitate under the surface | Magnetic property | ||
| B 3 (T) | W 17/50(w/kg) | ||||||||
| Comparative example 1 | 0.7 | MgO | - | - | - | Glassy membrane | - | 1.90 | 0.81 |
| Comparative example 2 | 0.7 | Al 2O 3 | 0.12 | - | - | Nonspecular surface | Have | 1.92 | 0.80 |
| The present invention 1 | 0.7 | Al 2O 3 | 0.20 | - | - | Minute surface | Do not have | 1.93 | 0.65 |
| The present invention 2 | 0.5 | Al 2O 3 | 0.05 | 0.10 | Add NaOH | Minute surface | Do not have | 1.93 | 0.66 |
| Comparative example 3 | 0.3 | Al 2O 3 | 0.03 | - | - | Nonspecular surface | Do not have | 1.94 | 0.78 |
| The present invention 3 | 0.3 | Al 2O 3 | 0.08 | - | - | Minute surface | Do not have | 1.96 | 0.60 |
| The present invention 4 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add KOH | Minute surface | Do not have | 1.95 | 0.61 |
| The present invention 5 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add LiOH | Minute surface | Do not have | 1.95 | 0.62 |
| Comparative example 4 | 0.2 | Al 2O 3 | 0.015 | - | - | Nonspecular surface | Have | 1.94 | 0.80 |
| The present invention 6 | 0.2 | Al 2O 3 | 0.08 | - | - | Minute surface | Do not have | 1.95 | 0.60 |
| The present invention 7 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaCI | Minute surface | Do not have | 1.96 | 0.60 |
| The present invention 8 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaNH 3 | Minute surface | Do not have | 1.95 | 0.61 |
| The present invention 9 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add potassium acetate | Minute surface | Do not have | 1.96 | 0.62 |
To contain 0.05% (weight) C, 3.3% (weight) Si, 0.07% (weight) Mn and 0.025% (weight) S, surplus comprises that the grain oriented electrical steel material of Fe and inevitable impurity handles, used method is common production stage, promptly be hot-rolled down to 2.5mm thickness, pickling simultaneously, then be cold-rolled to final thickness 0.30mm, under 900 ℃ of temperature, carry out process annealing simultaneously through 2 minutes.Then, the cold-strip that obtains is like this handled with the decarburizing annealing that different atmosphere and different annealing times carry out.Oxygen amount in this steel plate is shown in table 3.Subsequently, a kind of spacer of annealing is coated on the steel band after this decarburization.
MgO commonly used is coated on some steel plates, and will contain different sorts as the alkali-metal aluminum oxide of impurity and with the different concns slurry coating on all the other steel plates.Then, carry out final annealing, used method is in the mixed atmosphere that contains 15% nitrogen and 85% hydrogen, with 15 ℃/time constant heating rate this sodium plate is heated to 1200 ℃ and under 1200 ℃ of temperature these steel plates were remained in 100% nitrogen atmosphere through 20 hours.Gas with atmosphere under 1200 ℃ is converted to hydrogen by nitrogen.At last, inject the steel plate that capable magnetic domain improvement processing imposes on final annealing with insulating coating with by the laser width of cloth.The product that obtains has the magnetic property that is shown in table 3.
Table 3
| Oxygen amount/per surface (g/m 2) | The kind of annealing spacer | Impurity Na concentration (weight %) in the annealing spacer | The basic metal amount (weight %) that adds the annealing spacer | The method that basic metal adds | The situation on steel surface | Have or not precipitate under the surface | Magnetic property | ||
| B 3 (T) | W 17/50(w/kg) | ||||||||
| Comparative example 1 | 0.7 | MgO | - | - | - | Glassy membrane | - | 1.85 | 1.21 |
| Comparative example 2 | 0.7 | Al 2O 3 | 0.12 | - | - | Nonspecular surface | Have | 1.87 | 1.17 |
| The present invention 1 | 0.7 | Al 2O 3 | 0.20 | - | - | Minute surface | Do not have | 1.87 | 1.07 |
| The present invention 2 | 0.5 | Al 2O 3 | 0.05 | 0.10 | Add NaOH | The border face | Do not have | 1.86 | 1.06 |
| Comparative example 3 | 0.3 | Al 2O 3 | 0.03 | - | - | Nonspecular surface | Have | 1.87 | 1.17 |
| The present invention 3 | 0.3 | Al 2O 3 | 0.08 | - | - | The border face | Do not have | 1.87 | 1.07 |
| The present invention 4 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add KOH | Minute surface | Do not have | 1.86 | 1.07 |
| The present invention 5 | 0.3 | Al 2O 3 | 0.03 | 0.05 | Add LiOH | Minute surface | Do not have | 1.86 | 1.07 |
| Comparative example 4 | 0.2 | Al 2O 3 | 0.015 | - | - | Nonspecular surface | Have | 1.86 | 1.18 |
| The present invention 6 | 0.2 | Al 2O 3 | 0.08 | - | - | Minute surface | Do not have | 1.87 | 1.06 |
| The present invention 7 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaCI | Minute surface | Do not have | 1.87 | 1.07 |
| The present invention 8 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add NaNH 3 | Minute surface | Do not have | 1.86 | 1.07 |
| The present invention 9 | 0.2 | Al 2O 3 | 0.015 | 0.05 | Add potassium acetate | Minute surface | Do not have | 1.86 | 1.07 |
Claims (7)
1. a production has the method for the grain-oriented electrical steel sheet of minute surface, described steel plate is a ribbon form, contain 0.02-0.1%C and 0.8-4.8%Si and lived through a series of conventional operations, this method comprises and is with or without the annealed hot rolling, once or at least secondary have process annealing to obtain the cold rolling of final thickness, be with or without the decarburizing annealing of nitriding treatment, apply a kind of annealing spacer that mainly contains the non-hydrated oxide compound, final annealing then, its improvement comprises:
Satisfy relational expression
[A]＞0.2×[O]
Wherein [A] is the total concn (weight %) of the alkali metal impurity of annealing in the spacer, and [O] is contained oxygen amount (g/m in the steel plate before final annealing just in time
2).
2. a production has the method for the grain-oriented electrical steel sheet of minute surface, described steel plate is a ribbon form, contain 0.02-0.1%C, 0.8-4.8% Si, 0.012-0.05% acid molten Al, N and 0.02-0.3%Mn and lived through a series of conventional operations less than 0.01%, comprise and be with or without the annealed hot rolling, once or at least secondary have process annealing to obtain the cold rolling of final thickness, the decarburizing annealing of nitriding treatment is arranged, apply a kind of annealing spacer and final annealing that mainly contains the non-hydrated oxide compound, its improvement comprises:
Satisfy relational expression
[A]＞0.2×[O]
Wherein [A] is the total concn (weight %) of the alkali metal impurity of annealing in the spacer, and [O] is contained oxygen amount (g/m in the steel plate before final annealing just in time
2).
3. a production has the method for the grain-oriented electrical steel sheet of minute surface, described steel plate is a ribbon form, contain 0.02-0.1%C, 0.8-4.8%Si, the molten Al of 0.012-0.05% acid, the N less than 0.01%, 0.02-0.3%Mn and 0.005-0.040%S and lived through a series of conventional operations, this method comprises and is with or without the annealed hot rolling, once or at least secondary have process annealing to obtain the cold rolling of final thickness, decarburizing annealing, apply a kind of annealing spacer that mainly contains non-hydrated oxide compound final annealing then, its improvement comprises:
Satisfy relational expression
[A]＞0.2×[O]
Wherein [A] is the total concn (weight %) of the alkali metal impurity of annealing in the spacer, and [O] is contained oxygen amount (g/m in the steel plate before final annealing just in time
2).
4. a production has the method for the grain-oriented electrical steel sheet of minute surface, described steel plate is a ribbon form, contain 0.02-0.1%C, 0.8-4.8%Si, the N less than 0.01%, 0.02-0.3%Mn and 0.005-0.040%S and lived through a series of conventional operations, this method comprises and is with or without the annealed hot rolling, once or at least secondary have process annealing to obtain the cold rolling of final thickness, decarburizing annealing, apply a kind of annealing spacer that mainly contains the non-hydrated oxide compound, final annealing then, its improvement comprises:
Satisfy relational expression
[A]＞0.2×[O]
Wherein [A] is the total concn (weight %) of the alkali metal impurity of annealing in the spacer, and [O] is contained oxygen amount (g/m in the steel plate before final annealing just in time
2).
5. the process of claim 1 wherein that the non-hydrated oxide compound mainly is made up of aluminum oxide.
6. the process of claim 1 wherein that the alkali metal impurity in the annealing spacer mainly is that one or more metals that are selected from the thing group of being made up of Li, Na or K are formed.
7. the process of claim 1 wherein that this annealing spacer contains one or more compounds that are selected from by in the thing group that oxyhydroxide, nitrate, vitriol, muriate or acetate constituted of Li, Na or K.
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| CN95109617A CN1054885C (en) | 1995-07-26 | 1995-07-26 | Method for producing grain-oriented electrical steel sheet having mirror surface and improved core loss |
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|---|---|---|---|
| CN95109617A CN1054885C (en) | 1995-07-26 | 1995-07-26 | Method for producing grain-oriented electrical steel sheet having mirror surface and improved core loss |
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| CN1054885C true CN1054885C (en) | 2000-07-26 |
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| JP4288054B2 (en) * | 2002-01-08 | 2009-07-01 | 新日本製鐵株式会社 | Method for producing grain-oriented silicon steel sheet |
| BRPI0711794B1 (en) * | 2006-05-24 | 2015-12-08 | Nippon Steel & Sumitomo Metal Corp | method for producing grain oriented magnetic steel sheet having a high magnetic flux density |
| KR101906962B1 (en) * | 2016-12-22 | 2018-10-11 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
| KR101919528B1 (en) | 2016-12-22 | 2018-11-16 | 주식회사 포스코 | Oriented electrical steel sheet and method for manufacturing the same |
| EP3653753B8 (en) * | 2017-07-13 | 2024-09-25 | Nippon Steel Corporation | Grain-oriented electrical steel sheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH032324A (en) * | 1989-05-29 | 1991-01-08 | Nippon Steel Corp | Manufacture of grain-oriented silicon steel sheet having excellent magnetic characteristics and film characteristics |
| JPH05295438A (en) * | 1992-04-16 | 1993-11-09 | Nippon Steel Corp | Production of grain-oriented silicon steel sheet excellent in magnetic property |
| JPH0617132A (en) * | 1992-07-02 | 1994-01-25 | Nippon Steel Corp | Ultralow iron loss grain-oriented silicon steel sheet having extremely high magnetic flux density and its production |
| JP3002324B2 (en) * | 1992-03-21 | 2000-01-24 | エヌオーケー株式会社 | Dispersion liquid filling device |
-
1995
- 1995-07-26 CN CN95109617A patent/CN1054885C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH032324A (en) * | 1989-05-29 | 1991-01-08 | Nippon Steel Corp | Manufacture of grain-oriented silicon steel sheet having excellent magnetic characteristics and film characteristics |
| JP3002324B2 (en) * | 1992-03-21 | 2000-01-24 | エヌオーケー株式会社 | Dispersion liquid filling device |
| JPH05295438A (en) * | 1992-04-16 | 1993-11-09 | Nippon Steel Corp | Production of grain-oriented silicon steel sheet excellent in magnetic property |
| JPH0617132A (en) * | 1992-07-02 | 1994-01-25 | Nippon Steel Corp | Ultralow iron loss grain-oriented silicon steel sheet having extremely high magnetic flux density and its production |
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