EP0752012B1 - Process for producing magnetic steel sheets with a glass coating - Google Patents
Process for producing magnetic steel sheets with a glass coating Download PDFInfo
- Publication number
- EP0752012B1 EP0752012B1 EP95912252A EP95912252A EP0752012B1 EP 0752012 B1 EP0752012 B1 EP 0752012B1 EP 95912252 A EP95912252 A EP 95912252A EP 95912252 A EP95912252 A EP 95912252A EP 0752012 B1 EP0752012 B1 EP 0752012B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- annealing separator
- additive
- mgo
- strip
- annealing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011521 glass Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 10
- 238000000576 coating method Methods 0.000 title description 5
- 239000011248 coating agent Substances 0.000 title description 4
- 229910000831 Steel Inorganic materials 0.000 title description 3
- 239000010959 steel Substances 0.000 title description 3
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 46
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 46
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 33
- 238000000137 annealing Methods 0.000 claims abstract description 26
- -1 sodium phosphate compound Chemical class 0.000 claims abstract description 15
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 7
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 238000005097 cold rolling Methods 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims 3
- 229910052810 boron oxide Inorganic materials 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 10
- 235000011008 sodium phosphates Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005261 decarburization Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 229910000379 antimony sulfate Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000000181 anti-adherent effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000012549 training Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010037867 Rash macular Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052840 fayalite Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Images
Classifications
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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
-
- 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
- C21D8/1283—Application of a separating or insulating coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
- C23D5/02—Coating with enamels or vitreous layers by wet methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
Definitions
- the invention relates to a method for producing Electrical sheets, especially grain-oriented ones Electrical sheets, with an evenly adhering Glass film and with improved magnetic properties, in which the hot strip initially produced and possibly annealed except for the final cold strip thickness with at least one Cold rolling stage is cold rolled, then to the an annealing separator rolled to the final thickness is applied and dried and then the cold-rolled strip coated in a high-temperature annealing is subjected, with an integral part of the Glow separator an aqueous magnesium oxide (MgO) dispersion and the glow separator is additionally at least one Has additive.
- MgO aqueous magnesium oxide
- decarburization annealing is carried out after rolling to the final thickness.
- the carbon is extracted from the material.
- An oxide layer forms as a base layer on the strip surface, the essential components of which are silicon dioxide (SiO 2 ) and fayalite (Fe 2 SiO 4 ).
- the strip is coated with a protective layer and subjected to a long-term annealing in the coil.
- the adhesive protection layer is intended to prevent the individual coil turns from sticking together during long-term annealing and, on the other hand, to form an insulation layer (glass film) with the base layer on the strip surface.
- the adhesive protection layer consists essentially of magnesium oxide (MgO).
- the MgO is slurried in water in the form of a powder, applied to the belt and dried. During this process, part of the magnesium oxide reacts with the water to form magnesium hydroxide (Mg (OH) 2 ). The amount of water bound to magnesium hydroxide, based on the total amount of oxide powder, is called the loss on ignition.
- Equation (I) shows the dehydration of the magnesium hydroxide, which starts at about 350 ° C. It is important for an optimally running process, both in terms of the insulation and the development of the magnetic properties, that the amount of water released is within certain limits.
- the water humidifies the predominantly hydrogen-containing annealing atmosphere and thus sets a corresponding oxidation potential.
- the annealing atmosphere must not be too dry because the glass film would be made too thin under such conditions. However, it must also not become too moist, because then it will be reoxidized too much and the glass film will have defects such as local flaking and poor adhesion.
- additives to MgO powder were introduced to improve the formation of the insulation layer and the magnetic properties of the finished product.
- These include titanium dioxide (TiO 2 ), boron compounds such as boron oxide (B 2 O 3 ) or sodium tetraborate (Na 2 B 4 O 7 ), as well as antimony compounds such as antimony sulfate (Sb 2 (SO 4 ) 3 ) in combination with a chloride, preferably antimony chloride SbCl 3 .
- TiO 2 titanium dioxide
- boron compounds such as boron oxide (B 2 O 3 ) or sodium tetraborate (Na 2 B 4 O 7 )
- antimony compounds such as antimony sulfate (Sb 2 (SO 4 ) 3 ) in combination with a chloride, preferably antimony chloride SbCl 3 .
- the additives used often also have disadvantages that reduce the product quality. Overall, the processing of such additives is cumbersome, since some of them have to be dissolved in previously
- the invention is based on the object of measures to meet, especially by modifying the Glow separators to the insulation properties and at the same time the magnetic properties of the Finished product to improve further.
- the Anti-adhesive layer can be applied more homogeneously quality-reducing phenomena, such as glow contours and to avoid local defects.
- one should easy handling can be guaranteed and the cost, am Standard measured, kept low.
- a readily water-soluble one Sodium phosphate compound is used.
- a readily water soluble sodium phosphate compound and a finely dispersed oxidic aluminum compound Glow separator can be added.
- the good water solubility of the sodium phosphate compound if necessary in combination with the finely dispersed distribution of the oxidic aluminum compound in the specified amounts ensure a homogeneous application of the adhesive protection, prevent coagulation within the aqueous Magnesium oxide dispersion and associated local Defects in the glass film and promote those in the Long-term annealing chemical reactions between the one on the belt surface Base layer and the adhesive protective layer to the glass film.
- a stronger than the standard Glass film formation that the interaction between the Annealing atmosphere and the strips are positively influenced the magnetic properties of the electrical sheets improved.
- a method with the generic measures has been known from EP 0 232 537 B1.
- a titanium compound such as TiO 2
- a boron compound such as B 2 O 3
- a sulfur compound such as SrS
- the MgO-based annealing separator is added to the MgO-based annealing separator as an additive, with the aim of improving the insulation properties, such as Adhesion and the appearance of the glass film to influence positively. This is achieved by hydrating the coating.
- the magnetic properties were also improved by the addition of such additives.
- JP-5-513 8021 describes a release agent based on MgO, which contains up to 50% by weight of Mg (OH) 2 and up to 5% by weight of Al (OH) 3 or Al (NO 3 ) 3 contains. It has been shown that the use of such a release agent for coating electrical sheets does not have an adverse effect on the magnetic properties of the product.
- JP-5-247 661 describes a process for the production of grain-oriented silicon steels which are coated with a glass layer.
- improvements in the magnetic properties and the surface properties of the coated steel are achieved by using release agent additives such as Sb 2 (SO 4 ) 3 , V 2 O s , SrS, Na 2 B 4 O 7 and Ca (H 2 PO 4 ) 2 .
- the positive influence on which the invention is based the magnetic properties is characteristic of the sodium phosphates.
- FIG. 1 shows the superiority of the samples produced by the method according to the invention with an MgO-based adhesive protection doped with sodium phosphate over other phosphate additives.
- HGO high permeability grain oriented tape samples were coated with MgO + 6% TiO 2 + the listed additives, dried and annealed.
- the sodium phosphates are readily water-soluble, allow thus an optimally homogeneous distribution within the Anti-adhesive layer.
- Sodium phosphates in the present case in particular using the example of Sodium pyrophosphate decahydrate are reported both the magnetic properties polarization and Magnetic loss, as well Isolation training improved.
- the Inhibitor test method is demonstrated that the Sodium pyrophosphate to a prematurely stronger one Glass film formation leads.
- the inhibitor test stops Process in which, in principle, high annealing certain annealing temperatures are canceled and the Samples can be assessed magnetically. In the present case the insulation training was also assessed.
- the magnetic properties of loss of magnetization P 1.7 and polarization J 800 were determined on the annealed strips.
- the aluminum compounds used as a further additive in addition to the sodium phosphate compound are aluminum oxides or hydroxides of the form Al 2 O 3 , AlO (OH) 3 and AL (OH), the effect of which is fully exploited when the corresponding particle sizes are small. The effect is particularly evident when the compounds are added in the form of sols (very fine particles / water mixtures).
- the average particle size should be less than 100 nm with the narrowest possible particle size distribution.
- the addition of these aluminum compounds leads to a considerable improvement in loss, similar to the case with the addition of titanium dioxide.
- the advantage of the aluminum compound as an additive over titanium dioxide is the lower dosage and the more homogeneous distribution of the particles. Another advantage lies in the fact that the aluminum compounds added also have the property of a ceramic binder, and the adhesive protective layer therefore adheres better to the tape.
- Table 6 and Figure 3 show the influence of the selected aluminum compounds on the magnetic loss. Influence of different oxidic aluminum compounds on the magnetic properties and the glass film appearance
- Boehmite AIO (OH) 0 0.5 2nd Glass film appearance
- the effect of the above additives is optimized, if suitable combinations of additives are used. This also has positive effects in combination with additives already used, such as titanium dioxide, Antimony sulfate and sodium tetraborate achieved. Related to the slurry properties and thus the homogeneity of the MgO layer turns out to be a combination of one finely dispersed oxidic aluminum compound and one well water-soluble sodium phosphate as optimal because with these additives significantly fewer local defects to be observed.
- the magnetic properties of loss of magnetization P 1.7 and polarization J 800 were determined on the annealed strips.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Soft Magnetic Materials (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Laminated Bodies (AREA)
- Glass Compositions (AREA)
- Insulating Bodies (AREA)
- Inorganic Insulating Materials (AREA)
- Cell Separators (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Elektroblechen, insbesondere von kornorientierten Elektroblechen, mit einem gleichmäßigen gut haftenden Glasfilm und mit verbesserten magnetischen Eigenschaften, bei dem das zunächst erzeugte und ggf. geglühte Warmband bis auf die Kaltband-Enddicke mit mindestens einer Kaltwalzstufe kaltgewalzt wird, anschließend auf das bis auf die Enddicke gewalzte Band ein Glühseparator aufgebracht und getrocknet wird und im Anschluß daran das so beschichtete Kaltband einer Hochtemperaturglühung unterworfen wird, wobei wesentlicher Bestandteil des Glühseparators eine wäßrige Magnesiumoxid(MgO)-Dispersion ist und der Glühseparator zusätzlich mindestens ein Additiv aufweist.The invention relates to a method for producing Electrical sheets, especially grain-oriented ones Electrical sheets, with an evenly adhering Glass film and with improved magnetic properties, in which the hot strip initially produced and possibly annealed except for the final cold strip thickness with at least one Cold rolling stage is cold rolled, then to the an annealing separator rolled to the final thickness is applied and dried and then the cold-rolled strip coated in a high-temperature annealing is subjected, with an integral part of the Glow separator an aqueous magnesium oxide (MgO) dispersion and the glow separator is additionally at least one Has additive.
Bei der Fertigung von kornorientiertem Elektroblech wird nach dem Walzen auf Enddicke eine Entkohlungsglühung durchgeführt. Dabei wird dem Werkstoff der Kohlenstoff entzogen. An der Bandoberfläche bildet sich dabei eine Oxidschicht als Grundschicht, deren wesentliche Bestandteile Siliziumdioxid (SiO2) und Fayalit (Fe2SiO4) sind. Im Anschluß an die Entkohlungsglühung wird das Band mit einer Klebschutzschicht beschichtet und im Coil einer Langzeitglühung unterzogen. Die Klebschutzschicht soll zum einen das Zusammenkleben der einzelnen Coilwindungen während der Langzeitglühung verhindern und zum anderen mit der Grundschicht auf der Bandoberfläche eine Isolationsschicht (Glasfilm) bilden. Die Klebschutzschicht besteht im wesentlichen aus Magnesiumoxid (MgO). Das MgO wird in Form eines Pulvers in Wasser aufgeschlämmt, auf das Band aufgetragen und getrocknet. Bei diesem Vorgang reagiert ein Teil des Magnesiumoxides mit dem Wasser zu Magnesiumhydroxid (Mg(OH)2). Die an Magnesiumhydroxid gebundene Menge Wasser, bezogen auf die Gesamtoxidpulvermenge, wird als Glühverlust bezeichnet.In the production of grain-oriented electrical sheet, decarburization annealing is carried out after rolling to the final thickness. The carbon is extracted from the material. An oxide layer forms as a base layer on the strip surface, the essential components of which are silicon dioxide (SiO 2 ) and fayalite (Fe 2 SiO 4 ). Following the decarburization annealing, the strip is coated with a protective layer and subjected to a long-term annealing in the coil. On the one hand, the adhesive protection layer is intended to prevent the individual coil turns from sticking together during long-term annealing and, on the other hand, to form an insulation layer (glass film) with the base layer on the strip surface. The adhesive protection layer consists essentially of magnesium oxide (MgO). The MgO is slurried in water in the form of a powder, applied to the belt and dried. During this process, part of the magnesium oxide reacts with the water to form magnesium hydroxide (Mg (OH) 2 ). The amount of water bound to magnesium hydroxide, based on the total amount of oxide powder, is called the loss on ignition.
Die auf die Isolation bezogenen wesentlichen Abläufe und Reaktionen zwischen Bandoberfläche und Klebschutzschicht während der Langzeitglühung sind nachfolgend vereinfacht zusammengefaßt:The essential processes and related to isolation Reactions between the tape surface and the protective layer during long-term annealing are simplified below summarized:
In der Vergangenheit wurden eine Reihe von Zusätzen zum MgO-Pulver eingeführt, die die Ausbildung der Isolationsschicht und die magnetischen Eigenschaften des Fertigproduktes verbessern sollen. Dazu zählen Titandioxid (TiO2), Borverbindungen, wie Boroxid (B2O3) oder Natriumtetraborat (Na2B4O7), sowie Antimonverbindungen, wie z.B. Antimonsulfat (Sb2(SO4)3) in Kombination mit einem Chlorid, vorzugsweise Antimonchlorid SbCl3. Die eingesetzten Zusätze weisen neben den positiven Einflüssen auf die jeweiligen Zielgrößen allerdings häufig auch Nachteile auf, die die Produktqualität herabsetzen. Insgesamt ist die Verarbeitung derartiger Zusätze umständlich, da diese z.T. in vorher erhitztem Wasser gelöst werden müssen. Besonders bei den schwer wasserlöslichen Salzen Natriumtetraborat und insbesondere Antimonsulfat führen nicht gelöste, grobe Partikel zu Inhomogenitäten in der Klebschutzschicht und nachfolgend zu lokalen Fehlstellen im Glasfilm. Bei Antimonsulfat kommt hinzu, daß die Verbindung teuer ist und in die Kategorie der "minder giftigen" Substanzen eingestuft wird. Eine inhomogene Verteilung von Titandioxid im Klebschutz führt zu Fehlstellen im Glasfilm.In the past, a number of additives to MgO powder were introduced to improve the formation of the insulation layer and the magnetic properties of the finished product. These include titanium dioxide (TiO 2 ), boron compounds such as boron oxide (B 2 O 3 ) or sodium tetraborate (Na 2 B 4 O 7 ), as well as antimony compounds such as antimony sulfate (Sb 2 (SO 4 ) 3 ) in combination with a chloride, preferably antimony chloride SbCl 3 . In addition to the positive influences on the respective target values, the additives used often also have disadvantages that reduce the product quality. Overall, the processing of such additives is cumbersome, since some of them have to be dissolved in previously heated water. Especially with the poorly water-soluble salts sodium tetraborate and in particular antimony sulfate, undissolved, coarse particles lead to inhomogeneities in the adhesive protective layer and subsequently to local defects in the glass film. In addition, with antimony sulfate, the compound is expensive and is classified in the category of "less toxic" substances. An inhomogeneous distribution of titanium dioxide in the adhesive protection leads to defects in the glass film.
Der Erfindung liegt nun die Aufgabe zugrunde, Maßnahmen zu treffen, insbesondere durch Modifizierung des Glühseparators, um die Isolationseigenschaften und gleichzeitig die magnetischen Eigenschaften des Fertigprodukts weiter zu verbessern. Dabei soll die Klebschutzschicht homogener aufgetragen werden können, um qualitätsmindernde Erscheinungen, wie Glühkonturen und lokale Fehlstellen, zu vermeiden. Daneben soll eine einfache Handhabung gewährleistet sein und die Kosten, am Standard gemessen, niedrig gehalten werden. The invention is based on the object of measures to meet, especially by modifying the Glow separators to the insulation properties and at the same time the magnetic properties of the Finished product to improve further. Thereby the Anti-adhesive layer can be applied more homogeneously quality-reducing phenomena, such as glow contours and to avoid local defects. In addition, one should easy handling can be guaranteed and the cost, am Standard measured, kept low.
Zur Lösung dieser Aufgabe wird bei dem gattungsgemäßen Verfahren erfindungsgemäß vorgeschlagen, daß als mindestens ein Additiv eine gut wasserlösliche Natriumphosphatverbindung verwendet wird. Gemäß einer weiteren vorteilhaften Ausgestaltung des erfindungsgemäßen Verfahrens können als weitere Additive eine gut wasserlösliche Natriumphosphatverbindung und eine feindisperse oxidische Aluminiumverbindung dem Glühseparator zugesetzt werden.To solve this problem is the generic Method proposed according to the invention that as at least one additive is a readily water-soluble one Sodium phosphate compound is used. According to one another advantageous embodiment of the The inventive method can be used as further additives a readily water soluble sodium phosphate compound and a finely dispersed oxidic aluminum compound Glow separator can be added.
Die gute Wasserlöslichkeit der Natriumphosphatverbindung, ggfs. in Kombination mit der feindispersen Verteilung der oxidischen Aluminiumverbindung in den angegebenen Mengen gewährleisten eine homogene Auftragung des Klebschutzes, verhindern Koagulationen innerhalb der wäßrigen Magnesiumoxiddispersion und damit verbundene lokale Fehlstellen im Glasfilm und fördern die in der Langzeitglühung ablaufenden chemischen Reaktionen zwischen der auf der Bandoberfläche befindlichen Grundschicht und der Klebschutzschicht zum Glasfilm. Durch eine gegenüber dem Standard stärker einsetzende Glasfilmbildung, die die Wechselwirkung zwischen der Glühatmosphäre und den Bändern positiv beeinflußt, werden die magnetischen Eigenschaften der Elektrobleche verbessert.The good water solubility of the sodium phosphate compound, if necessary in combination with the finely dispersed distribution of the oxidic aluminum compound in the specified amounts ensure a homogeneous application of the adhesive protection, prevent coagulation within the aqueous Magnesium oxide dispersion and associated local Defects in the glass film and promote those in the Long-term annealing chemical reactions between the one on the belt surface Base layer and the adhesive protective layer to the glass film. By using a stronger than the standard Glass film formation that the interaction between the Annealing atmosphere and the strips are positively influenced the magnetic properties of the electrical sheets improved.
Ein Verfahren mit den gattungsgemäßen Maßnahmen ist aus
der EP 0 232 537 B1 bekannt gewesen. Bei diesem bekannten
Verfahren wird dem Glühseparator auf MgO-Basis als
Additiv eine Titanverbindung, wie TiO2, und/oder eine
Borverbindung, wie B2O3, und/oder eine Schwefelverbindung,
wie SrS, mit dem Ziel zugesetzt, die Isolationseigenschaften,
wie Haftung und das Aussehen des Glasfilms,
positiv zu beeinflussen. Erreicht wird dies durch eine
Hydratation der Beschichtung. Auch die magnetischen
Eigenschaften wurden durch den Zusatz solcher Additive
verbessert.A method with the generic measures has been known from
In der JP-5-513 8021 wird ein Trennmittel auf der Basis von MgO beschrieben, welches als Zusätze bis zu 50 Gew.-% Mg(OH)2 sowie bis zu 5 Gew.-% Al(OH)3 oder Al(NO3)3 enthält. Es wurde gezeigt, daß sich die Verwendung eines solchen Trennmittels zur Beschichtung von Elektroblechen nicht ungünstig auf die magnetischen Eigenschaften des Produkts auswirken.JP-5-513 8021 describes a release agent based on MgO, which contains up to 50% by weight of Mg (OH) 2 and up to 5% by weight of Al (OH) 3 or Al (NO 3 ) 3 contains. It has been shown that the use of such a release agent for coating electrical sheets does not have an adverse effect on the magnetic properties of the product.
Die JP-5-247 661 beschreibt ein Verfahren zur Herstellung von kornorientierten Siliciumstählen, die mit einer Glasschicht beschichtet sind. Bei diesem Verfahren werden durch Verwendung von Trennmitteladditiven wie Sb2(SO4)3, V2Os, SrS, Na2B4O7 und Ca(H2PO4)2 Verbesserungen der magnetischen Eigenschaften sowie der Obenflächenbeschaffenheit des beschichteten Stahls erzielt.JP-5-247 661 describes a process for the production of grain-oriented silicon steels which are coated with a glass layer. In this process, improvements in the magnetic properties and the surface properties of the coated steel are achieved by using release agent additives such as Sb 2 (SO 4 ) 3 , V 2 O s , SrS, Na 2 B 4 O 7 and Ca (H 2 PO 4 ) 2 .
Der der Erfindung zugrunde liegende positive Einfluß auf die magnetischen Eigenschaften ist charakteristisch für die Natriumphosphate.The positive influence on which the invention is based the magnetic properties is characteristic of the sodium phosphates.
Fig. 1 zeigt die Überlegenheit der nach dem erfindungsgemäßen Verfahren hergestellten Proben mit einem Natriumphosphat dotierten Klebschutz auf MgO-Basis gegenüber anderen Phosphatzusätzen. Dabei wurden HGO (high permeability grain oriented) Bandproben mit MgO + 6% TiO2 + den aufgeführten Zusätzen beschichtet, getrocknet und hochgeglüht.FIG. 1 shows the superiority of the samples produced by the method according to the invention with an MgO-based adhesive protection doped with sodium phosphate over other phosphate additives. HGO (high permeability grain oriented) tape samples were coated with MgO + 6% TiO 2 + the listed additives, dried and annealed.
Die Natriumphosphate sind gut wasserlöslich, ermöglichen damit eine optimal homogene Verteilung innerhalb der Klebschutzschicht. Durch die bevorzugte Verwendung der Natriumphosphate, vorliegend insbesondere am Beispiel des Natriumpyrophosphat Decahydrat ausgewiesen, werden sowohl die magnetischen Eigenschaften Polarisation und Ummagnetisierungsverlust, als auch die Isolationsausbildung verbessert. Im Inhibitortestverfahren wird nachgewiesen, daß das Natriumpyrophosphat zu einer vorzeitig stärkeren Glasfilmbildung führt. Der Inhibitortest stellt ein Verfahren dar, bei dem prinzipiell Hochglühungen bei bestimmten Glühtemperaturen abgebrochen werden und die Proben magnetisch beurteilt werden. Im vorliegenden Fall wurden zusätzlich die Isolationsausbildungen bewertet.The sodium phosphates are readily water-soluble, allow thus an optimally homogeneous distribution within the Anti-adhesive layer. Through the preferred use of the Sodium phosphates, in the present case in particular using the example of Sodium pyrophosphate decahydrate are reported both the magnetic properties polarization and Magnetic loss, as well Isolation training improved. in the Inhibitor test method is demonstrated that the Sodium pyrophosphate to a prematurely stronger one Glass film formation leads. The inhibitor test stops Process in which, in principle, high annealing certain annealing temperatures are canceled and the Samples can be assessed magnetically. In the present case the insulation training was also assessed.
Jeweils 3 Bandproben aus 3 Bändern kornorientierten
Elektroblechs der Güte HGO (high permeability
grainoriented) und der Dicke 0,23 mm wurde zum einen mit
einer wäßrigen Magnesiumoxiddispersion und zum anderen
mit einer wäßrigen Magnesiumoxiddispersion, der 0,75 %
Natriumpyrophosphat Decahydrat, bezogen auf 100 %
Magnesiumoxid, zugesetzt wurde, beschichtet. Nachdem die
Bandproben entsprechend dem Stand der Technik hochgeglüht
wurden, wurden die magnetischen Kenngrößen bestimmt.
Tabelle 1 gibt die magnetischen Kenngrößen Polarisation
J800 und Ummagnetisierungsverlust P1,7 zum Vergleich der
beiden Beschichtungen wieder.
6 Bandproben aus kornorientiertem Elektroblech (HGO) der
Nenndicke 0,23 mm, deren chemische Zusammensetzung
willkürlich innerhalb des Analysenbereichs
29 Bandproben aus kornorientiertem Elektroblech (HGO) der
Nenndicke 0,23 mm, deren chemische Zusammensetzung
willkürlich innerhalb des Analysenbereichs
Elektroblechproben der Dicke 0,29 mm und der chemischen
Zusammensetzungen
%
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%
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%
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%
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%
%
Bänder aus kornorientiertem Elektroblech der Nenndicke
0,23 mm, die im Verfahren nach dem Stand der Technik bis
einschließlich der Entkohlung processiert wurden, wurden
mit einem Trennmittel auf der Basis Magnesiumoxid und
6 Gew.-Teilen Titandioxid, bezogen auf 100 Gew.-Teile
MgO, sowie den in Tabelle 5 aufgeführten Zusätzen
beschichtet und anschließend entsprechend dem Stand der
Technik hochgeglüht. An den hochgeglühten Bändern wurden
die magnetischen Eigenschaften Ummagnetisierungsverlust
P1,7 und Polarisation J800 bestimmt.
Die als weiteres Additiv neben der Natriumphosphatverbindung verwendeten Aluminiumverbindungen sind Aluminiumoxide bzw. -hydroxide der Form Al2O3, AlO(OH)3 und AL(OH) deren Wirkung dann voll ausgeschöpft wird, wenn die entsprechenden Partikelgrößen klein sind. Die Wirkung zeigt sich besonders deutlich, wenn die Verbindungen in Form von Solen (feinste Partikel/Wasser-Gemische) zugegeben werden. Die Partikelgröße sollte im Mittel kleiner als 100nm bei einer möglichst engen Partikelgrößenverteilung sein. Die Zugabe dieser Aluminiumverbindungen führt zu einer erheblichen Verlustverbesserung, ähnlich wie es bei der Zugabe von Titandioxid der Fall ist. Der Vorteil der Aluminiumverbindung als Zusatz gegenüber Titandioxid sind die geringer dosierten Zugaben und die homogenere Verteilung der Partikel. Ein weiterer Vorteil liegt in der Tatsache, daß die zugegebenen Aluminiumverbindungen auch die Eigenschaft eines keramischen Binders haben, die Klebschutzschicht demnach besser am Band haftet.The aluminum compounds used as a further additive in addition to the sodium phosphate compound are aluminum oxides or hydroxides of the form Al 2 O 3 , AlO (OH) 3 and AL (OH), the effect of which is fully exploited when the corresponding particle sizes are small. The effect is particularly evident when the compounds are added in the form of sols (very fine particles / water mixtures). The average particle size should be less than 100 nm with the narrowest possible particle size distribution. The addition of these aluminum compounds leads to a considerable improvement in loss, similar to the case with the addition of titanium dioxide. The advantage of the aluminum compound as an additive over titanium dioxide is the lower dosage and the more homogeneous distribution of the particles. Another advantage lies in the fact that the aluminum compounds added also have the property of a ceramic binder, and the adhesive protective layer therefore adheres better to the tape.
4 Bandproben aus kornorientiertem Elektroblech der
Nenndicke 0,23 mm, deren chemische Zusammensetzung
willkürlich innerhalb des Analysenbereichs
%
%
%
%
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Die Wirkung der obengenannten Zusätze wird optimiert, wenn geeignete Kombinationen von Zusätzen benutzt werden. Dabei werden auch positive Effekte in Kombination mit bereits eingesetzten Zusätzen, wie Titandioxid, Antimonsulfat und Natriumtetraborat erzielt. Bezogen auf die Slurryeigenschaften und damit auf die Homogenität der MgO-Schicht erweist sich eine Kombination einer feindispersen oxidischen Aluminiumverbindung und eines gut wasserlöslichen Natriumphosphates als optimal, da mit diesen Zusätzen deutlich weniger lokale Fehlstellen beobachtet werden.The effect of the above additives is optimized, if suitable combinations of additives are used. This also has positive effects in combination with additives already used, such as titanium dioxide, Antimony sulfate and sodium tetraborate achieved. Related to the slurry properties and thus the homogeneity of the MgO layer turns out to be a combination of one finely dispersed oxidic aluminum compound and one well water-soluble sodium phosphate as optimal because with these additives significantly fewer local defects to be observed.
Proben aus einem Band aus kornorientiertem Elektroblech der Nenndicke 0,23 mm, die im Verfahren nach dem Stand der Technik bis einschließlich der Entkohlung processiert wurden, wurden mit einem Trennmittel auf der Basis Magnesiumoxid und den in Tabelle 7 aufgeführten Zusätzen beschichtet und anschließend entsprechend dem Stand der Technik hochgeglüht. An den hochgeglühten Bändern wurden die magnetischen Eigenschaften Ummagnetisierungsverlust P1,7 und Polarisation J800 bestimmt. Samples from a strip of grain-oriented electrical sheet with a nominal thickness of 0.23 mm, which were processed in the process according to the prior art up to and including decarburization, were coated with a release agent based on magnesium oxide and the additives listed in Table 7 and then in accordance with the status of technology glowed. The magnetic properties of loss of magnetization P 1.7 and polarization J 800 were determined on the annealed strips.
Claims (7)
- A method for producing electric sheets, in particular grain-oriented electric sheets, with an evenly well-adhering glass film and with improved magnetic properties, in which the hot rolled strip which is produced at first and is optionally annealed is cold-rolled up to the end thickness of the cold strip with at least one cold rolling stage, thereafter an annealing separator is applied to the strip which is rolled up to the end thickness, and is dried, and thereafter the cold strip which is thus coated is subjected to a high-temperature annealing, with a hydrous magnesium oxide (MgO) dispersion being an important component of the annealing separator and the annealing separator being provided with at least one additive, characterised in that a favourably water-soluble sodium phosphate compound is used as at least one additive.
- A method according to claim 1, characterised in that at least two additives are used, namely a favourably water-soluble sodium phosphate compound and a finely dispersed oxidic aluminium compound.
- A method according to claim 1 or 2, characterised in that 0.05 to 4.0 % sodium phosphate, relating to the MgO quantity, is added to the annealing separator as additive.
- A method according to claim 1 or 2, characterised in that 0.3 to 1.5 % of sodium pyrophosphate decahydrate, relating to the MgO quantity, is added to the annealing separator as additive.
- A method according to claims 2, 3 or 4, characterised in that 0.05 to 4.0 % of the finely dispersed oxidic aluminium compound, relating to the MgO quantity, is added to the annealing separator as additive.
- A method according to claims 2, 3, 4 or 5, characterised in that the oxidic aluminium compound is used with a particle size below 100 nm.
- A method according to claim 1 to 6, characterised in that further additives such as titanium dioxide, boron oxide, sodium tetraborate, antimony sulphate, metal chloride, preferably antimony chloride, are added to the annealing separator.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4409691 | 1994-03-22 | ||
DE4409691A DE4409691A1 (en) | 1994-03-22 | 1994-03-22 | Process for the production of electrical sheets with a glass coating |
PCT/EP1995/001020 WO1995025820A1 (en) | 1994-03-22 | 1995-03-18 | Process for producing magnetic steel sheets with a glass coating |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0752012A1 EP0752012A1 (en) | 1997-01-08 |
EP0752012B1 true EP0752012B1 (en) | 1998-08-26 |
Family
ID=6513410
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95912252A Expired - Lifetime EP0752012B1 (en) | 1994-03-22 | 1995-03-18 | Process for producing magnetic steel sheets with a glass coating |
Country Status (10)
Country | Link |
---|---|
US (1) | US5863356A (en) |
EP (1) | EP0752012B1 (en) |
JP (1) | JP3730254B2 (en) |
KR (1) | KR100367985B1 (en) |
AT (1) | ATE170226T1 (en) |
CZ (1) | CZ292216B6 (en) |
DE (2) | DE4409691A1 (en) |
PL (1) | PL178890B1 (en) |
RU (1) | RU2139945C1 (en) |
WO (1) | WO1995025820A1 (en) |
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JP3475258B2 (en) * | 1994-05-23 | 2003-12-08 | 株式会社海水化学研究所 | Ceramic film forming agent and method for producing the same |
DE19750066C1 (en) * | 1997-11-12 | 1999-08-05 | Ebg Elektromagnet Werkstoffe | Process for coating electrical steel strips with an annealing separator |
DE102004014596A1 (en) * | 2004-03-23 | 2005-10-27 | Trithor Gmbh | Non-stick coating for the production of composite material wires |
JP5633178B2 (en) * | 2010-04-27 | 2014-12-03 | Jfeスチール株式会社 | Annealing separator for grain-oriented electrical steel sheet |
DE102010038038A1 (en) * | 2010-10-07 | 2012-04-12 | Thyssenkrupp Electrical Steel Gmbh | Process for producing an insulation coating on a grain-oriented electro-steel flat product and electro-flat steel product coated with such an insulation coating |
CN102453793B (en) * | 2010-10-25 | 2013-09-25 | 宝山钢铁股份有限公司 | Annealing isolation agent used for preparing mirror surface-oriented silicon steel with excellent magnetic property |
KR101453235B1 (en) * | 2011-01-12 | 2014-10-22 | 신닛테츠스미킨 카부시키카이샤 | Grain-oriented magnetic steel sheet and process for manufacturing same |
JP5360272B2 (en) * | 2011-08-18 | 2013-12-04 | Jfeスチール株式会社 | Method for producing grain-oriented electrical steel sheet |
CN103857827B (en) * | 2011-10-04 | 2016-01-20 | 杰富意钢铁株式会社 | Orientation electromagnetic steel plate annealing separation agent |
DE102015114358B4 (en) | 2015-08-28 | 2017-04-13 | Thyssenkrupp Electrical Steel Gmbh | Method for producing a grain-oriented electrical strip and grain-oriented electrical strip |
KR101909218B1 (en) * | 2016-12-21 | 2018-10-17 | 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 |
JP6939767B2 (en) | 2018-12-27 | 2021-09-22 | Jfeスチール株式会社 | Annealing separator for grain-oriented electrical steel sheets and manufacturing method of grain-oriented electrical steel sheets |
JP6939766B2 (en) * | 2018-12-27 | 2021-09-22 | Jfeスチール株式会社 | Annealing separator for grain-oriented electrical steel sheets and manufacturing method of grain-oriented electrical steel sheets |
CN111906142B (en) * | 2020-06-24 | 2022-08-16 | 浙江博星工贸有限公司 | Process for controlling mechanical property of cold-rolled stainless steel strip |
CN114014529B (en) * | 2021-12-17 | 2023-02-21 | 中国建筑材料科学研究总院有限公司 | Isolating agent for fire polishing of borosilicate glass beads |
CN114854960B (en) * | 2022-03-30 | 2023-09-05 | 武汉钢铁有限公司 | Annealing isolating agent for reducing surface defects of oriented silicon steel and use method thereof |
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-
1994
- 1994-03-22 DE DE4409691A patent/DE4409691A1/en not_active Withdrawn
-
1995
- 1995-03-18 US US08/704,579 patent/US5863356A/en not_active Expired - Lifetime
- 1995-03-18 WO PCT/EP1995/001020 patent/WO1995025820A1/en active IP Right Grant
- 1995-03-18 AT AT95912252T patent/ATE170226T1/en not_active IP Right Cessation
- 1995-03-18 RU RU96119243A patent/RU2139945C1/en active
- 1995-03-18 PL PL95316139A patent/PL178890B1/en unknown
- 1995-03-18 JP JP52437895A patent/JP3730254B2/en not_active Expired - Lifetime
- 1995-03-18 CZ CZ19962738A patent/CZ292216B6/en not_active IP Right Cessation
- 1995-03-18 KR KR1019960705227A patent/KR100367985B1/en not_active IP Right Cessation
- 1995-03-18 DE DE59503345T patent/DE59503345D1/en not_active Expired - Lifetime
- 1995-03-18 EP EP95912252A patent/EP0752012B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US5863356A (en) | 1999-01-26 |
CZ292216B6 (en) | 2003-08-13 |
KR100367985B1 (en) | 2003-08-02 |
DE4409691A1 (en) | 1995-09-28 |
CZ273896A3 (en) | 1997-04-16 |
JPH09510503A (en) | 1997-10-21 |
KR970701795A (en) | 1997-04-12 |
PL178890B1 (en) | 2000-06-30 |
ATE170226T1 (en) | 1998-09-15 |
JP3730254B2 (en) | 2005-12-21 |
PL316139A1 (en) | 1996-12-23 |
RU2139945C1 (en) | 1999-10-20 |
EP0752012A1 (en) | 1997-01-08 |
WO1995025820A1 (en) | 1995-09-28 |
DE59503345D1 (en) | 1998-10-01 |
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