EP2252722B1 - Verfahren zur herstellung eines kornorientierten elektrobands - Google Patents

Verfahren zur herstellung eines kornorientierten elektrobands Download PDF

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Publication number
EP2252722B1
EP2252722B1 EP09711112A EP09711112A EP2252722B1 EP 2252722 B1 EP2252722 B1 EP 2252722B1 EP 09711112 A EP09711112 A EP 09711112A EP 09711112 A EP09711112 A EP 09711112A EP 2252722 B1 EP2252722 B1 EP 2252722B1
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Prior art keywords
phosphate
phosphate solution
solution
colloid
magnetic strip
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German (de)
English (en)
French (fr)
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EP2252722A2 (de
Inventor
Christof Holzapfel
Carsten Schepers
Heiner Schrapers
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ThyssenKrupp Electrical Steel GmbH
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ThyssenKrupp Electrical Steel GmbH
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • 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
    • C21D8/1288—Application of a tension-inducing coating
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/24—Magnetic cores
    • H01F27/25—Magnetic cores made from strips or ribbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0213—Manufacturing of magnetic circuits made from strip(s) or ribbon(s)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12465—All metal or with adjacent metals having magnetic properties, or preformed fiber orientation coordinate with shape

Definitions

  • the invention relates to a method for producing a grain-oriented electrical tape which is coated with a phosphate layer.
  • a phosphate-coated, grain-oriented electrical steel which can be produced by the process of the present invention can be used as a core material in a transformer.
  • Electrical steel is a well-known material of the steel industry with special magnetic properties.
  • the material usually has a thickness of 0.2 mm to 0.5 mm and is produced by a complex manufacturing process, consisting of cold rolling and heat treatment processes.
  • the metallurgical properties of the material, the degree of deformation of the cold rolling processes and the parameters of the heat treatment steps are coordinated so that targeted recrystallization processes occur.
  • These recrystallization processes lead to the typical for the material "Goss texture", in which the direction of the easiest magnetization in the rolling direction of the finished strips.
  • Base material for electrical steel is a silicon steel sheet.
  • grain-oriented electrical steel and non-grain-oriented electrical steel.
  • non-grain oriented electrical steel the magnetic flux is set to no particular direction, so that it is the same in all directions form good magnetic properties (isotropic magnetization).
  • Anisotropic electrical steel exhibits strongly anisotropic magnetic behavior. This is due to a uniform orientation of the crystallites (crystallographic texture). In the case of grain-oriented electrical steel, efficient production of grain growth is carried out by the complex production. Its grains show a nearly ideal texture with a slight misorientation in the final annealed material - the "Goss texture” named after its inventor.
  • the surfaces of electrical steel are usually coated with oxide layers and inorganic phosphate layers. These should act essentially electrically insulating.
  • Grain-oriented electrical steel is particularly suitable for applications in which it depends on a particularly low loss of magnetization loss and particularly high demands on permeability or polarization are made, as in power transformers, distribution transformers and higher quality small transformers.
  • the main application is grain-oriented electrical steel as a core material in transformers.
  • the cores of the transformers consist of stacked electrical steel panels (lamellas).
  • the electric strip boards are stacked so that the rolling direction with the easiest magnetization is always aligned in the direction of the effective coil magnetic field.
  • the energy loss in Ummagnethnes revitalizen in the alternating field is minimal. Due to this connection, the total energy loss of a transformer depends, among other things, on the quality of the electrical tape used in the core.
  • noise generation also plays a role in transformers. This is based on a known as magnetostriction physical effect and is among other things influenced by the properties of the electrical steel core material used.
  • a two-ply layer system with a ceramic-like layer disposed on the electrical tape (commonly referred to as a glass film) and a phosphate film disposed on the glass film.
  • This layer system is intended to ensure the required for the application in the stack electrical insulation of the slats.
  • the layer system can also influence the magnetic properties of the core material. By a tensile stress transmitted from the layer system to the base material, the magnetic reversal losses can be lowered again. In addition, the magnetostriction and thus the transformer noise are minimized by the tensile stress.
  • the layer system usually consists of a glass film and an overlying phosphate layer. Both layers should exert permanent tensile stresses on the metallic core material.
  • the phosphate solution of the prior art may contain a colloidal component.
  • the tensile stress is generated by the colloid component, the phosphate itself acts as a binder.
  • Such systems of phosphate solutions / colloids are governed by laws commonly referred to as sol / gel transformation and known in various coating technologies.
  • sol / gel transformation it is advantageous if the sol / gel transition takes place after application of the phosphate solution to the strip surface, ie during the drying process.
  • the combination of a phosphate with a colloid component is not enough.
  • the sol / gel transition is sensitive to the pH of the solution, to contaminants with foreign substances, especially foreign ions, and to the temperature of use.
  • pure phosphate / colloid mixtures are too sensitive in terms of their stability.
  • the phosphate / colloid mixtures according to the prior art are additionally admixed with an addition of hexavalent chromium, which is usually brought into the solution as chromium trioxide or chromic acid.
  • hexavalent chromium which is usually brought into the solution as chromium trioxide or chromic acid.
  • chromium in particular hexavalent chromium
  • hexavalent chromium is used in the phosphatization of electrical steel special importance.
  • chromium is considered to play an important role.
  • the use of chromium is highlighted in the prior art in particular because hexavalent chromium improves the applicability of the phosphate solution on the strip surface and thus enables the creation of a homogeneous finished strip insulation layer.
  • hexavalent chromium prevents the formation of sticky finished film layers and modifies the interaction of the phosphate solution with the strip material such that no iron goes into solution.
  • hexavalent chromium influences the polymerization of the colloidal solution component such that it does not take place until the layer is dried at higher temperatures. This prevents uncontrolled polymerization or gel formation during the application of the phosphate solution to the strip surface-which would inevitably lead to time-consuming production stoppages.
  • hexavalent chromium in phosphate / colloid mixtures is essentially due to the fact that the transition from sol to gel is controlled so that it does not take place until the layer is dried during baking.
  • JP 2000 178760 A describes a method for producing a grain-oriented electrical tape coated with a phosphate layer, wherein a phosphate solution containing a colloid component and an organic acid is applied to the electrical steel strip.
  • a phosphate solution containing a colloid component and an organic acid is applied to the electrical steel strip.
  • the solution is chromium-free
  • the colloid stabilizer is used in an amount of 0.1 to 5 wt.% Based on the total weight of aluminum, magnesium and / or calcium phosphate
  • colloidal silica is used as a colloid component
  • the pH implicit ⁇ 3 the electrical tape provided with the phosphate solution is fired at a temperature of more than 800 ° C.
  • US Pat. No. 3,562,011 describes a process for preparing a grain-oriented electrical tape coated with a phosphate layer wherein a phosphate solution containing colloidal silica and 0.5% by weight of sodium oxide as a colloid stabilizer is applied to the electrical steel strip.
  • the tape can be used as a core material in a transformer.
  • JP 2007 023329 A describes a method for producing a grain-oriented electrical tape coated with a phosphate layer, wherein a chromium-free phosphate solution (magnesium phosphate) containing colloidal silica and ferric oxide is applied to the electrical steel strip.
  • a chromium-free phosphate solution magnesium phosphate
  • the electric tape provided with the phosphate solution is fired at a temperature of more than 800 ° C.
  • the object of the present invention is to provide a method for producing a phosphate layer on grain-oriented electrical steel, which makes it possible to dispense with the use of hexavalent chromium, without the above-mentioned disadvantages in the production to be accepted.
  • a homogeneous application of the phosphate solution and thus homogeneous finished layer qualities should be achieved.
  • This object is achieved by a method for producing a coated with a phosphate layer grain-oriented electrical tape in which on the electrical tape, a phosphate solution is applied, which contains a colloid component and at least one phosphoric acid ester as a colloid stabilizer (A) as an additive, and that the Phosphod solution has a content of hexavalent chromium of less than 0.2% by weight.
  • the phosphate solution contains a colloidal component is understood according to the invention that a proportion the phosphate solution consists of solid particles or supramolecular aggregates with sizes of a few nanometers to a few micrometers.
  • the size of the colloid component in the phosphate solution is in the range of 5 nm to 1 ⁇ m, preferably in the range of 5 nm to 100 nm, and more preferably in the range of 10 nm to 100 nm.
  • the proportion of the colloid component in the phosphate solution may vary.
  • the proportion of the colloid component in the phosphate solution is in the range of 5 wt% and 50 wt%, more preferably 5 wt% and 30 wt%.
  • a colloid component the most diverse substances can be used. Conveniently, these substances should not be phosphoric acid-soluble.
  • oxides preferably with Cr 2 O 3 , ZrO, SnO 2 , V 2 O 3 , Al 2 O 3 , SiO 2 , preferably as aqueous suspensions.
  • Particularly suitable is SiO 2 .
  • a colloid component which is particularly suitable according to the invention is thus silica sol. Excellent results are obtained with silica sol having a content of SiO 2 in water of from 10 to 50% by weight, preferably from 20 to 40% by weight. SiO 2 particularly useful particle sizes are 5 to 30 nm, preferably 10 to 20 nm.
  • the inventive method is characterized in that the phosphate solution contains a phosphoric acid ester as a colloid stabilizer (A) as an additive.
  • A a colloid stabilizer
  • This procedure can ensure that the transition from sol to gel takes place only during the drying of the phosphate layer.
  • colloid stabilizers allows homogeneous application of the phosphate solution resulting in homogeneous
  • phosphoric acid ester as colloidal stabilizer (A) thus makes it possible to dispense with the use of hexavalent chromium in the phosphate solution in the phosphating of electrical sheet, which largely avoids the problems that usually occur in chromium-free production using colloid-containing phosphate solutions can be.
  • Colloid stabilizers according to the invention are additives which stabilize colloids and prevent an uncontrolled sol / gel transition or coagulation of the solid.
  • colloid stabilizers furthermore ensure a temperature insensitivity in the range of application before application of the phosphate solution and make the system insensitive to foreign substances, in particular foreign ions.
  • phosphoric acid esters can be used as colloid stabilizer, provided that they are stable in acidic solutions. Furthermore, it is advantageous if the phosphoric acid esters do not disturb the stability of the colloidal solution and do not adversely affect the quality of the applied phosphate layer. It is also advantageous if the phosphoric acid esters have the lowest possible toxicity as colloid stabilizers. Furthermore, the phosphoric acid ester used should not interfere with the other, optionally present in the phosphate solution additives in a way that the additives are hindered in their individual effect.
  • a phosphoric acid ester is used as the colloid stabilizer.
  • the term "phosphoric acid ester” according to the invention organic esters of phosphoric acid with the formula OP (OR) 3 understood, which act as colloid stabilizers.
  • the term “phosphonic acid ester” refers to organic esters of phosphonic acid with the formula R (O) P (OR) 2 , which act as colloid stabilizers.
  • the radicals R can hereby independently of one another be hydrogen, an aromatic or an aliphatic group, it not being possible for all the radicals R to be hydrogen at the same time.
  • the term aliphatic group includes alkyl, alkenyl and alkynyl groups.
  • Alkyl groups include saturated aliphatic hydrocarbon groups having 1 to 8 carbon atoms.
  • An alkyl group may be straight or branched.
  • Particularly suitable alkyl groups according to the invention are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, n-pentyl, n-heptyl.
  • An alkyl group may be further substituted with one or more substituents. Suitable substituents are in particular aliphatic radicals.
  • substituents are alkoxy groups, nitro groups, sulfoxy groups, mercapto groups, sulfonyl groups, sulfinyl groups, halogen, sulfamide groups, carbonylamino groups, alkoxycarbonyl groups, alkoxyalkyl groups, aminocarbonyl groups, aminosulfonyl groups, aminoalkyl groups, cyanoalkyl groups, Alkylsulfonyl groups, sulfonylamino groups and hydroxyl groups.
  • alkenyl refers to an aliphatic carbon group having 2 to 10 carbon atoms and at least one double bond.
  • An alkenyl group may be straight-chain or branched. Particularly preferred alkenyl groups according to the invention are allyl, 2-butenyl and 2-hexynyl.
  • An alkenyl group may optionally be substituted with one or more substituents. Suitable substituents are those already mentioned above as alkyl substituents.
  • alkynyl refers to an aliphatic carbon group having 2 to 8 carbon atoms and at least one triple bond.
  • An alkynyl group may be straight-chain or branched.
  • an alkynyl group may be substituted with one or more substituents. Suitable substituents are those already mentioned above as alkyl substituents.
  • substituents for the aliphatic groups are aryl groups, aralkyl groups or cycloaliphatic groups.
  • Aryl refers to monocyclic groups such as phenyl, bicyclic groups such as indenyl, naphthalenyl, tricyclic groups such as fluorenyl or a benzo-linked group having three rings.
  • Aryl may also be substituted by one or more substituents. Suitable substituents are those already mentioned above for alkyl substituents.
  • Aralkyl refers to an alkyl group substituted with an aryl group.
  • cycloaliphatic refers to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic hydrocarbon ring bonded to a single bond to the rest of the molecule. Cycloaliphatic rings are 3 to 8-membered monocyclic rings and 8 to 12-membered bicyclic rings.
  • a cycloaliphatic group includes a cycloalkyl group and cycloalkenyl groups.
  • Aralkyl may also be substituted by one or more substituents. Suitable substituents are those already mentioned above as alkyl substituents.
  • substituents for the aliphatic groups are the abovementioned substituents in which one or more carbon atoms are substituted by heteroatoms.
  • ethyl phosphates in particular monoethyl phosphate and / or diethyl phosphate as phosphoric acid ester.
  • Particularly suitable is the product ADACID VP 1225/1 from Kebo Chemie.
  • the inventive method thus allows the use of a chromium-free phosphate solution.
  • the phosphate solution may still contain chromium.
  • the phosphate solution contains a chromium content of less than 0.2% by weight, preferably less than 0.1% by weight and in particular less than 0.01% by weight.
  • the phosphate solution further contains at least one additive selected from the group consisting of pickling inhibitors (B) and wetting agents (C).
  • pickle inhibitors (B) and / or wetting agents (C) the properties of the grain-oriented electrical tape produced by the method according to the invention can be further improved. Accordingly, the use of a phosphate solution containing in addition to the colloid stabilizer (A) at least one pickling inhibitor (B) and at least one wetting agent (C) is particularly preferred according to the invention.
  • Additives belonging to Group B are pickle inhibitors.
  • the term "pickling inhibitors" refers to additives which influence the chemical interaction of the phosphate solution with the strip surface in such a way that no or only small amounts of iron go into solution.
  • the use of pickling inhibitors thus prevents contamination of the phosphate solution with iron ions and the phosphate solution has constant properties over a long time.
  • This procedure is advantageous because an enrichment of the phosphate solution with iron reduces the chemical resistance of the phosphate layer on the electrical steel strip.
  • Particularly advantageous is the use of pickle inhibitors in a colloidal system, as it is used according to the invention, since the sol / gel transition strongly depends on foreign ions. Consequently, by adding pickling inhibitors, the stability of the colloidal system can be considerably improved.
  • Beizinhibitor (B) a variety of additives, provided that they are stable in acidic solutions. It is also advantageous if the pickle inhibitor the quality of the applied phosphate layer not adversely affected. It is further advantageous if the pickle inhibitor has the lowest possible toxicity.
  • the pickling inhibitors used should be adapted to the phosphate solution used. Furthermore, the pickling inhibitors used should not adversely affect the stability of the colloid constituents.
  • the Beizinhibitor used should not interact with the other additives in the phosphate solution so that the additives are hindered in their individual effect.
  • thiourea derivatives C 2-10 -alkynols, triazine derivatives, thioglycolic acid, C 1-4 -alkylamines, hydroxy-C 2-8 -thiocarboxylic acid and / or fatty alcohol polyglycol ethers are particularly effective pickling inhibitors.
  • pickling inhibitors in the form of thiourea derivatives pickling inhibitors according to the invention are understood which have the thiourea structure as the basic skeleton. From 1 to 4 hydrogen atoms of the thiourea may be replaced by suitable substituents. Particularly suitable substituents according to the invention are aliphatic groups as already defined above.
  • Suitable substituents on the nitrogen atoms of the thiourea backbone are aryl groups, aralkyl groups or cycloaliphatic groups as defined above.
  • a particularly suitable thiourea derivative according to the invention is C 1-6 -dialkylthiourea, preferably C 1-4 -dialkylthiourea.
  • the alkyl substituents are unsubstituted.
  • diethylthiourea in particular 1,3-diethyl-2-thiourea.
  • the product Ferropas7578 Alufinish is especially suitable.
  • Pickling inhibitors which are likewise particularly suitable according to the invention are C 2-10 -alkenols, in particular C 2-6 -alkanols, where alkyne has the abovementioned meaning.
  • particularly suitable C 2-6 -Alkindiole the alkyne substituents are unsubstituted and have a double bond.
  • Even more preferred according to the invention is butyne-1,4-diol, in particular but-2-yne-1,4-diol and prop-2-yn-1-ol.
  • pickling inhibitors are triazine derivatives.
  • a pickling inhibitor in the form of a triazine derivative is understood according to the invention as a pickling inhibitor which contains the triazine skeleton.
  • one or more hydrogen atoms of the triazine skeleton may be substituted by suitable substituents.
  • suitable substituents are those already mentioned above for alkyl substituents.
  • fatty alcohol polyglycol ethers are fatty alcohol polyglycol ethers.
  • Fatty alcohol polyglycol ethers according to the invention are understood to mean the reaction product of fatty alcohols with an excess of ethylene oxide.
  • Fatty alcohols particularly suitable according to the invention have from 6 to 30, preferably from 8 to 15, carbon atoms.
  • the proportion of ethylene oxide groups in the polyglycol ether is preferably high enough to render the fatty alcohol polyglycol ether water-soluble. Accordingly, preferably at least as many -O-CH 2 -CH 2 groups should be present in the molecule as carbon atoms in Alcohol.
  • the water solubility can also be achieved by suitable substitution such as, for example, esterification with sulfuric acid and conversion of the ester into the sodium salt.
  • suitable substitution such as, for example, esterification with sulfuric acid and conversion of the ester into the sodium salt.
  • the hydrogen atoms in the fatty alcohol polyglycol ethers may also be substituted with suitable substituents. Suitable substituents are the substituents already mentioned above for alkyl groups.
  • thioglycolic acid and hexamethylenetetramine for use as a pickling inhibitor.
  • Additives of group C are wetting agents.
  • a wide variety of wetting agents can be used, as long as they are stable in acidic solutions.
  • the wetting agents do not adversely affect the quality of the applied phosphate layer.
  • the wetting agents have the lowest possible toxicity.
  • the wetting agents used should not adversely affect the stability of the colloid constituents.
  • the wetting agent used should not interact with the other additives present in the phosphate solution in such a way that the additives are hindered in their individual action.
  • fluorosurfactants are outstandingly suitable as wetting agents.
  • An advantage of fluorosurfactants is that they are stably applicable in a variety of phosphate solutions, even in Cr (VI) -containing phosphate solutions.
  • fluorosurfactant is understood according to the invention to mean a surfactant which has a perfluoroalkyl radical as the hydrophobic group, where alkyl has the meaning defined above.
  • Fluorosurfactants are distinguished from non-fluorinated surfactants in that they cause a significant reduction in the surface tension of the water even in extremely low concentrations.
  • fluorosurfactants have high chemical and thermal stability.
  • Suitable surfactant components of the fluorosurfactant preferably used according to the invention are the most varied surfactants in question, provided they are stable in acidic solutions.
  • the fluorosurfactants do not disturb the stability of the colloid solution and do not adversely affect the quality of the applied phosphate layer. It is further advantageous if the fluorosurfactants have the lowest possible toxicity.
  • C 1-9 -Tetraalkylammoniumperfluor-C 5-10 alkyl sulfonates according to the invention are particularly suitable fluorosurfactants.
  • a particularly suitable wetting agent is the NC 709 product from Schwenk, which contains tetraethylammonium perfluorooctane sulfonate.
  • the amounts in which the various additives A to C are contained in the phosphate solution can be varied in a wide range. Practical experiments have shown that particularly good results are achieved when the colloid stabilizer (A) in an amount of 0.001 to 20 wt.%, Preferably in an amount of 0.01 to 10 wt.% and in particular in an amount of 0, 1 to 2 wt.% Is used.
  • the pickling inhibitor (B) is suitably used in an amount of 0.001 to 10% by weight, preferably in an amount of 0.005 to 1% by weight, and more preferably in an amount of 0.01 to 0.08% by weight.
  • the wetting agent (C) is suitably used in an amount of 0.0001 to 5% by weight, preferably in an amount of 0.001 to 1% by weight, and more preferably in an amount of 0.01 to 0.1% by weight, respectively based on the total weight of the phosphate solution.
  • the phosphate solution according to the invention may contain a wide variety of phosphates.
  • the phosphate solution may contain calcium, magnesium, manganese phosphate and / or mixtures thereof. Due to their good water solubility, primary phosphates (monophosphates) are particularly preferred according to the invention. Particularly good results are achieved with a phosphate solution containing aluminum and / or magnesium phosphate. Very particular preference is given to phosphate solutions which contain Al (H 2 PO 4 ) 3 , in particular in an amount of from 40 to 60% by weight.
  • Basis for the phosphate solution is preferably water; however, other solvents may of course be used used, provided they have a similar reactivity and polarity as water.
  • the concentration of the phosphate in the phosphate solution is preferably 5 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight and in particular 40 to 60% by weight.
  • baking phosgenation within the scope of flash annealing has proven to be particularly suitable for forming the phosphate layer on the electrical steel strip.
  • the phosphate solution is first applied to the strip and then baked at temperatures of more than 700 ° C., preferably more than 800 ° C., in particular about 850 ° C. Burning in a continuous furnace has proven particularly useful.
  • the phosphate solution contains a colloid component.
  • This embodiment is advantageous because with the colloid component during the drying of the phosphate layer, a tensile stress can be transferred to the electrical steel.
  • the tensile stress leads to a significant reduction in the re-magnetization losses when using the electrical tape.
  • the magnetostriction and thus the occurrence of noise when used in transformers can be minimized.
  • a particularly suitable colloid component according to the invention is colloidal silica.
  • the pH of the phosphate solution is important.
  • a further increase in the tensile stress on the electrical steel can be achieved by applying a glass film between the phosphate layer and the electrical steel strip.
  • a ceramic-like layer which preferably contains predominantly Mg 2 SiO 4 and embedded sulfides.
  • the glass film is preferably formed in a manner known per se during the high-temperature annealing of magnesium oxide and silicon oxide.
  • a grain-oriented electrical steel coated with a phosphate layer which has been produced by the method according to the invention, is characterized in that the content of chromium in the phosphate layer is less than 0.2 wt.%, Preferably less than 0.1 wt.% ,
  • a glass film is arranged between the phosphate layer and the electrical strip.
  • the phosphate layer and the optional glass film can be arranged on the top and / or bottom of the electrical tape.
  • phosphate layer and glass film are arranged on top and bottom of the electrical tape.
  • the grain-oriented electrical steel obtained is suitable for a wide variety of applications.
  • a particularly noteworthy use of the obtained grain-oriented electrical tape is the use as a core material in a transformer.
  • the phosphate solution or the phosphate / colloid mixture is placed in a beaker. Subsequently, the additive to be evaluated is added with stirring. A weighed electric tape specimen with a bright metallic surface is dipped in the solution and weighed after various immersion times. The weight loss (pickling loss) is calculated from the measurements. The method is partly carried out at different temperatures.
  • the phosphate solution or the phosphate / colloid mixture is placed in a beaker. Subsequently, the additive to be evaluated is added with stirring. A weighed electric tape sample with a metallic bright surface is immersed in the solution. After various aging times, the turbidity of the solution is evaluated and checked for gelation. The test is carried out at different temperatures.
  • the sol / gel transformation can, as exemplified in FIG. 1 shown viscometrically very well.
  • Equal volumes of the solutions to be evaluated are placed on a glass plate with underlying graph paper. After a lapse of 10 minutes, the areas to which the liquids have spread are determined. For this, the areas are approximated by circular areas and the diameters of the circles are given as area equivalent.
  • the solutions were evaluated according to method 1. The results of the evaluation are in FIG. 3 shown.
  • Result The basic solution interacts strongly with the steel sample. The weight loss of the steel sample is very large, which suggests a strong accumulation of the phosphate solution with iron ions. CrO 3 has a strong inhibiting effect on the solution and thus suppresses the contamination of the phosphate solution with iron ions. The effect is clearly visible on the sample surfaces. The surface of the sample from the base solution is dull to black. The sample surface of the solution mixed with CrO 3 is unchanged bright metallic.
  • FIG. 3 shows, the additives H27 and H29 act as pickling inhibitors. However, they have lower activity-inhibiting effects than CrO 3 .
  • Additive H15 shows a similar effect to CrO 3 .
  • the interaction between the phosphate solution and the Steel sample is strongly inhibited.
  • the surface of the sample from the solution with additive H15 remains unchanged for a long time, while the sample from the base solution has a strong pickling attack.
  • Additive H15 leads to an inhibition of the pickling reaction in the phosphate / silica sol mixture, as already documented above. Additive H15, however, does not contribute to the stabilization of the colloid. Additive H28, on the other hand, acts on the colloidal system, in which it apparently retards the polymerization. An addition of 3 M% leads to the fact that after 8 hours of aging at 50 ° C, despite the presence of steel in the solution, the degree of turbidity has increased little. The colloid is therefore still far removed from the sol / gel transformation.
  • the colloid stabilizer Additive H28 has no effect on the chemical interaction of the solution with the steel surface, as indicated by the strong pickling loss in FIG. 6 and foaming on the solution surface. However, the additive acts on the sol / gel transformation to delay the transition to the gel. This can be seen in the turbidity of the solutions.
  • the solutions in the beakers doped with additive H28 show a significantly lower degree of turbidity than the solutions in the beakers without the additive H28.
  • the phosphate solution mixed with additive H28 is considerably more stable. While the sol / gel transformation in the phosphate / colloid mixture already after 3 Hours, the transition can be pushed to about 6 hours using the additive H28.

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EP09711112A 2008-02-12 2009-02-12 Verfahren zur herstellung eines kornorientierten elektrobands Active EP2252722B1 (de)

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EP3715480A1 (en) 2019-03-26 2020-09-30 Thyssenkrupp Electrical Steel Gmbh Iron-silicon material suitable for medium frequency applications
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DE102008008781A1 (de) 2009-08-20
EP2252722A2 (de) 2010-11-24
CN101970718A (zh) 2011-02-09
RU2469125C2 (ru) 2012-12-10
WO2009101129A2 (de) 2009-08-20
AU2009214137B2 (en) 2013-09-19
KR101515541B1 (ko) 2015-04-27
KR20100107530A (ko) 2010-10-05
WO2009101129A3 (de) 2009-11-26
RU2010137852A (ru) 2012-03-27
AU2009214137A1 (en) 2009-08-20
JP2011515573A (ja) 2011-05-19
ATE552362T1 (de) 2012-04-15
BRPI0908151B1 (pt) 2019-03-19
JP5667450B2 (ja) 2015-02-12
BRPI0908151A2 (pt) 2015-08-11
PL2252722T3 (pl) 2012-09-28

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