EP3921454A1 - Composition aqueuse pour revêtement d'acier à grains orientés - Google Patents

Composition aqueuse pour revêtement d'acier à grains orientés

Info

Publication number
EP3921454A1
EP3921454A1 EP20702148.6A EP20702148A EP3921454A1 EP 3921454 A1 EP3921454 A1 EP 3921454A1 EP 20702148 A EP20702148 A EP 20702148A EP 3921454 A1 EP3921454 A1 EP 3921454A1
Authority
EP
European Patent Office
Prior art keywords
aqueous composition
composition according
calculated
grain
silicon dioxide
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.)
Pending
Application number
EP20702148.6A
Other languages
German (de)
English (en)
Inventor
Marek Machno
Johann Schellenberg
Gerhard Typpelt
Karl Rametsteiner
Christian Breitwieser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Helios Austria GmbH
Original Assignee
Rembrandtin Coatings GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rembrandtin Coatings GmbH filed Critical Rembrandtin Coatings GmbH
Publication of EP3921454A1 publication Critical patent/EP3921454A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • 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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14766—Fe-Si based alloys
    • H01F1/14775—Fe-Si based alloys in the form of sheets
    • H01F1/14783—Fe-Si based 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
    • 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 present invention relates to aqueous compositions which are suitable for coating grain-oriented steel ("GO", “grain oriented steel”), which is used, for example, in transformers.
  • GO grain-oriented steel
  • Grain-oriented electrical steel sheet is used for the production of transformers, dynamos and high-performance generators in order to guarantee the required soft magnetic properties.
  • Grain-oriented steel is essentially a low-carbon steel (carbon content of about 0.01% to about 0.1%) which has a high silicon content of about 2.5% to about 7.0%.
  • the grain orientation is achieved through selected rolling, annealing and tempering steps. Sheets of this steel are ultimately dipole-oriented in the rolling direction and magnetizable. Such steel sheets are often produced as steel strips with a thickness of approx. 0.2 to approx. 0.4 mm. In order to protect them from corrosion until they are processed (transport, punching, etc.), they are usually provided at the factory, i.e. Immediately after their production, the sheet metal is provided with an approximately 1 to 2 ⁇ m layer of Mg silicate ("forsterite"). This is done by coating with MgO, which in an annealing process (“hood annealing”) with superficial silicon from the steel, reacts to the silicate. This coating is referred to in the following as "primer coating”.
  • the basecoat offers sufficient temporary protection against corrosion and is essentially electrically insulating.
  • Sheet steel to a temperature between 400 ° and 1100 ° C for periods between about 4 minutes to 10 minutes he heats, whereby a protective phosphate layer ausbil det.
  • compositions for coating grain-oriented steel that can be used directly without mixing several components and that can also be stored for a longer period of time without quality restrictions.
  • the present invention relates to an aqueous composition for coating grain-oriented steel
  • the aluminum cations present in the composition calculated as AI2O3, manganese cations, calculated as MnO, dihydrogen phosphate, hydrogen phosphate and / or phosphate anions, calculated as P2O5, colloidal silicon dioxide, calculated as S1O2, and optionally iron cations, calculated as FeO, the sum formula (AI2O3) 2 (MnO) 1.8-2.4 (FeO) 0-0.2 (P2O5) 5-7 ( SiC> 2)> 30 result.
  • the storage-stable composition according to the invention makes it possible to protect grain-oriented steel in a corrosion-resistant manner and to insulate it electrically without the composition comprising environmentally harmful metals such as chromium. Since the composition according to the invention can be applied directly to the steel or to steel primed with forsterite.
  • Another aspect of the present invention relates to a process for the production of an aqueous composition for coating grain-oriented steel comprising the step of mixing aluminum cation releasing compounds, manganese cation releasing compounds, dihydrogen phosphate, hydrogen phosphate and / or phosphate anion releasing compounds , colloidal silicon dioxide and optionally iron cation releasing compounds as defined in the present patent application (see claim 1).
  • the individual components are dissolved in water as described above.
  • a method for mixing such compounds with water Verbin are written sufficiently be ⁇ in the art. By mixing these components, it is possible, please include to produce storage-stable compositions.
  • Yet another aspect of the present invention relates to a method for coating grain-oriented steel comprising applying an aqueous composition according to the present invention or an aqueous composition preparable by a method according to the present invention.
  • Another aspect of the present invention relates to grain-oriented steel, preferably grain-oriented
  • Yet another aspect of the present invention relates to grain-oriented steel, preferably grain-oriented steel sheet, comprising a coating obtainable by applying an aqueous composition according to the present invention or an aqueous composition producible by a method according to the present invention.
  • the aqueous composition of the invention comprises, besides water, aluminum cations, manganese cations, dihydrogen phosphate, hydrogen phosphate and / or phosphate anions, kol ⁇ loidales silicon dioxide and optionally iron cations in a specific molar ratio to one another.
  • This ratio is expressed in the empirical formula (AI2O3) 2 (MnO) 1.8-2.4 (FeO) 0-0.2 (P2O5) 5-7 (S1O2)> 30, whereby the aluminum cations contained in the composition as AI2O3 calculated Manganka ⁇ functions calculated as MnO, dihydrogen phosphate, hydrogen phosphate ⁇ and / or phosphate anions calculated as P2O5, calculated kol ⁇ loidales silica as S1O2 and optionally egg ⁇ senkationen be calculated as FeO.
  • the metal cations are preferably used as metal hydroxides, metal oxides or Metal salts added to the aqueous composition. Dihydrogen phosphate, hydrogen phosphate and / or phosphate anions can be added to the compositions either as phosphoric acid or as phosphates.
  • the above-mentioned components are added to the aqueous composition according to the invention in an amount such that the empirical formula (AI2O3) 2 (MnO) 1.8- 2.4 (FeO) 0- 0.2 (P2O5) 5-7 (S1O2) 30-100, preferably (AI2O3) 2 (MnO) 1.8- 2.4 (FeO) 0-0.2 (P2O5) 5-7 (S1O2) 30- 80, even more preferred
  • the aqueous composition according to the invention can also comprise other metal cations (besides aluminum and manganese cations) in addition to or instead of iron cations.
  • the total molar ratio of these metal cations, calculated as oxide to the other components in the composition, corresponds to that of the iron cations (see Claim 1).
  • This aqueous composition can be used for coating grain-oriented steel, in particular grain-oriented steel sheet.
  • Grain-oriented sheet steel is susceptible to corrosion after its production, so it is coated with a primer (usually an aqueous MgO dispersion). Since this basic coating can usually only insufficiently protect the steel sheet from corrosion due to micropores and macropores in the coating, it is necessary to provide the steel sheet with a basic coating. This (additional) coating can be achieved by the aqueous composition according to the invention.
  • Pores in the base coat can be detected, for example, by applying a dilute permanganate solution. Depending on the extent of the porosity, such a solution is discolored depending on the time and concentration, triggered by the access of Mn VII ions to the steel surface exposed at certain points and their oxidation products (associated with the reduction of Mn VII to Mn II / III). If such a porosity is found in such a test, can by means of the coating or composition according to the invention, this deficiency can also be eliminated. The pores in the first coating are closed and at the same time sustainable corrosion protection is established, which is also characterized by excellent electrical insulation.
  • the aqueous composition of the present invention forms a highly effective corrosion protection, based on a dense layer of silicates and phosphates.
  • This coating also has the following properties: hydrolysis resistance, resistance to annealing up to 1000 ° C, electrical insulation, good adhesion to the base coating (forsterite layer) or directly on a steel surface, no stickiness under processing conditions, damping of the magnetostriction oscillation
  • compositions described therein contain chromate in order to ensure the desired anti-corrosion properties of the silicate / phosphate matrix used.
  • Cr VI compounds are increasingly undesirable, including from a legal perspective, because of their harmful effects on human health and the environment.
  • the Al2O3: MnO ratio is 1: 1 to 1: 1.2, even more preferably 1: 1.1 to 1: 1.2.
  • the Si0 2 : P 2 C> 5 ratio should preferably be more than 4.3. According to a preferred embodiment of the present invention, this ratio is more than 4.3 and less than 16.7, even more preferably more than 4.3 and less than 13.3. If the ratio Si0 2 : P 2 C> 5 is less than 4.3, there could be problems with the hydrolysis and / or corrosion resistance of the coating that can be produced with the composition according to the invention.
  • the ratio A ⁇ 2q3: R2q5 is preferably greater than 1: 2.5 in order to ensure adequate SiCk colloid resistance.
  • the proportion of P2O5 must be adjusted stoichiometrically.
  • some of the manganese in a second coating can be replaced or supplemented by iron oxide .
  • Mn-Fe mixed phosphates are particularly sparingly soluble and thus contribute positively to the homogeneity of the base coating (pore closure) and to the stability of the second coating (resistance to hydrolysis).
  • the number of S1O2 in the empirical formula according to claim 1 is 30 to 100, preferably 30 to 80, even more preferably 30 to 70.
  • the number of P2O5 in the sum formula is 5.4 to 6.8, preferably 5.6 to 6.6, even more preferably 5.8 to 6.4.
  • the aluminum cations, manganese cations, dihydrogen phosphate, hydrogen phosphate and / or phosphate anions and optional iron cations present in the composition according to the invention can be introduced into them by mixing various salts, hydroxides, oxides and / or acids with water. According to a preferred embodiment of the present invention, the composition according to the invention therefore comprises aluminum hydroxide and / or aluminum phosphate.
  • Manganese cations are preferably added to the aqueous composition according to the invention as manganese (II) oxide, manganese) oxalate and / or manganese (II) hydroxide.
  • iron cations as iron (II) oxide and / or iron (II) oxalate are added to the aqueous composition according to the invention, iron (II) oxalate being particularly preferred.
  • the composition according to the invention can comprise other or further metal cations which are capable of forming poorly soluble phosphates or pyrophosphates.
  • the composition according to the invention preferably contains metal cations, calculated as metal oxides, minus aluminum and manganese cations in the same stoichiometric ratio to one another as given in the empirical formula according to claim 1 for iron cations, calculated as iron oxide.
  • the colloidal silicon dioxide contained in the aqueous composition is free of charges.
  • colloidal silicon dioxide comprising charged metal ions or the like are less preferred or not desired. Therefore, the colloidal silicon dioxide in the aqueous composition according to the invention is essentially free of surface charges.
  • the colloidal silicon dioxide comprises silicon dioxide particles, preferably spherical silicon dioxide particles, in the size between 5 and 80 nm, preferably between 5 and 60 nm, even more preferably between 5 and 40 nm.
  • the silicon dioxide particles in the composition according to the invention preferably have a specific surface area of 400 to 450 m 2 / g at a size of 5 nm and a specific surface area of 180 to 200 m 2 / g at a size of 15 nm Size of 20 nm has a specific surface area of 130 to 150 m 2 / g, with a size of 25 nm a specific surface area of 100 to 120 m 2 / g, with a size of 30 nm a specific surface area of 90 to 110 m 2 / g, with a size of 35 nm a specific surface area of 60 up to 70 m 2 / g, with a size of 40 nm a specific surface area of 40 to 50 m 2 / g.
  • the ratio of the sum of the specific surface area of the particles of the colloidal silicon dioxide to the total number of moles of all metal oxides is 1: 10,000 to
  • the molar ratio of the sum of the metal ions, calculated as their oxides, in particular the sum of the aluminum cations, calculated as Al2O3, and manganese cations, calculated as MnO, to silicon dioxide in the composition 1: 6.5 to 1: 26.5, preferably 1: 6.8 to 1:20, even more preferably 1: 7.5 to 1:18, even more preferably 1: 8 to 1:16.
  • the molar ratio of the sum of the metal ions, calculated as their oxides, in particular the sum of the aluminum cations, calculated as Al2O3, and manganese cations, calculated as MnO, to silicon dioxide in the composition is preferably 1 : 9 to 1:13, even more preferably 1:10 to 1:12, if a surface is coated with the aqueous composition with a layer thickness of less than 1.5 gm, preferably less than 1 gm.
  • the molar ratio is the sum the metal ions, calculated as their oxides, in particular the sum of the aluminum cations, calculated as Al2O3, and mangankations, calculated as MnO, to silicon dioxide in the composition preferably 1:10 to 1:14, even more preferably 1:11 to 1 : 13, if a surface is coated with the aqueous composition with a layer thickness of 2 to 10 gm, preferably 2 to 5 gm.
  • the aqueous composition according to the invention has a solids content between 10% and 70%, preferably from 20% to 60%, even more preferably from 25% to 40%.
  • Another aspect of the present invention relates to a process for the production of an aqueous composition for coating grain-oriented steel comprising the step of mixing aluminum cation releasing compounds, manganese cation releasing compounds, dihydrogen phosphate, hydrogen phosphate and / or phosphate anion releasing compounds , colloidal silicon dioxide and optionally iron cation releasing compounds as defined above.
  • Ion-releasing compounds are compounds that are capable of releasing ions in water (e.g. metal ions such as aluminum). Ion-releasing compounds can be salts, oxides, oxalates or hydroxides.
  • Yet another aspect of the present invention relates to a method for coating grain-oriented steel comprising the application of an aqueous composition according to the present invention or an aqueous composition producible by a method according to the present invention.
  • the grain-oriented steel is primed with forsterite.
  • the grain-oriented steel to be coated can comprise a base coating in order to protect it from rapid corrosion after its production protect.
  • the basecoat preferably comprises forsterite.
  • the grain-oriented steel has the shape of a sheet.
  • Such sheets can, for example, be used to manufacture transformers.
  • the aqueous composition in an amount of 1 to 50 g / m 2 , preferably from 2 to 40 g / m 2 , even more preferably from 3 to 30 g / m 2 , still more preferably from 4 to 20 g / m 2 , applied to the grain-oriented steel.
  • the aqueous composition is preferably applied to grain-oriented steel by means of a dipping process, rolling process or spraying process.
  • the grain-oriented steel coated with the aqueous composition is treated at a temperature of 500 ° C to 900 ° C, preferably 600 ° C to 850 ° C.
  • the aqueous composition is applied to the grain-oriented steel in a layer thickness of 100 nm to 20 ⁇ m, preferably 200 nm to 10 ⁇ m.
  • Another aspect of the present invention relates to grain-oriented steel, preferably grain-oriented
  • Still another aspect of the present invention relates to grain-oriented steel, preferably grain-oriented steel sheet, comprising a coating obtainable by applying an aqueous composition according to the present invention or an aqueous composition producible by a method according to the present invention.
  • Aqueous composition for coating grain oriented steel comprising
  • composition aluminum cations, calculated as AI2O3, manganese cations, calculated as MnO, dihydrogen phosphate, hydrogen phosphate and / or phosphoric ⁇ phatanionen, calculated as P2O5, colloidal silica, calculated as S1O2, and, optionally, iron cations, calculated as FeO, the sum formula (AI2O3) 2 (MnO) 1.8-2.4 (FeO) 0-0.2 (P2O5) 5-7 (SiO2) ⁇ 30 result.
  • Aqueous composition according to embodiment 1, wherein the number of S1O2 in the empirical formula is 30 to 100, preferably 30 to 80, even more preferably 30 to 70.
  • Aqueous composition according to embodiment 1 or 2 is.
  • Forms 1 to 3 this comprising aluminum hydroxide and / or aluminum phosphate.
  • manganese (II) oxide Man comprises ⁇ ganin) oxalate and / or manganese (II) hydroxide.
  • this iron oxide iron (I I) oxide and / or iron (I I) oxalate comprises.
  • Forms 1 to 6 the colloidal silicon dioxide being free from surface charges.
  • colloidal silicon dioxide silicon dioxide particles preferably spherical silicon dioxide oxide particles, in size between 5 and 80 nm, preferably between 5 and 60 nm, even more preferably between 5 and 40 nm.
  • tallow oxides from 1: 25,000 to 1: 100,000, preferably from
  • Forms 1 to 10 the ratio of the sum of the specific surface area of the particles of the colloidal silicon dioxide to the total number of moles of all metal oxides being 1: 10,000 to 1: 200,000, preferably 1: 20,000 to 1: 150,000, even more preferably 1: 25,000 to 1: 100,000, more preferably 1: 30,000 to 1: 80,000.
  • Forms 1 to 11 the molar ratio of the sum of the metal ions, calculated as their oxides, to silicon dioxide in the composition 1: 6.5 to 1: 26.5, preferably 1: 6.8 to 1:20, even more preferably 1 : 7.5 to 1:18, even more preferably 1: 8 to 1:16.
  • Formation forms 1 to 12 the molar ratio of the sum of the metal ions, calculated as their oxides, to silicon dioxide in the composition being preferably 1: 9 to 1:13, even more preferably 1:10 to 1:12 when a surface is coated with the aqueous composition with a layer thickness of less than 1.5 gm, preferably less than 1 gm.
  • Aqueous composition according to one of embodiments 1 to 13, wherein the molar ratio of the sum of the metal ions, calculated as their oxides, to silicon dioxide in the composition is preferably 1:10 to 1:14, even more preferably 1:11 to 1:13 if a surface is coated with the aqueous composition with a layer thickness of 2 to 10 gm, preferably 2 to 5 gm.
  • a process for the production of an aqueous composition for coating grain-oriented steel comprising the step of mixing aluminum cation releasing compounds, manganese cation releasing compounds, dihydrogen phosphate, hydrogen phosphate and / o compounds releasing phosphate anions, colloidal silicon dioxide and optionally iron cations releasing compounds as defined in any one of embodiments 1 to 15.
  • aqueous composition in an amount of 1 to 50 g / m 2 , preferably from 2 to 40 g / m 2 , even more preferably from 3 to 30 g / m 2 , even more preferably from 4 to 20 g / m 2 to which grain oriented steel is applied. 21.
  • aqueous composition is applied to the grain-oriented steel by means of a dipping process, rolling process or spraying process.
  • the grain-oriented steel coated with the aqueous composition being treated at a temperature of 500 ° C to 900 ° C, preferably 600 ° C to 850 ° C.
  • the aqueous composition being applied to the grain-oriented steel in a layer thickness of 100 nm to 20 gm, preferably 200 nm to 10 gm.
  • Grain-oriented steel preferably grain-oriented steel sheet, obtainable by a method according to one of the embodiments 17 to 23.
  • Grain-oriented steel preferably grain-oriented steel sheet, comprising a coating obtainable by applying an aqueous composition according to one of embodiments 1 to 15 or an aqueous composition producible by a method according to embodiment 16.
  • Example 1 Production of aqueous compositions for coating grain-oriented steel
  • compositions 2 to 9 By adapting the stoichiometric ratios of the components listed above, the following additional compositions (compositions 2 to 9) could be produced:
  • Composition 5 ('without iron oxide)
  • Composition 7 iron oxide instead of iron oxalate in the phosphate-containing solution
  • compositions 2 to 7 were also on a
  • Me x O y denotes the sum of all metal ions calculated as their oxides
  • Comparative composition 2 (Example 1 from
  • Comparative composition 3 (example 2 from DE 2247269 (Al, Cr))
  • Comparative composition 4 (example B3 from WO 2014/180610 (Al, Mn, Zn, Mg))
  • the comparative compositions 1 to 4 were - as described in Example 1 - applied to a primed GO sheet in an amount of 5 g / m 2 , dried briefly in air and baked at 820 ° C. for 60 seconds.
  • Me x O y denotes the sum of all metal ions calculated as their oxides
  • Example 3 Testing the compositions and coatings from Examples 1 and 2
  • compositions which are used for coating grain-oriented steel are their ability to protect the coated steel from corrosion.
  • Base coating coated with the compositions according to the case 1 and 2 were packed tightly in a water- and vapor-impermeable film and stored for 8 hours at 90 ° C in a heating cabinet. The surface of the coated metal sheets was then visually assessed.
  • Inclusions in the finished coating can also represent a relevant criterion for the quality of the composition according to the invention. Any inclusions were visually recorded and assessed.
  • Sheet metal is generally undesirable, as bubbles are precursors for later corrosion. Blistering can be assessed visually.
  • compositions 1 to 5 and 7 have a long shelf life of more than three months and the coatings produced with them have high hydrolysis resistance and extremely low susceptibility to corrosion.
  • the comparative compositions from the prior art have a low storage stability in a ready-to-use mixture.
  • the hydrolysis stability of the coatings produced with it is also not optimal.
  • Composition 6 also shows that a lower molar ratio between Al2O3 and MnO (2: 1.75) in the composition leads to a lower storage stability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne une composition aqueuse destinée au revêtement d'acier à grains orientés et comprenant - des cations aluminium, - des cations manganèse, - des anions dihydrogénophosphate, d'hydrogénophosphate et/ou de phosphate, - du dioxyde de silicium colloïdal et - éventuellement des cations fer, les cations aluminium, calculés sous la forme Al2O3, les cations manganèse, calculés sous la forme MnO, les anions dihydrogénophosphate, d'hydrogénophosphate et/ou de phosphate, calculés sous la forme P2O5, le dioxyde de silicium colloïdal, calculé sous la forme SiO2, et éventuellement les cations fer, calculés sous la forme FeO, lesquels sont tous présents dans la composition, répondant à la formule brute (Al2O3)2(MnO)1,8-2,4(FeO)0-0,2(P2O5)5-7(SiO2)≥30.
EP20702148.6A 2019-02-06 2020-02-04 Composition aqueuse pour revêtement d'acier à grains orientés Pending EP3921454A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19155700.8A EP3693496A1 (fr) 2019-02-06 2019-02-06 Composition aqueuse destinée au revêtement d'acier à grains orientés
PCT/EP2020/052666 WO2020161094A1 (fr) 2019-02-06 2020-02-04 Composition aqueuse pour revêtement d'acier à grains orientés

Publications (1)

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EP3921454A1 true EP3921454A1 (fr) 2021-12-15

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WO2024210189A1 (fr) * 2023-04-05 2024-10-10 日本製鉄株式会社 Liquide de traitement de film isolant pour tôles d'acier électrique à grains orientés, son procédé de fabrication et procédé de fabrication de tôle d'acier électrique à grains orientés
WO2024210188A1 (fr) * 2023-04-05 2024-10-10 日本製鉄株式会社 Liquide de traitement de film de revêtement isolant pour tôle d'acier électromagnétique à grains orientés et procédé de production de tôle d'acier électromagnétique à grains orientés

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JP7575386B2 (ja) 2024-10-29
US20220112605A1 (en) 2022-04-14
EP3693496A1 (fr) 2020-08-12
CN113412343B (zh) 2023-03-28
KR20210124278A (ko) 2021-10-14
WO2020161094A1 (fr) 2020-08-13
BR112021014908A2 (pt) 2021-09-28
CN113412343A (zh) 2021-09-17
JP2022519691A (ja) 2022-03-24

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