DE1621530A1 - Process for the treatment of magnetic sheets - Google Patents

Process for the treatment of magnetic sheets

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Publication number
DE1621530A1
DE1621530A1 DE19671621530 DE1621530A DE1621530A1 DE 1621530 A1 DE1621530 A1 DE 1621530A1 DE 19671621530 DE19671621530 DE 19671621530 DE 1621530 A DE1621530 A DE 1621530A DE 1621530 A1 DE1621530 A1 DE 1621530A1
Authority
DE
Germany
Prior art keywords
calcium phosphate
insulation
magnetic sheets
treatment
layer
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
DE19671621530
Other languages
German (de)
Inventor
Peter Brussig
Dipl-Ing Petros
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.)
Transformatoren und Roentgenwerk GmbH
Original Assignee
Transformatoren und Roentgenwerk 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 Transformatoren und Roentgenwerk GmbH filed Critical Transformatoren und Roentgenwerk GmbH
Publication of DE1621530A1 publication Critical patent/DE1621530A1/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/22Orthophosphates containing alkaline earth metal cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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
    • C23C22/74Chemical 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets 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
    • H01F1/14Magnets 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
    • H01F1/147Alloys characterised by their composition
    • H01F1/14766Fe-Si based alloys
    • H01F1/14775Fe-Si based alloys in the form of sheets
    • H01F1/14783Fe-Si based alloys in the form of sheets with insulating coating

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

Description

Verfahren zur Behandluhg von Magnetblechen Die Erfindung betrifft ein Verfahren zur Behandlung von mit einer glühfesten Isolationsschicht versehenen 1:Iagnetblechen nach den mechanischen Trennprozessen. s:agnetbleähe zum Aufbau von lammelierten Magnetkernen für Wechselflüsse müssen an ihrer Oberfläche eine Is olierschicht tragen. Dieben den Verfahrens wo auf mechanischem Wege eine Is alierschicht aufgebracht wird!. zB, durch Aufkleben von Papier oder durch Überziehen mit einer zusammenhängenden Sohehtt die an der Oberflache der Magnetbleche haftet' sind auch Verfahren bekannt, bei denen die Isolierschicht durch eine chemische Reaktion zwischen einer Lösung.Method for treating magnetic sheets The invention relates to a method for the treatment of provided with a heat-resistant insulating layer 1: Magnetic sheets after the mechanical separation processes. s: agnetblenah to build Laminated magnetic cores for alternating fluxes must have an insulating layer on their surface wear. Thieves in the process where an insulating layer is applied by mechanical means will!. for example, by gluing paper on or by covering with a coherent one Sohehtt that sticks to the surface of the magnetic sheets are also known processes where the insulating layer is produced by a chemical reaction between a solution.

und der zu isolierenden Oberfläche erzeugt wird. So ist es bekannt, auf die Magnetbleche .eine Phosphorsäurelösung aufzubringen und diese bei etwa 5oooC: einzubrennen. Ferner ist es bekannte zur Erzeugung von Isolationsschichten auch Manganphosphatbäder oder Zinkphosphatbäder anzuwen,-den. Diese Phosphatschichten sind aber höchstens bis 6oooC als wärmebeständig anzusehen. Dagegen lassen sich auch wärmebeständigere j?hosphatschichten erzeugen, wenn man in ebenfalls bekannter Weise als schichtbildende Hauptkomponente Erdalkaliphosphate anwendet. Dabei soll die Lösung zur Behandlung der Magnetbleche wenigstens einen Gehalt von 6 g/1 Phosphorpentoxid ( P205? aufweisen und maximal 6 g/1 Eisen enthalten: Als Erdalkalimetall ist Galzium angegeben worden, welches beispielsweise in Form von Doppelsuperphosphat, ev. mit Zusatz von Calziumnitrat gelöst wird. Die Massen der in das Bad einzugebenden Chemikalien sind dabei so gewählt' daß die Lösung 24 bis 25 g/1 Calzium, 2o g/3 Phosphorsäure und 58 g/1 , Nitrat enthält. Eine derartige Lösung muß bei et-Wa 6ooC l o Linüten auf das LIagnetblech cinwir::en und erzeugt eine etwa. 8 bis tarkef fein -kristalline Schicht, aie an Luft kurzzeitig einer Temgeratur von höchstens 8oooC aAsüesetzt ererden kann. Na aber die bei dem Bearbeitungsprozeß und auch bei dem lachgl!Jhprozeß von kornorientierten Blechen erforderlichen Teitlperzturen über 800°C liegen' haben sich bei diesen Blechen Isolierschichten durchgesetzt, die als Keramiküberzüge aufgebracht werden und z.B, unter dem Namen Car! lite-Is olation bzw. Surahammer bekanntgeworden sind* Biese Isolierachichten werden hinlänglich dünn r#iugetrz:.,gen, s o daß ein gü us tiger Füllfaktor erreicht wird. Sie sind elektrisch gut isolierend und halten die bei dem Bearbetungs- und Nachglühprozeß eintretenden Temperaturen gut aus. Allerdings zeigt sich bei der Bearbeitung voll derart. isolierten kiagnetblecheng die meist in hollis angeliefert werden und zunächst auf Ldngsteilanlagen mittels Rollenscheren geschnitten werden müssen, daß die Isolation im Bereich der Schnittkanten teilweise abplatzt* Ferner ist die Isolation auch nicht gleichbleibend gleichmäßig auf das Blech aufgetragen; vielmehr kommen immer wieder Chargen vors wo-die Isolation Poren aufweist. Derartige Fehler in der Isolation führen aber zu einer Erhöhung der Wirbelstromverluste in dem LIagnetkern. :. Es ist Zweck der Erfindung, die durch Vlirbelströme verursachten Eisenverluste in Magnetkernen, in denen V'iechselflüsse auftreten, so gering wie möglich zu halten.and the surface to be insulated is generated. It is known to apply a phosphoric acid solution to the magnetic sheets and to burn them in at about 500oC. It is also known to use manganese phosphate baths or zinc phosphate baths for producing insulation layers. However, these phosphate layers are to be regarded as heat-resistant up to a maximum of 600oC. On the other hand, it is also possible to produce more heat-resistant phosphate layers if alkaline earth phosphates are used as the main layer-forming component in a likewise known manner. The solution for treating the magnetic sheets should have a content of at least 6 g / 1 phosphorus pentoxide (P205?) And contain a maximum of 6 g / 1 iron: Galzium has been specified as the alkaline earth metal, for example in the form of double superphosphate, possibly with the addition of calcium nitrate The masses of the chemicals to be added to the bath are chosen so that the solution contains 24 to 25 g / l calcium, 20 g / 3 phosphoric acid and 58 g / l nitrate Pin lo lines onto the magnetic sheet and create an approx. 8 to Tarkef, finely crystalline layer, which can briefly be exposed to a temperature of 8oooC or less in air. Well, however, the Teitlperzturen required in the machining process and also in the laughing! Jhd process of grain-oriented sheets are above 800 ° C 'have established with these sheets insulating layers that are applied as ceramic coatings and, for example, under the name Car! lite insulation or surah hammer have become known. They have good electrical insulation and can withstand the temperatures occurring during the machining and afterglow process. However, this is fully evident in the processing. insulated kiagnetblecheng which are mostly delivered in hollis and first have to be cut on longitudinal part lines using roller shears so that the insulation partially flakes off in the area of the cut edges * Furthermore, the insulation is not evenly applied to the sheet metal; rather, batches always occur where the insulation has pores. However, such faults in the insulation lead to an increase in the eddy current losses in the magnet core. :. It is the purpose of the invention to keep the iron losses caused by vortex currents in magnetic cores in which animal fluxes occur as low as possible.

Aufgabe der Erfindung ist es, durch fehlerhafte Isolation verursachte 1'lirbelstromverluste zu senken, . Diese Aufgabe wird erfindungsgemäß gelöst g indem das Iviagnetblech vor dem Glühprozeß einem i'hosphatierbad, welches auf der .Basis von Calziumphosphaten arbeitety ausgesetzt wird. Durch diesen Prozeß wird das I4agnetblech-nach den mechanischen Trennprozessen mit einer Nachisolationsschicht überzogen, die ev, vorhandene Fehler in der Keramikisolation überdeckt und vor allem die metalliscl blanken Stellen in dem Bereich der Schnittkanten insbesondere aber die nicht gtnz vermeidbaren Grate nachträglich wieder oder überhaupt isoliert. Um diesen Nac his olierprozeß sogleich zwischen Trennprozeß und Glühprozeß vollziehen zu können' muß eine rasch arbeitende Phosphatierlösung Anwendung finden' weil sonst die Badlängen bei den gegebenen Durchlaufgeschwindgkeiten unvertretbare Abmessun- gung annehmen. Außerdem müssen die fhöspha tschich- ten die.. Temperaturen aushalten, die bei dem NachglUhprozeü auftreten. Zwar könnte z#u ch prinzipiell die Nachisolation im Anschluß an den Glühprozeß aufgebracht werden m das hätte aber den Nachteil, daß ein weiterer Einbrennprozeß nötig märe. Gelingt es hingegen, die Isolationsschichten so temperaturfest zu machen, daß sie den Temperaturen des Nachglühprozesses widerstehen; so kann der Nachglühprozeß sogleich als Einbrennprozeß ausgenutzt werden® Diese zusätzlichen Bedingungen werden erfüllt y wenn gemäß einer Weiterbildung der :rfndztug die Badlösungen ca.. 2oo g/1 2 es -CG lziumphos,phat und 15o g/1 Ortho-;Phö.sph.ors#iure -aufweisen. zr*Jur-Beschleunigung des Prozesses können auch noch bekannte Beschleuniger eingesetzt werden, wozu sich Galziumnitrat eignet! welches in irrengen von mindestens 13- gjl beigegeben wird. Um das IUachis olierverfahmeri kost enginstig betreiben zu .können.. werden besonders preis.-günstige Chemikalien eingesetzt, Da aber primäres Calziumphosphat verhältnismäßig teuer ist, wird dasselbe unmittelbar in der Anlage erzeugt, indem das relativ billige Calziumcarbonat mit 'Wasser aufgeschwemmt und-anschließend Ortho- Phosphorsäure zugegeben wird« Wrd das Bad 3.n der angegebenen Zusammensetzung betrieben, so ergibt sich auch daß nur geringe Mengen von Beschleunigern -nämlich ca. 13 g/l Galzfumnitrat optimale Ergebnisse erzielen, was mit Rücksicht auf die-Preise von Galziumnitrat sich besonders kostenaUns tig auswirkt, ,Die angegebene Rezeptur e=öglioht es die Bauer des Tauchprozesses auf 2o - C a s abzuktrzenDie erzeugte Phosphatschicht hält kurzzeitig eine Temperatur bis zu 9oo:°C ohne Anwendung einer iz.erten. Atmosphäre beim Glühprozeß aus. Während dieser kurzen Tauchzeit bildet sich in der liösung eine wenige Angström-starke amorphe Calzium-Rsen# rhösphatschicht auf der freiliegenden Eisenfläche. Auf dieser sowie auf der vorhandenen Isolierung bleibt ferner eine etwa oll bis 0l3 mm starke Nachisolierschicht zurück, die z.B. durch Abquetact walzen auf 1o bis 3o reduziert wird. Nach Durchlauf durch den Glühofen bei c a. 82o0 G und einer Zeit von 2o bis 6o Sekunden ist die Nachisolierschicht eingebrannt und weist jetzt eine Stärke von weniger als auf. Das ist wichtigi um durch die Nachisolierung nicht den Füllfaktor maßgeblich zu beeinflussen. Die an den Schnittkanten verbleibenden dickeren Nachfis olierschiehten beeinflussen dagegen- den Füllfaktor nicht Ja sie sich in dem Bereich anlagern! wo keine Keramikschicht vorhanden ist. Durch den Einbrennprozaß hat sich eine Calzium-Phosphatschicht gebildetl, die sowohl Wasser als auch Transformatorenöl unlöslich ist,The object of the invention is to reduce eddy current losses caused by faulty insulation. According to the invention, this object is achieved in that, prior to the annealing process, the metal sheet is exposed to a phosphating bath which is based on calcium phosphates. As a result of this process, the magnetic sheet is covered with a post-insulation layer after the mechanical separation process, which covers any existing defects in the ceramic insulation and, above all, the bare metal areas in the area of the cut edges, but especially the unavoidable burrs, afterwards or at all. In order to be able to carry out this curing process immediately between the separating process and the annealing process, 'a rapidly working phosphating solution must be used' because otherwise the bath lengths at the given throughput speeds are unacceptable. accept it. In addition, the fhöspha Tschich- Tend to withstand the temperatures that occur during the afterglow process. In principle, the post-insulation could be applied after the annealing process, but this would have the disadvantage that a further baking process would be necessary. If, on the other hand, it is possible to make the insulation layers so temperature-resistant that they withstand the temperatures of the afterglow process; werden® so the post annealing may immediately utilized as a burn-in process, these additional conditions are fulfilled if y according to a further development of the: it -CG lziumphos, phosphate rfndztug the bath solutions ca .. 2oo g / 1 2 and 15o g / 1 ortho; Phö.sph .ors # iure. zr * Jur acceleration of the process, known accelerators can also be used, for which galcium nitrate is suitable! which is added in errors of at least 13 gjl. In order to be able to operate the IUachis olierverfahmeri at low cost ... chemicals are used that are particularly inexpensive, but since primary calcium phosphate is relatively expensive, it is produced directly in the plant by flooding the relatively cheap calcium carbonate with water and then using Ortho - phosphoric acid is added "Wrd the bathroom 3.n the composition given operated, the result is also that only small amounts of accelerators -namely about 13 g / l Galzfumnitrat best results, what with regard to the prices of Galziumnitrat particularly The specified recipe e = Öglioht the builder of the immersion process to shorten it to 2o - C as The phosphate layer that is produced briefly maintains a temperature of up to 900: ° C without the use of an icing. Atmosphere during the annealing process. During this short immersion time, a few Angstrom thick amorphous calcium carbonate oxide layer forms on the exposed iron surface. On this as well as on the existing insulation there remains an approximately oll to 0.13 mm thick post-insulation layer, which is rolled down to 1o to 3o, for example by Abquetact is reduced. After passing through the annealing furnace at c a. 82o0 G and a time of 20 to 60 seconds, the post-insulating layer is burned in and now has a thickness of less than on. This is important so that the post-insulation does not significantly influence the fill factor. On the other hand, the thicker Nachfis olierschiehten remaining on the cut edges do not affect the fill factor. Yes, they are deposited in the area! where there is no ceramic layer. As a result of the baking process, a calcium phosphate layer has formed, which is insoluble in both water and transformer oil,

Claims (3)

Patent ans p r ü ehe 1. Verfahren zur Behandlung von mit einer glühfesten Isolationsschicht versehenen Magnetblechen nach den mechanischen Trennprozesseng dadurch gekennzeicbnett daß das Magnetblech vor dem bekannten Glühprozeß einer Phosphat.erlösung ausgesetzt wird, welche auf der Basis von Calziumphosp hat en arbeitet zum Zwecke der Erzeugung ,einer Na:chisolati on. Patent anp r ü ehe 1. Process for the treatment of with an anneal resistant Insulation layer provided magnetic sheets after the mechanical separation process thereby gekennzeicbnett that the magnetic sheet before the known annealing process of a Phosphat.erlösung is exposed, which has been working on the basis of Calziumphosp for the purpose of creation, of a na: chisolation. 2. Verfahren nach Anspruch 1 9 .dadurch gekennzeichnet. daß die Calziumphosphatlösung ca. Zoo g/1 primäres Calziumphosphat C4 (H2 2o4)2
und ca. 15o g/! Ortho-Phosphorsäure ( H3?o4) enthält.
2. The method according to claim 1 9. Characterized. that the calcium phosphate solution approx. Zoo g / 1 primary calcium phosphate C4 (H2 2o4) 2
and about 15o g /! Contains orthophosphoric acid (H3? O4).
3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Calziumphosphatlösung als Beschleuniger cam 15 g/! Galziumnitrat Eca (N03)2 enthält.
® Verfahren nach iinspruch 1 und 2, dadurch gekennzeichnet$ daß das primäre Calziumphosphat [Cla (H3P04)21durch Vermischen einer Auischwem-
mang von Calziumcarb onat (Ca CO.) mit Ortho-2hophorsäure ( 113 f'04) in, der Anlage erzeugt
3. The method according to claim 1 and 2, characterized in that the calcium phosphate solution as an accelerator cam 15 g /! Galcium Nitrate Contains Eca (N03) 2.
® Method according to iins Claims 1 and 2, characterized in that the primary calcium phosphate [Cla (H3P04) 21 by mixing a floodplain
mang of calcium carbonate (Ca CO.) with ortho-2hophorsäure (113 f'04) in the plant
DE19671621530 1967-11-23 1967-11-23 Process for the treatment of magnetic sheets Pending DE1621530A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEV0034879 1967-11-23

Publications (1)

Publication Number Publication Date
DE1621530A1 true DE1621530A1 (en) 1971-06-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2383510A1 (en) * 1977-03-09 1978-10-06 Centro Speriment Metallurg STEEL COATING SOLUTION FOR MAGNETIC USE AND INSULATING COATING OBTAINED FROM THIS SOLUTION
FR2601699A1 (en) * 1986-07-18 1988-01-22 Permelec Electrode Ltd PROCESS FOR THE PRODUCTION OF A COMPOSITE MATERIAL COATED WITH A CALCIUM PHOSPHATE
EP0905279A1 (en) * 1997-08-19 1999-03-31 Sermatech International Inc. Phosphate bonding composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2383510A1 (en) * 1977-03-09 1978-10-06 Centro Speriment Metallurg STEEL COATING SOLUTION FOR MAGNETIC USE AND INSULATING COATING OBTAINED FROM THIS SOLUTION
FR2601699A1 (en) * 1986-07-18 1988-01-22 Permelec Electrode Ltd PROCESS FOR THE PRODUCTION OF A COMPOSITE MATERIAL COATED WITH A CALCIUM PHOSPHATE
EP0905279A1 (en) * 1997-08-19 1999-03-31 Sermatech International Inc. Phosphate bonding composition
US5968240A (en) * 1997-08-19 1999-10-19 Sermatech International Inc. Phosphate bonding composition

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