US3773629A - Method of enameling strips and sheets of steel - Google Patents

Method of enameling strips and sheets of steel Download PDF

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Publication number
US3773629A
US3773629A US00132195A US3773629DA US3773629A US 3773629 A US3773629 A US 3773629A US 00132195 A US00132195 A US 00132195A US 3773629D A US3773629D A US 3773629DA US 3773629 A US3773629 A US 3773629A
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percent
work piece
combination according
acid
volume
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US00132195A
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English (en)
Inventor
W Sieckmann
K Jurging
J Zwach
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Fried Krupp AG Hoesch Krupp
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Hoesch AG
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    • 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
    • C23DENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D3/00Chemical treatment of the metal surfaces prior to coating

Definitions

  • the present invention relates to a multi-stage method of one-layer enameling steel bands and steel sheets according to which the bands, strips or sheets are degreased, are rinsed in cold water between each method step and after an intermediate treatment are enameled.
  • the metal sheet to be enameled is first electrolytically degreased and after a rinsing in water is chemically or electrolytically pickled in sulfuric acid or in a mixture of formic acid and nitric acid and is again rinsed. Following the pickling step, the metal sheet is plated electrolytically in a nickel bath with nickel and subsequently is enameled. If the enameling is not carried out shortly after the nickel plating step, the nickel-plated metal sheet is electrolytically coated with a zinc coat which is removed prior to the enameling step. However, this method does not yield a sufficient adherence of the enamel coat to the steel sheet.
  • the band, strip or sheet is descaled chemically or anodically in a 3 to 8 volume percent nitric acid, and is furthermore characterized in that upon the thus prepared band, strip or sheet there is deposited a metallic layer of iron and one or two of r the metals nickel, cobalt and manganese which layer is cathodically electrodeposited from one or more electrolytic baths at a temperature within the range of from room temperature to 80C, said layer being adapted in wet condition to be wiped off.
  • the method according to the present invention is furthermore characterized in that one or two of the metals nickel, cobalt, manganese are added to the electrolyte up to a total concentration of 50 grams per liter of these foreign metals.
  • the band, strip or sheet is chemically or anodically posttreated in an acid over a period of from 10 to a maximum of seconds. Subsequently, the thus treated material is a rectilinear or branch linked aliphatic hydrocarbon residue with from 1 to 6 carbon atoms, and- /or bb. a methacrylate the ester group of which consists of an aliphatic straight linked or branch linked hydrocarbon residue with from 1 to 6 carbon atoms,
  • said lacquer or enamel following the stoving being deformable and at the temperatures employed during the enameling step depolymerizes completely and without residues by volatilization while the enamel frits melt into a unitary coat or cover on the band or sheet.
  • the lacquer or enamel with reference to the solid body comprises as essential ingredientsthe following components:
  • nitric acid for the abovereferred to descaling treatment, it is advantageous, depending on the successive method steps, chemically to descale the strip, band or sheet in' nitric acid of from 3 to 8 percent by volume at room temperature for a period of from 30 to 60 seconds, or to descale the strip, band or sheet anodically in nitric acid of from 3 to 8 percent by volume at a current density of from 10 amperes per square decimeter at room temperature for a period of about 10 seconds.
  • a quantity of from 10 percent by volume of sulfuric acid may be added to the bath, or the bath may during an anodic descaling at a temperature of from 40 to C consist merely of a sulfuric acid of 10 percent by volume.
  • the metallic layer adapted to be wiped off For purposes of applying the metallic layer adapted to be wiped off, various embodiments are possible. According to a preferred manner, following the descaling step, upon the strip, band or sheet there is from an electrolyte containing a bivalent iron, iron electrodeposited at a current density of from 5 to amperes per square decimeter within a period of from 10 to 30 seconds. Subsequently, from a nickel electrolyte, for instance of the Watt type or the citric acid type, nickel is cathodically electrodepositedat a current density of from 3 to l0 amperes per square decimeter in a period of from 6 to seconds.
  • an electrolyte containing a bivalent iron, iron electrodeposited at a current density of from 5 to amperes per square decimeter within a period of from 10 to 30 seconds Subsequently, from a nickel electrolyte, for instance of the Watt type or the citric acid type, nickel is cathodically electrodepositedat a current density of
  • a cobalt containing sulfate electrolyte instead of employing a nickel electrolyte, also a cobalt containing sulfate electrolyte may be employed in which instance the cobalt is electrodeposited onto the strip, band or sheet at a current density of from 3 to 10 amperes per square decimeter in a period of from 6 to 15 seconds.
  • the said metals be electrodeposited upon the strip, band or sheet at a current density of from 5 to 20 amperes per square decimeter in a period of from 10 to 30 seconds.
  • the respective strip, band or sheet is advantageously immersed in a nitric acid of from 3 to 8 percent by volume at room terperature for a period of from 5 to 20 seconds whereas, with an anodic posttreatment in a sulfuric acid of 10 percent by volume, a current density of 10 amperes per square decimeter at a room temperature of from 40 to 80C and a treatment time of approximately 10 seconds will be required.
  • EXAMPLE ll 1. Anodic degreasing in soda lye at a temperature of C., a current density of 15 amperes per square decimeter in a time period of six seconds,
  • Anode material soft carbon steel
  • EXAMPLE Ill 1. Anodic degreasing in soda lye at a temperature of 80 C. and a current density of 15 amperes per square decimeter in a time period of six seconds,
  • cathodic electrodeposition of zinc from an electrolyte of the composition 320 grams per liter zinc sulfate 20 grams per liter ammonium chloride, the pH-value of which is by means of sulfuric acid adjusted to 2.0 at a current density of 30 amperes 'per square decimeter and at a temperature of 60 C. in a time period of 10 seconds, l0. rinsing and drying,
  • EXAMPLE IV A sheet strip belt or the like treated and dried in conformity with the method steps 1 to 8 of the preceding EXAMPLES l-lli has applied thereto in any standard manner for instance by painting, immersing, spraying, or rolling a lacquer having worked thereinto white or colored pigmented enamel frits in a quantity of from 50 to 80 percent by weight.
  • the lacquer is applied in the form of a liquid mixture in organic solvent and with regard to the solid body contains as essential ingredients:
  • aa an acrylate the ester group of which consists of a rectilinear or branch-linked aliphatic hydrocarbon residue with from one to six carbon atoms, and/or bb. a methacrylate the ester group of which consists of an aliphatic straight-linked or branch-linked hydrocarbon residue with from one to six carbon atoms.
  • the coat of lacquer is subsequently at a temperature of from 150 to 350 C., preferably from 160 to 300 C., burned or stoved into the sheet strip or belt in a time period of from 30 minutes to seconds while at the mentioned lower temperatures, longer burning or stoving times and at the higher temperatures correspondinglyshorter burning or stoving times are to be employed.
  • the subsequent depolymerization of the lacquer components occurs over a range of temperature,"and that therefore the burning orstoving temperatures which preferably are by about 20 C. higher thanithemelting point of the inserted frits can'- not be increased at will.
  • the lacquer film burned into the strip sheet or belt has a smooth, dull or mat, or nonglossy appearance while the color-"tone depends on the enamel frit worked into thefla cjquer.
  • Theiburn'ed-in or stoved lacquer film is hard arid mechanic'ally resistant, especially against scratches, impacts and blows.
  • the belt strip or sheet provided with the coat of lacquer is deformable and can be deep drawn so that no difficulties will be encountered in shaping the sheet strip or belttreated in the above mentioned manner in conformity with the desires of the respective manufacturer.
  • the lacquer film is heated to a temperature of over approximately 500 C., preferably ata temperature over 700 C. on, depolymerized completely in a furnace and without residues while the lacquer ingredients are volatilized and the enamel frits melt to a uniform flawless enamel coat.
  • a method in combination according to claim 10, in which said lacquer with regard to the solid body comprises:

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Glass Compositions (AREA)
  • Paints Or Removers (AREA)
US00132195A 1970-04-09 1971-04-07 Method of enameling strips and sheets of steel Expired - Lifetime US3773629A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2016989A DE2016989C3 (de) 1970-04-09 1970-04-09 Verfahren zum Einschichtemaillieren von Bändern und Blechen

Publications (1)

Publication Number Publication Date
US3773629A true US3773629A (en) 1973-11-20

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US00132195A Expired - Lifetime US3773629A (en) 1970-04-09 1971-04-07 Method of enameling strips and sheets of steel

Country Status (11)

Country Link
US (1) US3773629A (enrdf_load_stackoverflow)
AT (1) AT316257B (enrdf_load_stackoverflow)
BE (1) BE765510A (enrdf_load_stackoverflow)
CA (1) CA974923A (enrdf_load_stackoverflow)
DE (1) DE2016989C3 (enrdf_load_stackoverflow)
ES (1) ES389127A1 (enrdf_load_stackoverflow)
FR (1) FR2089510A5 (enrdf_load_stackoverflow)
GB (1) GB1316890A (enrdf_load_stackoverflow)
NL (1) NL7104638A (enrdf_load_stackoverflow)
NO (1) NO130692C (enrdf_load_stackoverflow)
SE (1) SE368033B (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923611A (en) * 1974-12-23 1975-12-02 Ferro Corp Direct-on ceramic coating of carbon-rich iron
US3971120A (en) * 1974-12-23 1976-07-27 Ferro Corporation Direct-on ceramic coating of carbon-rich iron
US4828662A (en) * 1987-05-12 1989-05-09 Mb Group Plc Electrolytic stripping of cobalt
US4910096A (en) * 1987-08-10 1990-03-20 Hille & Muller Cold-rolled steel strip with electrodeposited nickel coating exhibiting a great diffusion depth
CN112877751A (zh) * 2021-01-06 2021-06-01 中国石油天然气集团有限公司 一种体积压裂用弯管内表面复合涂层及其制备方法和应用

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923611A (en) * 1974-12-23 1975-12-02 Ferro Corp Direct-on ceramic coating of carbon-rich iron
US3971120A (en) * 1974-12-23 1976-07-27 Ferro Corporation Direct-on ceramic coating of carbon-rich iron
US4828662A (en) * 1987-05-12 1989-05-09 Mb Group Plc Electrolytic stripping of cobalt
US4910096A (en) * 1987-08-10 1990-03-20 Hille & Muller Cold-rolled steel strip with electrodeposited nickel coating exhibiting a great diffusion depth
CN112877751A (zh) * 2021-01-06 2021-06-01 中国石油天然气集团有限公司 一种体积压裂用弯管内表面复合涂层及其制备方法和应用

Also Published As

Publication number Publication date
DE2016989C3 (de) 1974-08-08
BE765510A (fr) 1971-10-08
NO130692C (enrdf_load_stackoverflow) 1975-01-22
NO130692B (enrdf_load_stackoverflow) 1974-10-14
NL7104638A (enrdf_load_stackoverflow) 1971-10-12
DE2016989B2 (de) 1973-12-20
ES389127A1 (es) 1974-04-01
DE2016989A1 (de) 1971-10-28
AT316257B (de) 1974-07-10
FR2089510A5 (enrdf_load_stackoverflow) 1972-01-07
SE368033B (enrdf_load_stackoverflow) 1974-06-17
GB1316890A (en) 1973-05-16
CA974923A (en) 1975-09-23

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