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US3337431A - Electrochemical treatment of metal surfaces - Google Patents

Electrochemical treatment of metal surfaces Download PDF

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Publication number
US3337431A
US3337431A US319952A US31995263A US3337431A US 3337431 A US3337431 A US 3337431A US 319952 A US319952 A US 319952A US 31995263 A US31995263 A US 31995263A US 3337431 A US3337431 A US 3337431A
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Prior art keywords
acid
chromium ion
trivalent chromium
per liter
chromic acid
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Kitamura Yoichi
Inui Tsuneo
Shuto Etsuro
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising

Definitions

  • the present invention relates to a process of electrochemical treatment to form a protective coating on surfaces of iron, steel, aluminum and aluminum alloys, and to electrolytes to be employed therein.
  • the present invention relates to a process of forming a hydrated chromium oxide coating which has high corrison resistance and provides an excellent base for the adhesion of paint, varnish, lacquer and other organic finishes, on surfaces of iron, steel, aluminum and aluminum alloys in a chromic acid solution.
  • electrolytic methods Conventionly a number of similar electrolytic methods have been reported. For example, the following electrolytes have been proposed:
  • a further object of the present invention is to provide metal surfaces which are better bases for the adhesion of organic coatings than in conventional electrolytic tinplate, even when they are mechanically formed and exposed to various conditions after coating.
  • the electrolytic bath is an aqueous solution consisting essentially of chromic acid, trivalent chromium ion in a definite proportion to hexavalent chominm ion and sulfuric acid in the presence of a fluorine compound, wherein the anode is lea-d or lead alloy and the cathode is one of the above mentioned metals to be coated.
  • a hydrated oxide film of chromium is formed on the metal surfaces.
  • pure iron, low carbon steels, pure aluminum and its alloys containing more than 90% of aluminum are the most suitable.
  • anode metals pure lead, pure lead, and its alloys containing more than 90% of aluminum are the most suitable.
  • lead-tin alloys lead-antimony alloys and lead-silver alloys are suitable.
  • the surface of metallic material should be cleaned by any conventional treatment such as degreasing with alkalis and pickling with acids for iron and steel, and cleaning with alkalis for aluminum and aluminum alloys.
  • the electrolyte employed in the present invention contains chromium ion which is mainly supplied by chromic acid.
  • the optimum concentration of chromic acid is within the range from 40 g./l. to 100 g./l. It the concentration of chromic acid is below 40 g./l., the film formed has inferior formability, decreased lacquer adhesion quality and weaker chemical resistance, and it the concentration 7 of chromic acid is above 100 g./l., the film is transformed from the state of hydrated chromium oxide to the state of metallic chromium with poorer corrison resistance.
  • Chromium ions existing in the electrolyte are the trivalent chromium ion and hexavalent chromium ion.
  • the optimum Weight ratio of hexavalent chromium ion to trivalent chromium ion ranges from 20 to 150, and the concentration of trivalent chromium ion should not exceed 2.5 g./l. If the Cr /Cr ratio becomes larger than 150, current efficiency goes down, the film formed becomes uneven and non-uniform. On the other hand, if the Cr /Cr ratio is smaller than 20, or trivalent chromium ion concentration exceeds 2.5 g./ 1., conductivity of the electrolyte goes down, bath voltage rises, current efliciency drops and, furthermore, formability of the film formed is lessened.
  • the present electrolyte initially contains reducing agents which serve to maintain the chromium ion in trivalent form in aqueous solution, thereby enabling continual operation.
  • the reducing agent must be a water soluble organic compound of simple structure, having alcoholic hydroxyl or phenolic hydroxyl groups. These hydroxyl groups are readily oxidized and readily decomposed or evaporated in a hot aqueous solution of chromic acid without leaving a precipitate. Heating an aqueous solution of chromic acid to which a reducing agent has been added for about 30 minutes at 60 0., provides the necessary amount of trivalent chromium ion.
  • the reducing agents include water soluble alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and monoethanolamine; polyalcohols, such as ethylene glycol, propylene glycol, glycerol, diethanolamine, triethanolamine, pentaerythritol, sorbitol and mannitol; phenol; and phenol sulfonic acids such as phenol-2,4-disulfonic acid,
  • 2-naphthol-3,6-disulfonic acid and 1,8-dihydroxynaphthalene-3,6-disulfonic acid.
  • Cresol, xylenol and polyphenols are not desirable, because they form a precipitate in the aqueous solutions of chromic acid.
  • the reducing agent may be present in such an amount that the required concentration of trivalent chromium ion is produced in the aqueous solution of chromic acid.
  • the bath of the present invention must contain sulfuric acid.
  • the sulfuric acid concentration in aqueous solutions of chromic acid should be in the range between 0.1 g./l. and 0.5 g./l. If the sulfuric acid concentration is lower than 0.1 g./l., it is hard to get a uniform film and to prevent yellow stains on the film which have a detrimental effect on appearance. As the sulfuric acid concentration increases, current efiiciency gradually goes up, but adhesion of the film formed to the base metal, formability and corrosion resistance of the film are decreased. Therefore the sulfuric acid concentration should not exceed 0.5 g./ 1. Accordingly, the sulfuric acid concentration should be maintained as low as possible within the range between 0.1 g./l. and 0.5 g./l. In case phenol sulfonic acids are employed as reducing agents, it is not necessary to conduct further addition of sulfuric acid, so far as the required concentration of sulfuric acid is obtained with the phenol sulfonic acids.
  • cathode metal It is quite easy to form a thin film of hydrated chromium oxide on the surface of cathode metal, by means of applying direct current electrolysis in the bath mentioned above, composed of chromic acid, trivalent chromium ion and sulfuric acid, in which the said chemicals are admixed in concentrations mentioned above, the cathode is the metal to be treated and the anode is lead or lead alloy.
  • Electrolytes of the present invention may further contain fluorides, acidic fluorides, fiuosilicates and fluoborates.
  • the fluorine compounds help to obtain higher current efliciency and better throwing power and more excellent stabilized films in a wider concentration range.
  • Hydrofluoric acid Hydrofluoric acid
  • fluorides such as sodium fluoride, potassium fluoride, ammonium fluoride and acidic fluorides, such as acidic sodium fluoride, acidic potassium fluoride, acidic ammonium fluoride, and hydrofluosilicic acid
  • fluosilicates such as sodium fluosilicate, potassium fluosilicate, ammonium fluosilicate, and hyd-rofluoboric acid
  • fluoborates such as sodium fiuoborate, potassium fluoborate, and ammonium fluoborate.
  • the amount of addition of these fluorine compounds should not exceed 1.0 g./l. When the amount exceeds the above range, formability, lacquer adhesion quality and corrosion resistance of the film formed are badly affected.
  • the conditions for the electrolysis of the present in vention are preferably as follows, namely, temperature of treatment; 40-70 C., current density; not less than 12.5 a./ sq. dm., time for treatment; l20 seconds.
  • An increase in temperature results in a decrease in current efficiency and accelerates the transformation of the film from hydrated chromium oxide to metallic chromium which leads to poorer corrosion resistance.
  • the increase in temperature will cause an increase in evaporation loss of water and make it diflicult to control the concentration of the electrolytic bath. Operations should be controlled at temperatures below 70 C., if possible.
  • a current density of not less than 12.5 a./sq. dm. is necessary, and is preferably not more than 40 a./sq. dm. If current density is lower than 12.5 a./sq. dm., corrosion resistance will not be imroved very much even if a longer treating time is employed.
  • Treating time depends on the thickness of the film required if the other conditions are settled. In general, however, treatment for 1 to 20 seconds may be suflicient and treatment for 6 to 9 seconds may readily give a film of about 2 milligrams per sq. dm.
  • the gradual color changes of the film according to conditions for the electrolyte and electrolysis are characteristic, by which one can understand the properties of the film formed to some extent.
  • the color changes are: blue bluish purple bluish white, as chromic acid concentration increases; bluish yellowbluish purpleebluish white, as trivalent chromium ion concentration increases; bluish purple bluish yellowyellow, as sulfuric acid concentration increases; blue bluish purplee bluish white, as a fluorine compound concentration increases; yellowbluish yellow+blue bluish purple, as temperature rises; bluish yellow bluebluish purple, as current density increases; and bluish purpleblue bluish yellow yellow as the amount of treating current increases.
  • chromic acid and trivalent chromium ion For the purpose of obtaining a bluish purple film of the desirable properties, it is preferable to employ medium concentration of chromic acid and trivalent chromium ion, lower sulfuric acid concentration, medium concentration of a fluorine compound, higher temperature and current density and smaller amount of treating current or shorter treating time.
  • a colorless or grayish white film is almost always formed in the case of application of the treatment described in the present invention to aluminum and aluminum alloys.
  • the iron and steel treated according to the present invention can withstand an outdoor exposure test for one month and also resist a salt spray test for 24 hours without any signs of rust, even if the thickness of the treated film is as thin as 0.05 micron.
  • the lacquered plate After applying a film of about 10 microns of modified alkyd or modified epoxy lacquer on the steel plate treated according to the present invention, the lacquered plate can be deeply drawn with a drawing ratio of 2.2 and when a piece of adhesive tape is applied firmly on the lacquered side of the deeply drawn cup and then pulled off quickly, the tape carries away no lacquer. Furthermore, the lacquer film adheres firmly on the cup, even when it is tested with the adhesive tape after the cup is immersed in boiling water for one hour.
  • the surface film formed according to the present invention easily withstands alkalis, salts, petroleum oils, fats and organic solvents, excepting strong acids.
  • the steel plate treated according to the present invention can be used as a material for cans and containers for detergents, soaps, industrial chemicals, petroleum oils and paints in place of tinplate which is susceptible to alkalis and salts.
  • metal articles treated according to the present invention have excellent lacquer adhesion quality as well as excellent corrosion resistance, heat resistance up to 300 C., and weldability as good as base metals, even if the applied film is extremely thin.
  • Example 1 A 0.25 mm. cold rolled low carbon steel sheet, so-called black plate, was cathodically cleaned for 20 seconds at a current density of 4 a./sq. dm. at C. in a 7% sodium hydroxide solution, then rinsed with water, pickled for 10 seconds at room temperatures in 7% sulfuric acid and again rinsed with water. Then, the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (:5) as an anode.
  • the composition of the bath was 40 g./l. of chromic acid, 0.50 g./l. of ethyl alcohol, 0.62 g./l.
  • the electrolytic treatment of the steel sheet was conducted in the electrolyte obtained by adding 0.5 g./l. of ethyl alcohol as a reducing agent to an aqueous solution of 40 g./l. chromic acid, heating the mixture for 30 minutes at 60 C. to produce 0.62 g./l. of trivalent chromium ion, and thereto adding 0.1 g./l. of sulfuric acid and then 0.05 g./l.
  • Example 2 the electrolyte was prepared by adding chemicals in same manner as in Example 1.
  • Example 2 The same kind of cold rolled low carbon steel sheet was subjected to the same pretreatments as described in Example 1, then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (95:5) as an anode.
  • the composition of the bath was 50 g./l. of chromic acid, 0.20 g./l. of monoethanolamine, 0.51 g./l. of trivalent chromium ion, 0.20 g./l. of sulfuric acid, 0.20 g./l. of ammonium fluoborate and the Cr /Cr ratio was 51.
  • the temperature was 60 C.
  • current density was 23 a./ sq. dm.
  • time for treatment was seconds.
  • the film formed was bluish purple and transparent, and the steel sheet thus treated showed only few signs of rust after being subjected to a salt spray test with a 5% sodium chloride solution for 24 hours at 35 C.
  • the lacquer adhesion quality after mechanical forming was the same as in Example 1.
  • Example 3 The same kind of cold rolled low carbon steel sheet was subjected to the same pretreatments as described in Example 1. Then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (95:5) as an anode.
  • the composition of the bath was 50 g./l. of chromic acid, 0.50 g./l. of phenol-2,4-disulfonic acid, 0.30 g./l. of trivalent chromium ion, and 0.60 g./l. of hydrofluosilicic acid and the Cr /Cr ratio was 87.
  • the temperature was 60 C.
  • current density was 20 a./sq. dm.
  • time for treatment was 1 5 seconds.
  • the film formed was bluish white, and the steel sheet thus treated had a similar corrosion resistance and lacquer adhesion quality as those in Example 2.
  • Example 4 A 0.4 mm. cold rolled steel sheet was subjected to the same pretreatments as described in Example 1. Then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (95 :5) as an anode.
  • the composition of the bath was 60 g./l. of chromic acid, 0.50 g./l. of phenol, 0.38 g./l. trivalent chromium ion, 0.50 g./l. of sulfuric acid, and 0.50 g./l. of sodium fluoride and the Cr /Cr ratio was 82.
  • the temperature was 45 C.
  • current density was 12.5 a./sq. dm. and time for treatment was 10 seconds.
  • the film formed was bluish purple and the treated steel sheet had properties similar to those in Example 2.
  • Example 5 A 0.5 mm. aluminum sheet (99.0%) was cleaned for 10 seconds at room temperature in a 4% sodium bicarbonate solution, rinsed with water and then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (95:5 as an anode.
  • the composition of the bath was 50 g./l. of chromic acid, 0.15 g./l. of ethyl alcohol, 0.20 g./l. of trivalent chromium ion, 0.20 g./l. of sulfuric acid, and 1.0 g./l. of ammonium fiuosilicate.
  • the Cr-'/Cr ratio was 130.
  • Example 6 The same kind of cold rolled steel sheet was subjected to the same pretreatments as in Example 4, and then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with lead-antimony (:5) as an anode.
  • the composition of bath was 50 g./l. of chromic acid, 0 .20 -g./l. of methyl alcohol, 0.40 -g./1. of trivalent chromium ion, 0.20 g./l.
  • Example 7 The same kind of cold rolled steel sheet was subjected to the same pretreatments as in Example 4 and then the sheet was put in an electrolytic bath and direct current Was passed, wherein the sheet acted as a cathode with lead-antimony (95 :5 as an anode.
  • the composition of bath was 50 g./1. of chromic acid, 0.20 g./l. of ethylene glycol, 0.37 g./l. of trivalent chromium ion, 0.10 g./l. of sulfuric acid, and 0.20 g./l. of acidic ammonium fluoride.
  • the Cr /Cr ratio was 70.
  • the temperature was 60 C.
  • current density was 24 a./sq.
  • Example 2 The film formed was bluish yellow and transparent, and the treated steel sheet had A 0.8 mm. cold rolled steel sheet was subjected to the same pretreatments as in Example 1, and then the sheet was put in an electrolytic bath and direct current was passed, wherein the sheet acted as a cathode with leadantimony (95 :5 as an anode.
  • the composition of bath was g./l. of chromic acid, 2.0 g./l.. of ethyl alcohol, 2.5 g./1. of trivalent chromium ion, 0.20 g./l. of sulfuric acid, and 0.10 g./l. hydrofluoboric acid.
  • the Cr /Cr ratio was 21.
  • the temperature was 70 C.
  • current density was 20 a./sq. dm. and time for treatment was 6 seconds.
  • the film formed was pale bluish white, and the steel sheet treated had properties similar to those in Example 2.
  • a method of forming a protective coating of hydrated chromium oxide on a metal surface which comprises preparing an electrolytic bath by adding to an aqueous solution consisting essentially of 40-100 grams per liter of chromic acid, a water soluble organic hydroxyl compound in such a stoichiometrical amount that not more than 2.5 grams per liter of trivalent chromium ion and 20-150 parts by weight of hexavalent chromium ion per part of trivalent chromium ion are formed, (ll-0.5 gram per liter of sulfuric acid and an inorganic fluorine compound present in an amount up to 1.0 gram per liter, and effecting electrolysis in said electrolytic bath using as cathode the metal to be coated and an anode of leadbase metal.
  • water soluble organic hydroxyl compound is selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, monoethanolamine, a polyhydric alcohol, phen01, phenol-2,4-disulfonic acid, catechol-3,5-disulfonic acid, phenol-2,4,6-trisulfonic acid, 2-naphthol-3,6-disultonic acid and 1,8-dihydroXynaphthalene-3,6-disulfonic acid.
  • a method according to claim 1 wherein the metal to be coated is selected from the 'group consisting of iron, steel, aluminum and aluminum base alloys.
  • inorganic fluorine compound is selected from the group consisting of hydrofluoric acid, hydrofluosilicic acid, hydrofluoboric acid and water soluble salts thereof.
  • An aqueous electrolytic bath consisting essentially of 40-100 grams per liter of chromic acid wherein chromium ion is present in such a manner that not more than 2.5 grams per liter of trivalent chromium ion and 20-150 parts by weight of hexavalent chromium ion per part of trivalent chromium ion are present, 0.1-0.5 gram per liter of sulfuric acid and an inorganic fluorine compound selected from the group consisting of hydrofluoric acid, hydrofiuosilicic acid, hy drofluoboric acid and water 8 soluble salts thereof present in an amount up to 1.0 gram per liter.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US319952A 1962-11-10 1963-10-30 Electrochemical treatment of metal surfaces Expired - Lifetime US3337431A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484343A (en) * 1964-07-13 1969-12-16 Toyo Kohan Co Ltd Amine solution treatment of cathodically chromated metal surfaces
US3518169A (en) * 1965-07-13 1970-06-30 Toyo Kahan Co Ltd Alkali solution treatment of cathodically chromated metal surface
US3519542A (en) * 1964-11-12 1970-07-07 Toyo Kohan Co Ltd Process for treating a cathodically chromated metal surface
US3539427A (en) * 1968-05-08 1970-11-10 Bell Telephone Labor Inc Process for surface treatment of lead and its alloys
FR2362056A1 (fr) * 1976-08-18 1978-03-17 Toyo Kohan Co Ltd Tole d'acier utile pour former des boites de conserves d'aliments et de boissons
FR2385818A1 (fr) * 1977-04-01 1978-10-27 Cockerill Procede de fabrication d'un produit etame ainsi que ce produit
US4137132A (en) * 1976-06-01 1979-01-30 Bnf Metals Technology Centre Chromite coatings, electrolytes, and electrolytic method of forming the coatings
WO2003048416A1 (fr) 2001-12-04 2003-06-12 Nippon Steel Corporation Materiau metallique revetu d'un film de revetement d'oxyde metallique et/ou d'hydroxyde metallique et procede de fabrication associe
US20100122909A1 (en) * 2008-11-18 2010-05-20 Toru Murakami Method of preparing chromium plating bath and method of forming plating film
KR101189988B1 (ko) 2012-02-28 2012-10-12 이길성 금속재의 표면처리용 용액 조성물 및 이의 제조방법
CN102965696A (zh) * 2012-11-28 2013-03-13 郑州市大有制版有限公司 高效凹版镀铬添加剂
US20170145580A1 (en) * 2014-08-07 2017-05-25 Henkel Ag & Co. Kgaa Continuous coating apparatus for electroceramic coating of metal coil or wire

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2541269B2 (ja) * 1987-08-27 1996-10-09 日本板硝子株式会社 酸化物薄膜の製造方法

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US1545498A (en) * 1924-05-16 1925-07-14 Chemical Products Corp Method of cleaning steel and imparting rust-inhibitive properties thereto and solution therefor
US2459365A (en) * 1942-04-03 1949-01-18 Permanente Metals Corp Electrolytic protective surface treatment of magnesium base alloys
US2733199A (en) * 1956-01-31 Electrolytic treatment of metal
US2998361A (en) * 1958-06-11 1961-08-29 Toyo Kohan Co Ltd Electrochemical treatment of metal surfaces and the products thereof
US3011958A (en) * 1960-04-04 1961-12-05 Cons Mining & Smelting Co Anodic treatment of zinc and zinc-base alloys
US3032487A (en) * 1958-05-30 1962-05-01 Yawata Iron & Steel Co Electrolytic treatment of ferrous metal surfaces
US3081238A (en) * 1958-09-03 1963-03-12 Quaker Chem Corp Electrolytic treatment of metal surfaces
DE1152591B (de) * 1959-05-27 1963-08-08 Metallgesellschaft Ag Verfahren zur Herstellung von UEberzuegen auf Zink und Zinklegierungen und Konzentrat zur Durchfuehrung des Verfahrens
US3118824A (en) * 1958-05-30 1964-01-21 Yawata Iron & Steel Co Electrolytic treatment of metal surfaces
US3138548A (en) * 1961-04-11 1964-06-23 Inland Steel Co Tin plate treatment

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DE630934C (de) * 1933-06-23 1936-06-09 Druidenau Eismaschinen Und Kue Verfahren zur Herstellung einer anlaufbestaendigen, nicht sichtbaren Oberflaechenschutzschicht auf Silber oder Silberlegierungen

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Publication number Priority date Publication date Assignee Title
US2733199A (en) * 1956-01-31 Electrolytic treatment of metal
US1545498A (en) * 1924-05-16 1925-07-14 Chemical Products Corp Method of cleaning steel and imparting rust-inhibitive properties thereto and solution therefor
US2459365A (en) * 1942-04-03 1949-01-18 Permanente Metals Corp Electrolytic protective surface treatment of magnesium base alloys
US3032487A (en) * 1958-05-30 1962-05-01 Yawata Iron & Steel Co Electrolytic treatment of ferrous metal surfaces
US3118824A (en) * 1958-05-30 1964-01-21 Yawata Iron & Steel Co Electrolytic treatment of metal surfaces
US2998361A (en) * 1958-06-11 1961-08-29 Toyo Kohan Co Ltd Electrochemical treatment of metal surfaces and the products thereof
US3081238A (en) * 1958-09-03 1963-03-12 Quaker Chem Corp Electrolytic treatment of metal surfaces
DE1152591B (de) * 1959-05-27 1963-08-08 Metallgesellschaft Ag Verfahren zur Herstellung von UEberzuegen auf Zink und Zinklegierungen und Konzentrat zur Durchfuehrung des Verfahrens
DE1152869B (de) * 1959-05-27 1963-08-14 Metallgesellschaft Ag Verfahren zur Herstellung von UEberzuegen auf Zink und Zinklegierungen
US3011958A (en) * 1960-04-04 1961-12-05 Cons Mining & Smelting Co Anodic treatment of zinc and zinc-base alloys
US3138548A (en) * 1961-04-11 1964-06-23 Inland Steel Co Tin plate treatment

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484343A (en) * 1964-07-13 1969-12-16 Toyo Kohan Co Ltd Amine solution treatment of cathodically chromated metal surfaces
US3519542A (en) * 1964-11-12 1970-07-07 Toyo Kohan Co Ltd Process for treating a cathodically chromated metal surface
US3518169A (en) * 1965-07-13 1970-06-30 Toyo Kahan Co Ltd Alkali solution treatment of cathodically chromated metal surface
US3539427A (en) * 1968-05-08 1970-11-10 Bell Telephone Labor Inc Process for surface treatment of lead and its alloys
US4137132A (en) * 1976-06-01 1979-01-30 Bnf Metals Technology Centre Chromite coatings, electrolytes, and electrolytic method of forming the coatings
FR2362056A1 (fr) * 1976-08-18 1978-03-17 Toyo Kohan Co Ltd Tole d'acier utile pour former des boites de conserves d'aliments et de boissons
FR2385818A1 (fr) * 1977-04-01 1978-10-27 Cockerill Procede de fabrication d'un produit etame ainsi que ce produit
EP1455001A1 (en) * 2001-12-04 2004-09-08 Nippon Steel Corporation Metal material coated with metal oxide and/or metal hydroxide coating film and method for production thereof
WO2003048416A1 (fr) 2001-12-04 2003-06-12 Nippon Steel Corporation Materiau metallique revetu d'un film de revetement d'oxyde metallique et/ou d'hydroxyde metallique et procede de fabrication associe
US20050067056A1 (en) * 2001-12-04 2005-03-31 Hiromasa Shoji Metal material coated with metal oxide and/or metal hydroxide coating film and method for production thereof
EP1455001A4 (en) * 2001-12-04 2005-05-18 Nippon Steel Corp METAL OXIDE-COATED METALLIC MATERIAL AND / OR METAL HYDORXIDE COATING FILM AND METHOD OF MANUFACTURING THEREOF
US7883616B2 (en) 2001-12-04 2011-02-08 Nippon Steel Corporation Metal oxide and/or metal hydroxide coated metal materials and method for their production
US20100122909A1 (en) * 2008-11-18 2010-05-20 Toru Murakami Method of preparing chromium plating bath and method of forming plating film
US8372259B2 (en) * 2008-11-18 2013-02-12 C. Uyemura & Co., Ltd. Method of preparing chromium plating bath and method of forming plating film
CN101760766B (zh) * 2008-11-18 2014-03-12 上村工业株式会社 制备铬镀液的方法和形成镀膜的方法
KR101189988B1 (ko) 2012-02-28 2012-10-12 이길성 금속재의 표면처리용 용액 조성물 및 이의 제조방법
CN102965696A (zh) * 2012-11-28 2013-03-13 郑州市大有制版有限公司 高效凹版镀铬添加剂
CN102965696B (zh) * 2012-11-28 2015-05-20 郑州市大有制版有限公司 高效凹版镀铬添加剂
US20170145580A1 (en) * 2014-08-07 2017-05-25 Henkel Ag & Co. Kgaa Continuous coating apparatus for electroceramic coating of metal coil or wire

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NL6403188A (ja) 1965-09-27
DE1236898B (de) 1967-03-16
NL129365C (ja)
BE645889A (ja) 1964-07-16
GB1056357A (en) 1967-01-25

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