EP0025396B1 - Verfahren zur Herstellung eines Materials für die Herstellung metallischer Verpackungen, insbesondere Konservendosen, aus einem beschichteten Stahlblech - Google Patents

Verfahren zur Herstellung eines Materials für die Herstellung metallischer Verpackungen, insbesondere Konservendosen, aus einem beschichteten Stahlblech Download PDF

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Publication number
EP0025396B1
EP0025396B1 EP80401265A EP80401265A EP0025396B1 EP 0025396 B1 EP0025396 B1 EP 0025396B1 EP 80401265 A EP80401265 A EP 80401265A EP 80401265 A EP80401265 A EP 80401265A EP 0025396 B1 EP0025396 B1 EP 0025396B1
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EP
European Patent Office
Prior art keywords
chromium
tin
bath
deposited
process according
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.)
Expired
Application number
EP80401265A
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English (en)
French (fr)
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EP0025396A1 (de
Inventor
Raymond Allouf
Claude Mergey
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Carnaud SA
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Carnaud SA
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 Carnaud SA filed Critical Carnaud SA
Publication of EP0025396A1 publication Critical patent/EP0025396A1/de
Application granted granted Critical
Publication of EP0025396B1 publication Critical patent/EP0025396B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component

Definitions

  • the present invention relates generally to mild steel sheets of the type usually used for the manufacture of metal packaging, and in particular of canned food.
  • the cans generally have a body closed by two bottoms.
  • the body is produced by rolling a strip, the lips of which should be assembled which are superimposed at the end of such rolling; the funds both form separate parts of such a body, which it is necessary to then assemble to the latter by crimping.
  • electric welding with a thumbwheel which constitutes a particular embodiment of resistance welding, in order to produce sealed linear welds, consists in passing the sheets to be welded along the weld line to be produced, between two electrodes. form of knurled tight against each other, and to pass between the knobs of repeated current pulses so that the welding spots partially overlap.
  • This resistance welding mode has particular constraints, linked to running. The clamping pressure passes through a maximum at the point of contact of the rollers, in coincidence with the point of welding; an approach phase, or prior pressurization, cannot be provided to reduce the contact resistances between sheets and electrodes before the current flows.
  • the tinned material obtained is usually called tinplate.
  • TFS tin-free steel
  • the subject of the present invention is a process for obtaining a material comprising, like TFS, a composite layer of metallic chromium and chromium oxide, but having in particular good aptitude for electric welding with a seam thanks to the limitation of the chromium oxide content of its coating and the presence of a thin tin underlay.
  • the materials according to the invention have a corrosion resistance greater than that of TFS due to the formation by diffusion in the solid state of a layer of tin-iron alloy during a heat treatment for polymerization of organic coatings.
  • the tin-based layer forming a first protective layer is remelted and is therefore made of an iron tin alloy; and, on the other hand, the coating which surmounts this first protective layer, and which itself forms a second protective layer resulting from a chroming operation of the type of that explained above, consists essentially of oxide of chromium, the metallic chromium content of this coating preferably being zero and always less than 0.005 g / m 2 , ie 0.5 kt g / cm 2 , of surface treated.
  • the first protective layer is exclusively an alloy of tin and iron, the tin initially deposited being systematically remelted for this purpose, and a chromium-based passivation coating is applied to the underlay thus produced.
  • This coating is obtained either by passage through a conventional cathodic passivation bath of electrolytic white iron based on sodium dichromate, or by passage through a conventional chromium plating bath of the type of that indicated above for obtaining a TFS material.
  • the deposit based on chromium and chromium oxide obtained is so small that the corrosion resistance which results therefrom is insufficient; in the second case, the deposit obtained must, without others, have a chromium oxide content which is too high for an electrical welding of the material obtained to be effectively possible.
  • French patent application No. 70 23705 published under No. 2,053,038 relates to the deposition of mixed chromium / chromium oxide coatings on sheet substrates, in particular zinc-plated or tinned, with the essential aim of improving the resistance to corrosion, the chromium / chromium oxide weight ratio being able to vary within wide limits, 4/1 to 1/30. It appears from this request that the study of mixed coating deposits focused on zinc-plated substrates as a priority. In particular on such substrates, the mixed coating would provide, without specifying the conditions for mixed coating, in addition to an improvement in corrosion resistance, less aggressiveness with respect to spot welding electrodes, a conventional process for sheet metal. 'steel.
  • the present invention more specifically relates to a process for the protection of a sheet of mild steel leading to a material which can be welded by means of the wheel, the protective coating comprising a tin underlayment of very reduced thickness.
  • the invention provides a process for the preparation of a material for the manufacture of metal packaging, in particular cans, from mild steel sheets, the material having, with good corrosion resistance, a electrical contact resistance sufficiently low to allow electrical seam welding during the manufacture of packaging, a process according to which a layer of tin of between 0.1 and 1.5 g / m 2 is deposited on the surface of the sheet surface covered, and on the tinned sheet a composite layer of chromium metal and chromium oxide, characterized in that, on the tin layer not alloyed with steel, the said composite layer is deposited so that it contains at least 5 micrograms of chromium metal per square centimeter of covered surface (5 ⁇ g / cm 2 ) and between 0.6 and 2.5 ⁇ g / cm 2 of chromium in the form of oxide, limits included.
  • the limits of thickness of the tin layer correspond, for the lower limit, to the minimum essential for obtaining the technical result sought, and, for the upper limit , to what should not be exceeded to save tin, the reduction in contact resistivity, with the specified composition of the chromium-based composite layer, becoming insignificant beyond.
  • the layer of tin must not have given rise to iron-tin intermetallic compounds.
  • the composite layer will contain at most 10 ⁇ g / cm2 of chromium metal.
  • Tinning can be achieved by electrolysis; it is a known technique which will not be described here in all its details.
  • the steel sheet, previously degreased, pickled and rinsed is treated as a cathode, the anode being made of pure tin.
  • the tinning can advantageously be carried out by a tinning pickling, as described in particular in French patent N ° 1,500,185 of August 8, 1966.
  • the advantage of such a tinning pickling is in particular to lead to a slight deposit of free tin, particularly adherent and uniform, and well suited to obtaining the desired material according to the invention.
  • the tinning pickling bath used consists, like an electrolytic tinning bath, of an aqueous acid solution containing stannous ions, but with a lower concentration of stannous ions and a higher acid content; the steel sheet, previously degreased and rinsed, is treated therein as a cathode, as previously, but, this time, the anode is made of a material having a high resistance to anodic dissolution, graphite or ferrosilicon for example.
  • the concentration of hydrogen ions from the acid in the bath be large enough with respect to the concentration of stannous ions for the cathode current yield of deposited metal to be low, less than 50%, and preferably between 5 and 25%.
  • Chrome plating in principle can also follow a known technique: the chrome plating bath used is then an electrolytic bath of the type described in French patent No. 1,365,368 mentioned above, that is to say say an electrolytic bath which is formed of a dilute aqueous solution of chromic anhydride, containing for example sulfuric acid as catalyst, and in which the worked sheet is taken as cathode.
  • a person skilled in the art also knows how to obtain compliance with the contents, specified above, of the composite layer, of chromium oxide, either that it conducts the chromium-plating operation accordingly, or that the latter results in a value higher than that which is sought, it implements a corrective process of dissolution by more or less prolonged stay of the treated sheet in the chromium plating bath without current flow, capable of bringing this content to the desired value.
  • a chromic anhydride chromating bath optionally with sulfuric acid as catalyst, the content expressed as chromium being between 25 and 50 g / l.
  • the content of the trivalent chromium Cr- 3 bath is at most equal to 0.5 g / l, to avoid the appearance of coloring zones (layers interference).
  • the chromium plating begins as soon as the tinned sheet is immersed in the chromating bath, the sheet being cathodic before entering the bath, or in the first bath if several successive baths are used.
  • the chrome plating operation applied to the tinned sheet is, as usual, followed by at least one rinsing, drying and surface lubrication, for example using sebacate of dioctyle or cotton oil.
  • the contact resistivity test method will be specified by which the suitability for seam welding is determined.
  • the two resistances of the material, in the state and after baking will be noted respectively R 25 and R 2oo . It will be noted that during the baking, the tin not originally alloyed partially diffuses into the steel substrate to give intermetallic iron-tin compounds, so that, predictably, the resistance R 200 will be greater than resistance R 25 .
  • a cold reduced mild steel sheet having a thickness of 0.21 mm is electrolytically degreased in a sodium carbonate solution at 10 g / l, then this sheet is pickled in dilute sulfuric acid.
  • the weight of the coating of free tin deposited is 0.25 g / m 2 .
  • the layer based on chromium and chromium oxide deposited contains 9.2 ⁇ g / cm 2 of metallic chromium and 2.1 ⁇ g / cm 2 of chromium oxide (adjusted by redissolution).
  • the treated sheet is rinsed with water, dried, and coated with a thin film of dioctyl sebacate.
  • the electrical resistance of the material obtained is, under the experimental conditions specified above, of
  • the composite layer comprises 7.4 ⁇ g / cm 2 of chromium metal and by subsequent dissolution, the content of chromium oxide is reduced to 1.6 ⁇ g / cm 2 .
  • the resistances measured are:
  • the weight of the coating of free tin deposited is 0.25 g / m 2 .
  • the metallic chromium content of the chromium and chromium oxide layer deposited during the following chromium plating operation is 7.1 ⁇ g / cm 2 and its chromium oxide content of 1.9 ⁇ g / cm 2 .
  • the electrical resistances of the material obtained are:
  • the weight of the coating of free tin deposited is 0.3 g / m 2.
  • the metallic chromium content of the chromium and chromium oxide-based layer deposited during the following chromium plating operation is 7.0 ⁇ mg / cm 2 and its chromium oxide content of 1.9 ⁇ g / cm 2 .
  • the electrical resistances of the product obtained are:
  • the resistor R 25 is less than 10 x 10- 5 ohms, and the resistance R 200 of less than 100 x 10- 5 ohms.
  • the materials obtained by the process according to the invention show, after baking, a resistance at most of the same order as the resistance of the material of the prior art in the raw state, this under conditions where the baking has caused the apparently complete disappearance of free tin, while the material of the prior art, by steaming, saw its contact resistance considerably increase. It would therefore seem that the presence of free tin during the deposition of the composite layer leads to an improvement in the electrical weldability with the thumbwheel, even when the free tin has disappeared, or at least when this free tin is no longer detectable. .
  • the invention is not limited to the examples described, but embraces all of the variant embodiments.
  • the conditions for depositing the tin or the chromium chromium oxide composite layer may be subject to variants such that a person skilled in the art will know how to use them on the basis of the data indicated in the description.
  • the method according to the invention aims to obtain a material having particular aptitudes for electric welding with a seam.
  • the invention is not limited to the use of this material in assemblies by seam welding.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)

Claims (7)

1. Verfahren zum Bearbeiten eines Materials für die Herstellung von metallischen Verpackungen, insb. Konservendosen aus Weicheisenblechen, wobei das Material neben einem guten Korrosionswiderstand, einen elektrischen Kontaktwiderstand ausreichend niedrig für eine Elektroschweissung mittels Rädchen während der Herstellung der Verpackung darbietet, gemäss welchem Verfahren man oberflächlich auf dem Blech eine Zinnschicht zwischen 0,1 und 1,5 g/m2 der bedeckten Fläche aufbringt und das verzinnte Blech mit einer zusammengesetzten Schicht aus Chrommetall und Chromoxyd versehen wird, dadurch gekennzeichnet, dass man die zusammengesetzte Schicht auf die mit dem Eisen nicht legierte Zinnschicht in der Weise aufbringt, dass sie wenigstens 5 Mikrogramm pro Quadratzentimeter der bedeckten Fläche (5 µg/cm2) an Chrommetall und zwischen 0,6 und 2,5 µg/cm2 Chrom in Form eines Oxydes enthält, wobei die Grenzwerte mitumfasst sind.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man die zusammengesetzte Schicht in der Weise aufbringt, dass sie höchstens 10 ILg/cm2 metallisches Chrom enthält.
3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem das Aufbringen der zusammengesetzten Schicht einen Durchgang des verzinnten Bleches als Katode durch ein elektrolytisches Bad umfaßt, welches eine verdünnte Lösung von Chromsäureanhydrid enthält, dadurch gekennzeichnet, daß man nach dem Niederschlagen einer zusammengesetzten Schicht aus metallischem Chrom und Chromoxyd den Gehalt dieser Schicht an Chromoxyd auf die spezifizierten Werte zurückführt.
4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, bei dem das Aufbringen der zusammengesetzten Schicht wenigstens einen Durchgang des verzinnten Bleches als Katode durch ein elektrolytisches Bad umfaßt, welches eine verdünnte Lösung von Chromsäureynhydrid enthält, dadurch gekennzeichnet, daß wenigstens in dem ersten Bad der Gehalt an Cr-3-lonen auf einen Wert von höchstens gleich 0,5 g/I gehalten wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man den spezifizierten Gehalt an Cr-3- Ionen dadurch aufrechterhält, daß man das Bad über einen Harz-Kationen-Austauscher leitet.
6. Verfahren nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, daß der gesamte Chromgehalt des Bades, als Chrom gerechnet, zwischen 25 g/I und 50 g/I liegt, wobei die Grenzwerte mitumfaßt sind.
7. Verfahren nach irgendeinem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß das verzinnte Blech wenigstens in das erste Bad unter Spannung, bezogen auf eine Anode, eingetaucht wird.
EP80401265A 1979-09-06 1980-09-05 Verfahren zur Herstellung eines Materials für die Herstellung metallischer Verpackungen, insbesondere Konservendosen, aus einem beschichteten Stahlblech Expired EP0025396B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7922322 1979-09-06
FR7922322A FR2465011A1 (fr) 1979-09-06 1979-09-06 Materiau constitue d'une tole d'acier protegee, son procede de fabrication, et ses applications, ntamment aux boites de conserve

Publications (2)

Publication Number Publication Date
EP0025396A1 EP0025396A1 (de) 1981-03-18
EP0025396B1 true EP0025396B1 (de) 1984-05-23

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EP80401265A Expired EP0025396B1 (de) 1979-09-06 1980-09-05 Verfahren zur Herstellung eines Materials für die Herstellung metallischer Verpackungen, insbesondere Konservendosen, aus einem beschichteten Stahlblech

Country Status (15)

Country Link
US (1) US4421828A (de)
EP (1) EP0025396B1 (de)
JP (1) JPS5644793A (de)
AR (1) AR220659A1 (de)
BR (1) BR8005687A (de)
CA (1) CA1146818A (de)
DE (1) DE3067949D1 (de)
DK (1) DK157942C (de)
ES (1) ES8106563A1 (de)
FR (1) FR2465011A1 (de)
GR (1) GR69954B (de)
MX (1) MX153870A (de)
PL (1) PL129065B1 (de)
PT (1) PT71768B (de)
ZA (1) ZA805489B (de)

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JPS5931598B2 (ja) * 1980-03-08 1984-08-02 東洋製罐株式会社 新規溶接罐及び製造法
JPS59598B2 (ja) * 1980-08-08 1984-01-07 新日本製鐵株式会社 溶接性にすぐれためつき鋼板
FR2516553B1 (fr) * 1981-11-16 1985-10-25 Lorraine Laminage Procede de revetement anti-corrosion de toles d'acier destinees a l'emballage et soudages electriquement, ainsi que toles obtenues
JPS6039159B2 (ja) * 1981-12-07 1985-09-04 東洋鋼鈑株式会社 塗料密着性の優れた光沢錫めつき鋼板の製造法
IT1212859B (it) * 1983-03-21 1989-11-30 Centro Speriment Metallurg Laminati piatti di acciaio rivestiti perfezionati
FR2553320B1 (fr) * 1983-10-14 1986-02-21 Carnaud Sa Procede de soudage a la molette de corps d'emballages cylindriques, du type boites a conserves en un materiau comportant sur au moins une des faces d'une tole un revetement conducteur de resistance de contact specifique superieure a 1 x 10-5 ohm/cm2
GB2157319A (en) * 1984-04-13 1985-10-23 Toyo Kohan Co Ltd Tin free steel and its production
NL189310C (nl) * 1984-05-18 1993-03-01 Toyo Kohan Co Ltd Beklede stalen plaat met verbeterde lasbaarheid en werkwijze voor de vervaardiging.
JPS61130500A (ja) * 1984-11-29 1986-06-18 Kawasaki Steel Corp Ｓｎ／Ｃｒ２層めつき鋼板の製造方法
JPS62124296A (ja) * 1985-11-25 1987-06-05 Toyo Kohan Co Ltd シ−ム溶接性，塗料密着性の優れた表面処理鋼板およびその製造方法
IT1214691B (it) * 1986-07-14 1990-01-18 Centro Speriment Metallurg Lamierino d'acciaio perfezionato per imballaggio di alimentari e procedimento per la sua produzione
CA2019861C (en) * 1990-06-26 1995-10-17 Hiroaki Kawamura Tin-plated steel sheet with a chromium bilayer and a copolyester resin laminate and method
CN104302814B (zh) 2012-03-30 2016-12-21 塔塔钢铁艾默伊登有限责任公司 用于包装应用的涂覆基材及用于制备所述涂覆基材的方法
BR112015011731B1 (pt) * 2012-11-21 2021-10-19 Tata Steel Ijmuiden Bv Substrato de aço revestido para aplicações em embalagens e seu processo de produção
DE102019109354A1 (de) * 2019-04-09 2020-10-15 Thyssenkrupp Rasselstein Gmbh Verfahren zur Passivierung der Oberfläche eines Schwarzblechs oder eines Weißblechs und Elektrolysesystem zur Durchführung des Verfahrens

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FR1258185A (fr) * 1960-06-01 1961-04-07 Soudronic Ag Machine à souder automatique pour le soudage en continu de tôles
US3296100A (en) * 1962-05-09 1967-01-03 Yawata Iron & Steel Co Process for producing anticorrosive surface treated steel sheets and product thereof
US3278401A (en) * 1966-01-12 1966-10-11 Nat Steel Corp Method of treating tin-containing surfaces
US3616304A (en) * 1966-01-26 1971-10-26 M & T Chemicals Inc Method for treating chromium-containing baths
FR1562485A (de) * 1967-04-21 1969-04-04
US3679554A (en) * 1969-01-13 1972-07-25 Nippon Kokan Kk Method for electrolytic treatment of steel surface in a chromate solution
NL7009495A (de) * 1969-06-27 1970-12-29
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US3642587A (en) * 1970-07-06 1972-02-15 United States Steel Corp Chromium electroplating process and product thereof
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GB1354970A (en) * 1971-07-06 1974-06-05 Nippon Kokan Kk Coated chromate treated metal sheet and a process therefor
FR2228857B1 (de) * 1973-05-09 1976-06-25 Kloeckner Werke Ag
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JPS5323833A (en) 1976-08-18 1978-03-04 Toyo Kohan Co Ltd Surface treated steel sheet for coating
JPS5326236A (en) * 1976-08-25 1978-03-10 Toyo Kohan Co Ltd Surface treated steel sheet for coating
LU77061A1 (de) 1977-04-01 1979-01-18

Also Published As

Publication number Publication date
PL129065B1 (en) 1984-03-31
DK157942B (da) 1990-03-05
DK379180A (da) 1981-03-07
MX153870A (es) 1987-01-29
DK157942C (da) 1990-08-06
PL226558A1 (de) 1981-07-10
DE3067949D1 (en) 1984-06-28
GR69954B (de) 1982-07-22
BR8005687A (pt) 1981-05-12
AR220659A1 (es) 1980-11-14
PT71768A (fr) 1980-10-01
ES494860A0 (es) 1981-08-01
US4421828A (en) 1983-12-20
FR2465011A1 (fr) 1981-03-20
ES8106563A1 (es) 1981-08-01
JPS5644793A (en) 1981-04-24
CA1146818A (fr) 1983-05-24
EP0025396A1 (de) 1981-03-18
FR2465011B1 (de) 1982-09-17
PT71768B (fr) 1981-06-26
ZA805489B (en) 1981-08-26

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