EP0577486B1 - Verfahren zum Korrosionsschutz von Metallgegenständen und hergestellte Metallgegenständen - Google Patents

Verfahren zum Korrosionsschutz von Metallgegenständen und hergestellte Metallgegenständen Download PDF

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Publication number
EP0577486B1
EP0577486B1 EP19930401649 EP93401649A EP0577486B1 EP 0577486 B1 EP0577486 B1 EP 0577486B1 EP 19930401649 EP19930401649 EP 19930401649 EP 93401649 A EP93401649 A EP 93401649A EP 0577486 B1 EP0577486 B1 EP 0577486B1
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EP
European Patent Office
Prior art keywords
volume
sheet
metal part
process according
metal
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 - Lifetime
Application number
EP19930401649
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English (en)
French (fr)
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EP0577486A1 (de
Inventor
Claude Morand
Philippe Antoine
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.)
Sollac SA
Original Assignee
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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Application filed by Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical Sollac SA
Publication of EP0577486A1 publication Critical patent/EP0577486A1/de
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

  • the subject of the present invention is a process for temporary protection against corrosion of a metal part, in particular of a metal sheet.
  • the sheets obtained are subjected to pickling, then they are stored in a warehouse.
  • the sheets are then often exposed directly to the aggressions of the ambient environment and corrode over time before reaching the user.
  • the sheets should be isolated from the ambient environment by covering them with a waterproof material which is resistant to attack by the ambient environment.
  • a known process for protecting metal sheets against corrosion for a period of at least three months consists in applying to the previously pickled and dried sheets a film formed of an oil, by soaking the sheets in an oil bath in order to give them a fatty coating with a surface density of the order of 1 to 3 g / m 2 .
  • the previously pickled products are first of all protected for a period of the order of a few days by corrosion inhibitors, such as amine-based corrosion inhibitors, for example the product RC 305 sold. by CRODA.
  • corrosion inhibitors such as amine-based corrosion inhibitors, for example the product RC 305 sold. by CRODA.
  • the products are protected more durably by applying a fatty protective film as described above or are delivered to the user without special protection.
  • the process consisting in applying to the pickled products having possibly undergone finishing operations a fatty film of oil, has several important drawbacks.
  • the user must before any use, for example painting, enameling or galvanizing, degrease the surfaces of said products for a long time to avoid unnecessary pollution of tools (shears, splitters) and installations, and to allow adhesion of coatings.
  • the object of the present invention is therefore to remedy the drawbacks of the prior art by proposing a method which makes it possible to protect effectively against corrosion of metal parts, in particular metal sheets, and to overcome the cleaning operations of said products. before use.
  • the subject of the invention also relates to a coated sheet as defined in claim 9 and to its uses as defined in claims 10 to 13.
  • the oil contained in the oily phase of the emulsion can consist of a vegetable or animal oil.
  • the mineral oil of the oily phase is a paraffinic type oil.
  • surfactant for the oily phase a surfactant of polyoxyethylene type.
  • a carboxylic acid, a barium or sodium alkyl sulfonate or a salt is advantageously used as an inhibitor of corrosion of the oily phase.
  • amine and fatty acid are advantageously used as an inhibitor of corrosion of the oily phase.
  • the aqueous emulsion is applied by spraying.
  • the prior drying operation promotes the reactivity of the sheet as well as the attachment mechanisms of the product which will be applied subsequently to said sheet.
  • a preferred example of the oily phase used in the aqueous emulsion consists of the product sold under the name PREVOX 6767 R by HENKEL.
  • the metal part is preferably a metal sheet, the dry film being formed on at least one face of said sheet.
  • the subject of the invention is also a metal sheet coated with a dry protective film against corrosion obtained by the process according to the invention, characterized in that the dry film comprises from 300 to 800 mg / m 2 of deposited product obtained from the applied emulsion, the quantity of product being determined by chemical determination of the surfactant according to standard NFT 73258.
  • the steel sheet is first pickled by pickling in acid baths, for example in hydrochloric acid, in order to remove the chemical substances, such as the iron oxides constituting the scale, adhering to the surface of the sheet. and which would interfere with the subsequent application of a coating. Then the sheet is immersed in the rinsing water tanks to remove all traces of acid.
  • acid baths for example in hydrochloric acid
  • the emulsion according to the invention is then applied by spraying onto the sheet.
  • a chemical dosage of the film is carried out in accordance with standard NFT 73258 relating to the determination of surfactants and detergents.
  • the product constituting the film is removed from a determined surface area equal to S (m 2 ) of the sheet by washing with chloroform.
  • the sample is collected in a 200 ml volumetric flask to which 10 ml of water are added.
  • a volumetric assay of the sample is then carried out using a mixed indicator, the hyamine, the hyamine solution being titrated at 0.004 mol / l until the pink color turns blue.
  • V the volume of hyamine poured (ml) and by S the sampling surface
  • the sheet, pickled with hydrochloric acid and rinsed, is heated to a temperature of 60 ° C. for drying, using hot air dryers.
  • an aqueous emulsion containing 5% by volume of an oily phase consisting of the product sold under the name PREVOX 6767 R by HENKEL is sprayed onto one face of the pickled steel sheet.
  • the spraying is carried out by means of conventional spray nozzles of the "VEEJET” type with an opening angle of 65 ° which makes it possible to cover a square of 25 cm side on substrate placed 20 cm from the nozzle.
  • the coated sheet is heated to a temperature of 90 ° C. by means of hot air dryers arranged in an appropriate manner.
  • a dry and thin film is thus formed on the surface of the pickled steel sheet to protect it against corrosion for a minimum of three months.
  • the coated sheet is then wound and placed in a storage hall.
  • the coils can be directly delivered to users without receiving any special treatment, these then have a period of three months to proceed with the transformation of the sheet in complete safety from corrosion.
  • a simple degreasing is sufficient to remove all traces of product on the surface of the sheet and users are also assured not to pollute their installations.
  • the coils can be unwound to complete the sheets and possibly be split before being delivered to users.
  • the sheet is previously pickled as described above in Example 1, rinsed and then dried using hot air dryers by heating to a temperature equal to 60 ° C to promote the reactivity of the sheet as well as the attachment mechanisms of the product.
  • An aqueous emulsion containing 5% by volume of an oily phase consisting of the product sold under the name 112 STS R by QUAKER is then sprayed onto one face of the pickled steel sheet and dried.
  • the spraying is carried out by means of conventional spray nozzles of the "VEEJET” type with an opening angle of 65 ° which makes it possible to cover a square of 25 cm side on a substrate placed 20 cm from the nozzle.
  • the sample is then assayed volumetrically using a 0.004 mol / l titrated hyamine solution as described above.
  • the sheet thus protected against corrosion for a period of at least three months can then be directly delivered to the user or undergo a finishing operation as explained for example 1.
  • test is carried out on test specimens of steel sheets of dimensions 50 ⁇ 100 mm which have been etched in a hydrochloric acid solution, the concentrations of free acidity and of ferrous chlorides being respectively equal to 80 g / l and 90 g / l, at a temperature of 85 ° C.
  • test pieces After pickling, the test pieces are then rinsed in two successive tanks of water and then dried by rotation of the test pieces.
  • aqueous emulsion containing 3% by volume of oily phase consisting of the product sold under the name PREVOX 6767 R by HENKEL (1) is then sprayed onto a first part of the test pieces.
  • aqueous emulsion containing 3% by volume of oily phase constituted by the product sold under the name RC 305 R by CRODA CHEMICALS (3) is also sprayed onto a third part of the test pieces.
  • This product known for its anti-corrosion properties, consists essentially of amines.
  • a test piece which has not undergone any corrosion treatment serves as a control sample (4).
  • test pieces are dried using hot air dryers whose temperature is also 90 ° C.
  • test pieces are then exposed to atmospheric conditions in a storage hall at a temperature of the order of 30 ° C and a relative humidity of the order of 70%.
  • the different test pieces are observed, taking into account the appearance of corrosion as a function of time.
  • the corrosion aspect is noted on a rating scale ranging from 1 to 4, the coefficient 1 being assigned to a test piece on which the first pits appear, the coefficient 4 corresponding to the entire corroded surface.
  • the curve shown in the appended figure represents the comparative evolution of corrosion over time for the four tests.
  • the sheets coated with the anticorrosion dry film according to the invention can undergo, without prior degreasing, the coating operations of the dip galvanizing, painting or enamelling type, while benefiting from very good anticorrosion protection, even after a long period of storage. In addition, degreasing the sheets remains very easy after prolonged storage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Claims (13)

  1. Verfahren zum zeitweiligen Schutz eines decapierten Metallstücks, insbesondere eines Blechs, gegen Korrosion, dadurch gekennzeichnet, daß es die Verfahrensstufen umfaßt, die bestehen in
    - dem Trocknen des metallischen Stücks,
    - dem Aufbringen einer Emulsion auf wenigstens einen Teil diesen metallischen Stücks, erhalten durch Dispergieren von 3 bis 13 Vol. % einer öligen Phase, die 75 bis 90 Vol. % wenigstens eines Mineralöls, 5 bis 10 Vol. % wenigstens eines oberflächenaktiven Mittels und 5 bis 15 Vol. % eines Korrosionsschutzmittels enthält, in Wasser,
    - Trocknen des überzogenen Metallstücks durch Erwärmen auf eine Temperatur zwischen 70° und 100°C derart, daß ein trockener Film erhalten wird, der 300 bis 800 mg/m2 des abgeschiedenen Produkts enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Mineralöl der Ölphase ein Öl vom Paraffintyp ist.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das oberflächenaktive Mittel der öligen Phase ein Tensid vom Polyoxyethylen-Typ ist.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Korrosionsschutzmittel der öligen Phase eine Carbonsäure, ein Alkylsulfonat von Barium oder von Natrium oder ein Salz eines Amins und einer Fettsäure ist.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die wäßrige Emulsion duch Zerstäuben aufgetragen wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die erste Stufe des Trocknens durchgeführt wird durch Erwärmen des Metallstücks auf eine Temperatur zwischen 30 und 90°C während einer Dauer zwischen 2 und 20 Sek.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das überzogene Metallstück während einer Dauer zwischen 2 und 20 Sek. getrocknet wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Metallstück ein Metallblech und der trockene Film wenigstens auf einer Seite dieses Blechs ausgebildet ist.
  9. Mit einem trockenen Schutzfilm gegen Korrosion beschichtetes Metallblech, erhalten nach dem Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Film 300 bis 800 mg/m2 des, ausgehend von der nach einem der vorhergehenden Ansprüche aufgetragenen Emulsion, erhaltenen abgeschiedenen Produkts umfaßt.
  10. Verwendung eines mit einem trockenen Film überzogenen Metallblechs, das durch vorheriges Trocknen des Metallblechs und Auftragen einer Emulsion erhalten wird, wobei die Emulsion erhalten wird durch Dispergieren von 3 bis 13 Vol. % einer öligen Phase, die 75 bis 90 Vol. % wenigstens eines Mineralöls, 5 bis 10 Vol. % wenigstens eines oberflächenaktiven Mittels und 5 bis 10 Vol. % wenigstens eines Korrosionsschutzmittels enthält, in Wasser, anschließendes Trocknen des Metallstücks durch Erwärmen auf eine Temperatur zwischen 70 und 100°C derart, daß ein trockener Film erhalten wird, der 300 bis 800 mg/m2 des abgeschiedenen Produkts enthält, zum direkten Aufbringen eines Überzugs ohne vorheriges Entfetten auf das Blech.
  11. Verwendung eines Blechs nach Anspruch 10 in der Malerei ohne vorheriges Entfetten.
  12. Verwendung eines Blechs nach Anspruch 10 zum Emaillieren ohne vorheriges Entfetten.
  13. Verwendung eines Blechs nach Anspruch 10 zur Tauchgalvanisierung ohne vorheriges Entfetten.
EP19930401649 1992-06-30 1993-06-25 Verfahren zum Korrosionsschutz von Metallgegenständen und hergestellte Metallgegenständen Expired - Lifetime EP0577486B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9208037 1992-06-30
FR9208037A FR2692912B1 (fr) 1992-06-30 1992-06-30 Procede de protection contre la corrosion de pieces metalliques et pieces metalliques obtenues par ce procede.

Publications (2)

Publication Number Publication Date
EP0577486A1 EP0577486A1 (de) 1994-01-05
EP0577486B1 true EP0577486B1 (de) 1997-04-09

Family

ID=9431353

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Application Number Title Priority Date Filing Date
EP19930401649 Expired - Lifetime EP0577486B1 (de) 1992-06-30 1993-06-25 Verfahren zum Korrosionsschutz von Metallgegenständen und hergestellte Metallgegenständen

Country Status (9)

Country Link
US (1) US5391396A (de)
EP (1) EP0577486B1 (de)
JP (1) JP3363209B2 (de)
KR (1) KR100298795B1 (de)
AT (1) ATE151451T1 (de)
CA (1) CA2099449C (de)
DE (1) DE69309556T2 (de)
ES (1) ES2101259T3 (de)
FR (1) FR2692912B1 (de)

Families Citing this family (11)

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US5389138A (en) * 1993-03-31 1995-02-14 Kay Chemical Company Oven pretreatment and cleaning composition containing silicone
CA2147939C (en) * 1994-04-28 1999-07-06 Elliott Y. Spearin In-line application of solid lubricant to steel strip
US5555756A (en) * 1995-01-24 1996-09-17 Inland Steel Company Method of lubricating steel strip for cold rolling, particularly temper rolling
FR2736935B1 (fr) * 1995-07-21 1997-08-14 Lorraine Laminage Solution aqueuse de traitement contre la corrosion de toles d'acier revetues sur une face de zinc ou d'alliage de zinc
FR2765595B1 (fr) 1997-07-01 1999-10-01 Lorraine Laminage Composition pour protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition
FR2767140B1 (fr) * 1997-08-07 1999-10-29 Lorraine Laminage Procede de traitement de surface de pieces metalliques
FR2789084B1 (fr) * 1999-01-28 2001-03-09 Lorraine Laminage Emulsion d'huile dans l'eau comprenant au moins un additif de lubrification
EP1038594A1 (de) * 1999-03-23 2000-09-27 Peter Damgaard Nielsen Verfahren zur Oberflächenbehandlung von Objekten durch Spritzen von flüssigen Behandlungsmitteln
DE19947233A1 (de) * 1999-09-30 2001-11-22 Chemetall Gmbh Verfahren zur Herstellung eines polymeren Filmes auf einer Metalloberfläche sowie Konzentrat und Behandlungsflüssigkeit hierfür
FR2805277B1 (fr) * 2000-02-18 2002-04-19 Usinor Procede de fabrication d'une piece metallique emaillee sans operation de degraissage
WO2010000454A1 (en) 2008-07-04 2010-01-07 Corus Uk Limited Method for coating a steel substrate, and coated steel substrate

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Also Published As

Publication number Publication date
ES2101259T3 (es) 1997-07-01
JP3363209B2 (ja) 2003-01-08
CA2099449A1 (fr) 1993-12-31
KR100298795B1 (ko) 2001-11-22
CA2099449C (fr) 2003-09-16
FR2692912A1 (fr) 1993-12-31
JPH06184770A (ja) 1994-07-05
KR940005373A (ko) 1994-03-21
EP0577486A1 (de) 1994-01-05
DE69309556D1 (de) 1997-05-15
DE69309556T2 (de) 1997-07-24
ATE151451T1 (de) 1997-04-15
US5391396A (en) 1995-02-21
FR2692912B1 (fr) 1995-06-30

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