EP0622478A1 - Verfahren zur Elektroplattierung eines Zinklegierungsüberzuges auf ein Stahlsubstrat und so beschichtetes Stahlsubstrat - Google Patents
Verfahren zur Elektroplattierung eines Zinklegierungsüberzuges auf ein Stahlsubstrat und so beschichtetes Stahlsubstrat Download PDFInfo
- Publication number
- EP0622478A1 EP0622478A1 EP94400625A EP94400625A EP0622478A1 EP 0622478 A1 EP0622478 A1 EP 0622478A1 EP 94400625 A EP94400625 A EP 94400625A EP 94400625 A EP94400625 A EP 94400625A EP 0622478 A1 EP0622478 A1 EP 0622478A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- potential
- layer
- hydrogen
- undercoating
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 70
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 51
- 238000009713 electroplating Methods 0.000 title abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 124
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 80
- 239000000956 alloy Substances 0.000 claims abstract description 80
- 239000011701 zinc Substances 0.000 claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 69
- 239000001257 hydrogen Substances 0.000 claims abstract description 69
- 239000011247 coating layer Substances 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 92
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 abstract description 17
- 229940075397 calomel Drugs 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Definitions
- the present invention relates to a method of electrodeposition on a surface of a steel substrate of a coating of a zinc-based metal alloy.
- the present invention also relates to a coated steel material comprising a steel substrate and a coating layer of a zinc-based metal alloy.
- a layer of a zinc-based alloy such as for example of the zinc / nickel, zinc / aluminum, or zinc / cobalt type deposited on a steel substrate has an excellent protective activity for said substrate against corrosion.
- steel materials coated with a zinc / nickel alloy are widely useful as corrosion resistant materials in the field of motor vehicles, household appliances and building materials, in particular for building.
- steel sheets coated with a layer of zinc on one side and a coating layer of a zinc-nickel alloy on the other side are commonly used.
- the first so-called cosmetic corrosion initiated mainly by mechanical aggression of the scratching or gravel type, can bring the bare steel into contact with the external atmosphere.
- the second so-called perforating corrosion most often occurs in the hollow bodies and progresses from the inside to the outside of the body.
- an electrodeposition process which consists in passing said substrate through an electrolyte bath containing zinc ions and nickel ions in chloride medium or in sulphate medium.
- the bath can have the following composition: ZnCl2: 2 to 3 moles per liter NiCl2: 0.2 to 1 mole per liter The rest being demineralized water or not, Bath temperature 50 to 70 ° C, pH: 4 to 5.
- the current density is adjusted to obtain the desired percentage of nickel in the zinc / nickel alloy (usually of the order of 12% nickel).
- the zinc / nickel alloy coating thus electrodeposited has a relatively deplorable adhesion property.
- one solution consists in depositing a first layer of nickel coating by chemical deposition by dipping without electric current, then depositing a layer of zinc / nickel alloy by electrodeposition on the first previously deposited nickel layer.
- the adhesion of the coating is better than in the case of a deposit by direct electrodeposition, but it is not completely satisfactory.
- the object of the invention is therefore to avoid the drawbacks mentioned above by proposing a method of electrodeposition on a surface of a steel substrate of a layer of a coating of a zinc-based metal alloy, of the type ZnX, of which X is the second element of this alloy, which ensures good adhesion of the coating to said steel substrate, without producing a coating layer by chemical dip coating.
- the subject of the invention is therefore a method of electrodeposition on a surface of a steel substrate of a coating layer of a zinc-based metal alloy, of the ZnX type, X being the second element of this alloy, characterized in that it is deposited between the surface of the substrate and the coating layer of said alloy, an undercoating layer of said alloy with a percentage of said element X such that the reduction potential of said alloy of said undercoating layer with respect to a saturated calomel electrode is greater than or equal to or substantially less than the release potential of the hydrogen on the steel of the substrate, to obtain the percentage of the second element X desired.
- the invention also relates to a coated steel material comprising a steel substrate and a coating layer of a zinc-based metal alloy of the ZnX type, X being the second element of this alloy, said coating layer being deposited by electrodeposition on a surface of said substrate, characterized in that it comprises between the surface of the substrate and the coating layer, a layer of under coating of said alloy with a percentage of the second element X such that the reduction potential of said alloy of the undercoating layer with respect to a saturated calomel electrode is greater than or equal to or substantially less than the potential for evolution of hydrogen on the substrate steel.
- the subject of the invention is also a coated steel material comprising a steel substrate and a coating layer of a zinc / nickel alloy with 12% nickel, said coating layer being deposited by electrodeposition on a surface of said substrate, characterized in that it comprises between the surface of the substrate and the coating layer, an undercoating layer of zinc / nickel alloy with 24% nickel and, on said undercoating layer, an intermediate layer undercoating of zinc / nickel alloy with 18% nickel.
- the invention will be described for a zinc-based metal alloy of the ZnX type, the second element X of this alloy being nickel, but which can also be, for example, iron, cobalt or chromium.
- the metal substrate is polarized to bring it to the reduction potential of the alloy to be deposited, that is to say that said substrate is polarized at the potential of -0.95 V / Ecs in the case of the zinc / nickel alloy with 12% nickel.
- the electrodeposition taking place in an aqueous acid medium for example in a bath containing ZnCl2, KCl, NiCl2 and H20 the pH of the solution is very acidic and there is a large number of H+ ions in solution.
- the hydrogen degassed in the form of bubbles and often these bubbles of hydrogen are formed below the coating layer preventing it from adhering to the surface of the metal substrate.
- Test pieces were coated with a coating layer of a zinc / nickel alloy with 12% nickel and a thickness of 6 ⁇ m.
- test pieces were electrodeposited, between the surface of the substrate and the coating layer of zinc / nickel alloy, of a layer of under coating of zinc / nickel alloy with a thickness of 0.04 ⁇ m with a different percentage of nickel depending on the test pieces.
- test pieces were the subject of electrodeposition, between the layer of undercoating of zinc / nickel alloy and the layer of coating of zinc / nickel alloy, of an intermediate layer of undercoating of a zinc alloy / nickel with a thickness of 0.04 ⁇ m, with a different percentage of nickel.
- the adhesion was classified in a range of 1 to 5, the coefficient 1 being reserved for the total tearing of the coating, the coefficient 5 has no tearing and the coefficients 2 to 4 according to the degree of tearing.
- test 1 a coating layer of zinc / nickel alloy with 12% nickel was directly electrodeposited on the surface of the steel substrate.
- the substrate was polarized to bring it to - 0.95V / DHW, potential for reduction of the zinc / nickel alloy to 12% nickel compared to a saturated calomel electrode.
- the deposition of the zinc / nickel alloy on the surface of the steel substrate begins and as far as the release of hydrogen is concerned, it is no longer the potential for its release on the steel that is required. take into account, but its release potential on the alloy that has been deposited.
- test 2 a layer of undercoating of zinc / nickel alloy with 15% nickel was first deposited before depositing the coating layer with 12% nickel.
- Test No. 4 gives a good adhesion result due to the potential for reduction of the zinc / nickel alloy to 21% nickel which is equal to -0.85V / DHW, that is to say quite close to -0.78V / DHW.
- Tests 5 to 9 show that it is possible to further improve the quality of the adhesion of the coating by depositing an intermediate layer of undercoating between the undercoating layer and the coating layer.
- the intermediate layer of zinc / nickel alloy undercoat has a percentage of nickel such that the reduction potential of said alloy is close to the potential for release of hydrogen on the zinc / nickel alloy previously deposited in the undercoat layer .
- Such successive depositions are carried out in a known manner, for example on a plating line of the CAROSEL type, in which the diffusion current in the bath is adjusted, of a first conducting roller to ensure a deposit of zinc / nickel alloy at 24% nickel and in the bath, a second conductive roller to ensure a deposit of zinc / nickel alloy with 18% nickel.
- the running speed of the steel strip forming the substrate is calculated to obtain the desired coating thickness, ie 0.04 ⁇ m.
- the release of hydrogen begins as soon as the steel substrate reaches -0.78V / DHW and the deposition of the zinc / nickel alloy begins when the substrate reaches - 0.80V / DHW, that is to say almost immediately after the release of hydrogen which is very limited.
- the evolution of hydrogen becomes active again when the steel substrate reaches the potential of evolution of hydrogen on the zinc / nickel alloy with 24% nickel and the deposition of the zinc / nickel alloy with 18% nickel begins when the potential of said substrate reached -0.90V / DHW.
- the steel substrate is polarized at -0.95V / DHW, potential for reduction of the zinc / nickel alloy to 12% nickel allowing its deposition on the steel substrate.
- the method according to the invention consists in depositing, between the surface of the steel substrate and the coating layer of zinc / nickel alloy, a undercoat layer of zinc / nickel alloy with a percentage of nickel such that the reduction potential of said alloy of said undercoat layer with respect to an electrode at saturated calomel is greater than or equal to or substantially less than the potential for evolution of hydrogen on the steel of the substrate, then to deposit, between the undercoating layer and the coating layer of zinc / nickel alloy, at least one layer intermediate undercoating with a percentage of nickel such that the reduction potential of the zinc / nickel alloy of the intermediate layer n of undercoating is greater than or equal to or substantially less than the potential for release of hydrogen on said alloy of the layer n-1 intermediate undercoat previously deposited, until depositing a layer of zinc / nickel alloy.
- the intermediate layer of zinc / nickel alloy undercoating can also be directly deposited with the desired percentage of nickel on the previously deposited undercoating layer.
- the reduction potential of the zinc-nickel alloy of the undercoating layer with respect to a saturated calomel electrode can be between the potential for hydrogen evolution on the steel of the substrate and said potential for hydrogen evolution minus 15%, or minus 10%, or minus 5% or minus 2%.
- the reduction potential of the zinc / nickel alloy of the intermediate undercoating layer may be between the hydrogen release potential on the previously deposited undercoat layer and said hydrogen release potential minus 15%, or minus 10%, or minus 5% or even minus 2%.
- the undercoating layer has a thickness greater than 0.01 ⁇ m and preferably greater than 0.02 ⁇ m.
- the intermediate undercoating layer or layers have a thickness greater than 0.01 ⁇ m.
- the method according to the invention is not limited to the deposition of a zinc / nickel alloy, but can very well be applied to the deposit of other zinc-based alloys, of the zinc / iron, zinc / chromium or zinc / cobalt type.
Landscapes
- 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)
- Coating With Molten Metal (AREA)
- Physical Vapour Deposition (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9305038A FR2704560B1 (fr) | 1993-04-28 | 1993-04-28 | Procede d'electrodeposition sur une surface d'un substrat en acier d'une couche d'un revetement d'un alliage a base de zinc et materiau d'acier revetu d'une couche de revetement d'un alliage a base de zinc. |
| FR9305038 | 1993-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0622478A1 true EP0622478A1 (de) | 1994-11-02 |
| EP0622478B1 EP0622478B1 (de) | 1997-08-06 |
Family
ID=9446542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94400625A Expired - Lifetime EP0622478B1 (de) | 1993-04-28 | 1994-03-23 | Verfahren zur Elektroplattierung eines Zinklegierungsüberzuges auf ein Stahlsubstrat und so beschichtetes Stahlsubstrat |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0622478B1 (de) |
| JP (1) | JPH06346280A (de) |
| AT (1) | ATE156524T1 (de) |
| CA (1) | CA2122198A1 (de) |
| DE (1) | DE69404730T2 (de) |
| ES (1) | ES2107144T3 (de) |
| FR (1) | FR2704560B1 (de) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10205751B4 (de) * | 2002-02-12 | 2004-09-30 | Robert Bosch Gmbh | Zündeinrichtung, insbesondere Zündkerze für Brennkraftmaschinen |
| DE202013001731U1 (de) | 2013-02-22 | 2013-03-11 | Dr.-Ing. Max Schlötter Gmbh & Co. Kg | Hochkorrosionsfeste Stahlteile |
| DK2770088T3 (en) | 2013-02-22 | 2017-05-15 | Dr Ing Max Schlötter Gmbh & Co Kg | Extremely corrosion resistant steel blanks and method of making them |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58130299A (ja) * | 1982-01-26 | 1983-08-03 | Nisshin Steel Co Ltd | 加工部の耐食性にすぐれたＺｎ−Ｎｉ合金電気めつき鋼板の製造法 |
| GB2157709A (en) * | 1984-04-13 | 1985-10-30 | Nisshin Steel Co Ltd | Process for preparing zn-ni-alloy-plated steel sheets |
| JPS6244594A (ja) * | 1985-08-21 | 1987-02-26 | Sumitomo Metal Ind Ltd | 自動車用高耐食性表面処理鋼板 |
| JPS62294198A (ja) * | 1986-06-12 | 1987-12-21 | Sumitomo Metal Ind Ltd | 自動車用防錆鋼板並びにその製造方法 |
-
1993
- 1993-04-28 FR FR9305038A patent/FR2704560B1/fr not_active Expired - Fee Related
-
1994
- 1994-03-23 DE DE69404730T patent/DE69404730T2/de not_active Expired - Fee Related
- 1994-03-23 ES ES94400625T patent/ES2107144T3/es not_active Expired - Lifetime
- 1994-03-23 EP EP94400625A patent/EP0622478B1/de not_active Expired - Lifetime
- 1994-03-23 AT AT94400625T patent/ATE156524T1/de not_active IP Right Cessation
- 1994-04-26 CA CA002122198A patent/CA2122198A1/fr not_active Abandoned
- 1994-04-28 JP JP6090797A patent/JPH06346280A/ja active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58130299A (ja) * | 1982-01-26 | 1983-08-03 | Nisshin Steel Co Ltd | 加工部の耐食性にすぐれたＺｎ−Ｎｉ合金電気めつき鋼板の製造法 |
| GB2157709A (en) * | 1984-04-13 | 1985-10-30 | Nisshin Steel Co Ltd | Process for preparing zn-ni-alloy-plated steel sheets |
| JPS6244594A (ja) * | 1985-08-21 | 1987-02-26 | Sumitomo Metal Ind Ltd | 自動車用高耐食性表面処理鋼板 |
| JPS62294198A (ja) * | 1986-06-12 | 1987-12-21 | Sumitomo Metal Ind Ltd | 自動車用防錆鋼板並びにその製造方法 |
Non-Patent Citations (3)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 11, no. 232 (C - 437)<2679> 29 July 1987 (1987-07-29) * |
| PATENT ABSTRACTS OF JAPAN vol. 12, no. 191 (C - 501)<3038> 3 June 1988 (1988-06-03) * |
| PATENT ABSTRACTS OF JAPAN vol. 7, no. 242 (C - 192)<1387> 27 October 1983 (1983-10-27) * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2704560B1 (fr) | 1995-08-11 |
| DE69404730T2 (de) | 1998-02-05 |
| JPH06346280A (ja) | 1994-12-20 |
| ATE156524T1 (de) | 1997-08-15 |
| DE69404730D1 (de) | 1997-09-11 |
| ES2107144T3 (es) | 1997-11-16 |
| EP0622478B1 (de) | 1997-08-06 |
| FR2704560A1 (fr) | 1994-11-04 |
| CA2122198A1 (fr) | 1994-10-29 |
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