WO1994003654A1 - Minimization of mounds in iron-zinc electrogalvanized sheet - Google Patents
Minimization of mounds in iron-zinc electrogalvanized sheet Download PDFInfo
- Publication number
- WO1994003654A1 WO1994003654A1 PCT/US1993/007144 US9307144W WO9403654A1 WO 1994003654 A1 WO1994003654 A1 WO 1994003654A1 US 9307144 W US9307144 W US 9307144W WO 9403654 A1 WO9403654 A1 WO 9403654A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- citric acid
- iron
- bath
- electrolyte
- Prior art date
Links
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 114
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010959 steel Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 6
- 239000007787 solid Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-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
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- This invention relates to iron-zinc electrogalvanized metal sheet and strip, and particularly to improved methods and electrolytes for providing electrogalvanized steel sheets and strip having enhanced surface smoothness essentially free of "mounds" caused by metal oxides occluded in the electrodeposited metal coating.
- Japanese published application No. 59/211594 discloses the production of Zn-Fe electroplated steel sheets wherein the deposited coating contains 7-35 weight percent Fe and is chemically single-phase.
- electrolyte baths contain chlorides of iron, zinc, ammonia and either ammonium citrate, 5 g/1, or citric acid, 2 g/1, together with sodium acetate, 10 g/1, and wherein plating was performed at 50"C (122"F) and a pH of 3.
- U.S. Patent No. 4,540,472 discloses the electrodeposition of Zn-Fe alloy coatings from an electrolyte bath containing chlorides of zinc, iron and potassium, together with an amount of sulfate ion, an adduct such as a polyethylene glycol, and a chelating agent such as citric acid in an amount from 0.5 g/1 to 5 g/1.
- This invention provides a method of electroplating elongated metal articles, such as steel sheet or strip, with a zinc-iron alloy coating, comprising passing the article to be plated through a chloride-containing electrolyte bath comprising a source of iron and zinc ions and from about 2 to 6 g/1, preferably about 2 to 3.5 g/1, and especially about 2 or 2.5 to about 3 g/1 of citric acid.
- the invention in another aspect, relates to an improved bath for the electrodeposition of zinc-iron coatings comprising a chloride-containing solution comprising iron and zinc ions and from about 2 to 6 g/1, preferably about 2.5 to 3.5, and especially about 2.5 to about 3 g/1 of citric acid, without other chelating or reducing agents.
- the electrolyte bath may contain a grain refining agent, such as a polyethylene glycol.
- Fig. 1 is a graph relating citric acid concentration to amount of solids in the electrolyte, for a commercial electrolyte solution and for filtered solutions to which known amounts of, respectively, iron scale and zinc scale are added.
- Figs. 2 and 3 are graphs relating citric acid concentration and solids content in the electrolyte versus running time for a commercial electroplating operation.
- Zinc-iron electroplated steel sheets are useful, e.g., in the fabrication of appliances and automobile body parts, such as hoods, where the appearance of the painted sheet is very important.
- citric acid serves as a chelating agent for ferric ion in chloride- containing electrolyte solutions for electroplating zinc-iron alloy coatings. As such, citric acid inhibits the precipitation of ferric hydroxide, and thus prevents increase in concentration of the undissolved solid contents of the electrolyte.
- the inventors have found that scaling of such large size particles from the iron anodes can be prevented or substantially reduced, so that mounds are not formed, by strictly controlling the amount of citric acid in the electrolyte, such that the total maximum solids in the electrolyte is about 0.5 g/1.
- citric acid may be used in maximum amount up to about 5 or 6 g/1, resulting in low concentrations of total suspended solids in the electrolyte.
- FIG. 1 shows that the solids level in the electrolyte falls with increasing citric acid content, up to a level of about 5 or 6 g/1, at which point the solids vs. citric acid concentration curves level off and become substantially constant.
- An exception is the laboratory-made electrolyte containing added zinc anode scale, in which increasing citric acid concentration has no solids lowering effect up to about 6 g/1 of citric acid.
- Fig. 1 shows that, in the filtered alloy solution containing 2 g/1 of iron oxide scale, increasing citric acid content to about 2 g/1 to 2.5 g/1 lowers iron scale to about 0.5 g/1, and 3 g/1 of citric acid results in lowering iron scale well below 0.5 g/1. From the same Fig., it is seen that about 6 g/1 of citric acid is required to reduce total solids content of a commercial electrolyte (including precipitated ferric hydroxide and anode scales) to about 0.5 g/1.
- a commercial electrolyte
- citric acid concentration of the electrolyte is accompanied by some decrease in plating efficiency, and decrease in solids content, particularly iron anode scale, is not great over a citric acid concentration of about 3 to 3.5 g/1.
- increased amounts of citric acid increase the cost of the electrolyte. Therefore, we prefer to limit the upper level of citric acid to a concentration of about 3.5, especially about 3, in the electrolyte baths of the invention.
- Substantially mound-free coatings can be produced in accordance with the invention in a process operated at a pH of 3 to 3.5, a temperature of about 125°F and at line speeds up to 700 fpm.
- the products so produced are lustrous, highly corrosion-resistant and of good adherence to the metal substrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940703792A KR100294366B1 (ko) | 1992-07-30 | 1993-07-29 | 마운드가없는철-아연전기아연도금된시이트의제조방법및이에사용되는전해질욕 |
| JP6505437A JPH07509540A (ja) | 1992-07-30 | 1993-07-29 | 電気亜鉛メッキした鉄−亜鉛シート中のマウンドの最少化 |
| EP93918494A EP0652981B1 (en) | 1992-07-30 | 1993-07-29 | Minimization of mounds in iron-zinc electrogalvanized sheet |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US922,994 | 1992-07-30 | ||
| US07/922,994 US5316653A (en) | 1992-07-30 | 1992-07-30 | Minimization of mounds in iron-zinc electrogalvanized sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994003654A1 true WO1994003654A1 (en) | 1994-02-17 |
Family
ID=25447938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1993/007144 WO1994003654A1 (en) | 1992-07-30 | 1993-07-29 | Minimization of mounds in iron-zinc electrogalvanized sheet |
Country Status (6)
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8190408B2 (en) * | 2010-03-22 | 2012-05-29 | Livermore Software Technology Corporation | Methods and systems for numerically predicting surface imperfections on stamped sheet metal parts |
| JP2016515936A (ja) * | 2013-04-15 | 2016-06-02 | シーメンス アクティエンゲゼルシャフト | 吸収媒体、吸収媒体を製造するための方法、並びに酸性ガスから硫化水素を分離するための方法及び装置 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2778787A (en) * | 1954-03-15 | 1957-01-22 | British Iron Steel Research | Electrodeposition of iron zinc alloys |
| EP0151235A1 (en) * | 1983-12-03 | 1985-08-14 | Kawasaki Steel Corporation | Process for preparing Zn-Fe base alloy electroplated steel strips |
| US4540472A (en) * | 1984-12-03 | 1985-09-10 | United States Steel Corporation | Method for the electrodeposition of an iron-zinc alloy coating and bath therefor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3220448C1 (de) * | 1982-05-29 | 1983-08-11 | Grundfos A/S, 8850 Bjerringbro | Pumpenaggregat fuer Heizungs- und Brauchwasseranlagen |
-
1992
- 1992-07-30 US US07/922,994 patent/US5316653A/en not_active Expired - Fee Related
-
1993
- 1993-07-29 WO PCT/US1993/007144 patent/WO1994003654A1/en active IP Right Grant
- 1993-07-29 EP EP93918494A patent/EP0652981B1/en not_active Expired - Lifetime
- 1993-07-29 JP JP6505437A patent/JPH07509540A/ja active Pending
- 1993-07-29 KR KR1019940703792A patent/KR100294366B1/ko not_active Expired - Fee Related
- 1993-08-02 TW TW082106213A patent/TW279906B/zh active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2778787A (en) * | 1954-03-15 | 1957-01-22 | British Iron Steel Research | Electrodeposition of iron zinc alloys |
| EP0151235A1 (en) * | 1983-12-03 | 1985-08-14 | Kawasaki Steel Corporation | Process for preparing Zn-Fe base alloy electroplated steel strips |
| US4540472A (en) * | 1984-12-03 | 1985-09-10 | United States Steel Corporation | Method for the electrodeposition of an iron-zinc alloy coating and bath therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0652981B1 (en) | 1996-03-27 |
| KR950701397A (ko) | 1995-03-23 |
| TW279906B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1996-07-01 |
| US5316653A (en) | 1994-05-31 |
| EP0652981A1 (en) | 1995-05-17 |
| JPH07509540A (ja) | 1995-10-19 |
| KR100294366B1 (ko) | 2001-09-17 |
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