EP4074867A1 - Bain alcalin de placage de zinc- fer - Google Patents

Bain alcalin de placage de zinc- fer Download PDF

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Publication number
EP4074867A1
EP4074867A1 EP20900205.4A EP20900205A EP4074867A1 EP 4074867 A1 EP4074867 A1 EP 4074867A1 EP 20900205 A EP20900205 A EP 20900205A EP 4074867 A1 EP4074867 A1 EP 4074867A1
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EP
European Patent Office
Prior art keywords
iron
plating bath
alkaline zinc
asd
describes
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.)
Withdrawn
Application number
EP20900205.4A
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German (de)
English (en)
Inventor
Mari Asano
Kiyohiko Watabe
Tsukasa Niwa
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.)
Yuken Industry Co Ltd
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Yuken Industry Co Ltd
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 Yuken Industry Co Ltd filed Critical Yuken Industry Co Ltd
Publication of EP4074867A1 publication Critical patent/EP4074867A1/fr
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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
    • 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
    • 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

  • the present invention relates to an alkaline zinc-iron plating bath that includes a zinc compound, an alkali hydroxide, a metal salt containing iron, and a complexing agent.
  • Patent Literature 1 Japanese Examined Patent Publication No. S62-238387
  • the present invention has an object to provide an alkaline zinc-iron plating bath having an improved current efficiency, that is, an alkaline zinc-iron plating bath capable of efficiently forming a thick plating film.
  • the alkaline zinc-iron plating bath of the present invention is characterized by that the alkaline zinc-iron plating bath includes a zinc compound, an alkali hydroxide, a metal salt containing iron, and a complexing agent; and the complexing agent is an aliphatic compound having five or more hydroxy groups.
  • the alkaline zinc-iron plating bath of the present invention prevents redissolution of the deposited plating film because an aliphatic compound having five or more hydroxy groups is used as the complexing agent, for example, due to the inhibitor effect thereof, and therefore can form a thick plating film efficiently.
  • the "alkaline zinc-iron plating bath" described in the present invention is an alkaline zinc-iron plating bath that includes a zinc compound, an alkali hydroxide, a metal salt containing iron, and a complexing agent; and the complexing agent is an aliphatic compound having five or more hydroxy groups.
  • the zinc compound is, for example, ZnO; and the metal concentration of zinc is preferably 5 to 40 g/L.
  • the alkali hydroxide is, for example, NaOH or KOH; and the NaOH content is preferably 30 to 200 g/L.
  • the metal salt containing iron is, for example, Fe 2 (SO 4 ) 3 , Fe(SO 4 ) ⁇ 7H 2 O, FeCl 3 , FeCl 2 , or Fe(OH) 3 ; and the metal concentration of iron is preferably 0.02 to 20 g/L, while more preferably 0.1 to 10 g/L.
  • the metal concentration of iron is preferably 1 g/L or more, while more preferably 3 g/L or more.
  • the eutectic rate of iron varies greatly depending on the current density.
  • the complexing agent that is an aliphatic compound having five or more hydroxy groups is used, the eutectic rate of iron can be made almost constant independent of the current density. Specifically, for example, when the current density is within the range of 0.5 to 10 ASD, it is possible to reduce the difference in the eutectic rate of iron.
  • the aliphatic compound having five or more hydroxy groups may have a chain structure or a cyclic structure. Further, the aliphatic compound having a chain structure may have a linear structure or a branched structure.
  • Illustrative examples of the aliphatic compound include a pentose, a hexose, a monosaccharide, a polysaccharide, and a sugar alcohol.
  • Illustrative examples of the aliphatic compound of the pentose include riburonic acid, arabinuronic acid, xylonic acid, lyxonic acid, ribitol, arabinitol, and xylitol.
  • Illustrative examples of the aliphatic compound of hexose include allose, altrose, glucose, mannose, gulose, idose, galactose, talose, allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, alluronic acid, altruronic acid, glucuronic acid, mannuronic acid, guluronic acid, iduronic acid, galacturonic acid, tartronic acid, allitol, altritol, sorbitol (glucitol), mannitol, iditol, and galactitol.
  • Illustrative examples of the aliphatic compound of monosaccharide include psicose (allulose), fructose, sorbose, tagatose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, fuculose, rhamnose, and sedoheptulose.
  • Illustrative examples of the aliphatic compound of polysaccharide include sucrose, lactose, maltose, trehalose, turanose, cellobiose, raffinose, melezitose, maltotriose, acarbose, stachyose, fructooligosaccharides (FOS), galactooligosaccharide (GOS), mannan oligosaccharide (MOS), lactose fructose oligosaccharide, glycogen, starch (amylose-amylopectin), cellulose, dextrin, glucan ( ⁇ 1,3-glucan), fructan (inulin-levan ⁇ 2 ⁇ 6), and chitin.
  • sucrose lactose, maltose, trehalose, turanose, cellobiose, raffinose, melezitose, maltotriose, acarbose, stachyose,
  • Illustrative examples of the aliphatic compound of the sugar alcohol include D-arabinitol, L-arabinitol, xylitol, ribitol (adonitol), D-iditol, galactitol (dulcitol), D-glucitol (sorbitol), mannitol, volemitol, and perseitol.
  • the molar ratio of the metal containing zinc and iron to the complexing agent is preferably 1:0.5 to 1:5. It is particularly preferable that the molar ratio of the metal containing zinc and iron to the complexing agent is 1:1 to 1:3. Further, when the molar ratio of the metal containing zinc and iron to the complexing agent is made 1:3, in the alkaline zinc-iron plating bath with the metal concentration of iron being 1.3 g/L or more, for example, the difference in the eutectic rates of iron can be made to 8% or less in the current density of 0.5 to 10 ASD.
  • the alkaline zinc-iron plating bath of the above-described raw materials is prepared as follows. Namely, first, a complexing agent (sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, maltose, or triethanolamine) is dissolved with water of about 40% of the total volume, and then, a metal salt containing iron (ferric sulfate solution, ferrous sulfate heptahydrate, or ferric chloride solution) is added thereto, followed by stirring this for about 2 hours. Thereby, an iron ion-containing liquid is prepared.
  • a complexing agent sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, maltose, or triethanolamine
  • a metal salt containing iron ferrric sulfate solution, ferrous sulfate heptahydrate, or ferric chloride solution
  • the film thickness ( ⁇ m) of the plating film and the eutectic rate of iron (%) were measured at any of 0.5 ASD (A/dm 2 : Ampere per Square Decimeter), 1 ASD, 3 ASD, 5 ASD, 8 ASD, and 10 ASD.
  • the measurement results of the film thickness ( ⁇ m) of the plating film obtained under the above conditions are described in Fig. 16 to Fig. 24 , and the measurement results of the eutectic rate (%) of iron are described in Fig. 25 to Fig. 33 .
  • Measurement results of the film thickness ( ⁇ m) of the plating film of Example and Comparative Example using the same raw materials except for the complexing agent are combined, which are illustrated by the graphs. These graphs are described in Fig. 34 to Fig. 86 .
  • the measurement results of the eutectic rate (%) of iron of the same are illustrated by the graphs; and these graphs are described in Fig. 87 to Fig. 139 .
  • the plating bath could not be prepared because of the precipitation occurred during the course of preparing the bath; accordingly, neither the film thickness ( ⁇ m) of the plating film nor the eutectic rate (%) of iron was measured.
  • the plating film in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is thicker as compared to the film thickness of the plating film in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent.
  • the film thickness of the plating film in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is thicker as compared to the film thickness of the plating film in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent.
  • any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose namely, by using the aliphatic compound having five or more hydroxy groups, it is possible to efficiently form a thick plating film.
  • the aliphatic compound having five or more hydroxy groups as the complexing agent, it is possible to improve the current efficiency of the alkaline zinc-iron plating bath.
  • the eutectic rate of iron when the iron ion concentration is low (iron ion concentration: 0.35 g/L), the eutectic rate of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose, and the eutectic rate of iron in the alkali zinc-iron plating bath using triethanolamine as the complexing agent are almost constant independent of the current density (ASD).
  • ASSD current density
  • the eutectic rate of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is almost constant independent of the current density (ASD), but the eutectic rate of iron in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent varies greatly depending on the current density (ASD).
  • the difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent is 6.4 to 45.3, while the difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is 0.8 to 41.2.
  • the difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using sodium gluconate or D-sorbitol as the complexing agent is 0.8 to 7.5.
  • the smallest difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is 0.8%, while the smallest difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent is 6.4%.
  • the largest difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is 41.2%, while the largest difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent is 45.3%.
  • the largest difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using sodium gluconate or D-sorbitol as the complexing agent is 7.5%.
  • the difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using, as the complexing agent, any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose is about 4 or less, while the difference in the eutectic rates of iron in the alkaline zinc-iron plating bath using triethanolamine as the complexing agent is about 15 or more.
  • any of sodium gluconate, xylitol, sorbitol, mannitol, glucose, fructose, lactose, and maltose that is, by using the aliphatic compound having five or more hydroxy groups, even when the iron ion concentration is high, the eutectic rate of iron can be made constant independent of the current density.
  • the molar ratio of the metal containing zinc and iron to the complexing agent is set at 1:1 to 1:5.
  • the molar ratio to the complexing agent is set at 1:0.5 to 1:5, it is possible to reduce the difference in the eutectic rates of iron independent of the current density.
EP20900205.4A 2019-12-11 2020-12-11 Bain alcalin de placage de zinc- fer Withdrawn EP4074867A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019223613 2019-12-11
PCT/JP2020/046345 WO2021117882A1 (fr) 2019-12-11 2020-12-11 Bain alcalin de placage de zinc- fer

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EP4074867A1 true EP4074867A1 (fr) 2022-10-19

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EP20900205.4A Withdrawn EP4074867A1 (fr) 2019-12-11 2020-12-11 Bain alcalin de placage de zinc- fer

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US (1) US20220411950A1 (fr)
EP (1) EP4074867A1 (fr)
JP (1) JPWO2021117882A1 (fr)
CN (1) CN114787424A (fr)
MX (1) MX2022006443A (fr)
WO (1) WO2021117882A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62238387A (ja) 1986-04-07 1987-10-19 Yuken Kogyo Kk ジンケ−ト型亜鉛合金めつき浴
JPH02141596A (ja) * 1988-11-21 1990-05-30 Yuken Kogyo Kk ジンケート型亜鉛合金メッキ浴
JPH02282493A (ja) * 1989-04-21 1990-11-20 Ebara Yuujiraito Kk 亜鉛―コバルト合金電気めっき液
JPH05112889A (ja) * 1991-08-19 1993-05-07 Yuken Kogyo Kk ジンケート型亜鉛−鉄合金メツキ浴
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
ES2788080T3 (es) * 2009-09-08 2020-10-20 Atotech Deutschland Gmbh Polímeros con grupos terminales amino y su uso como aditivos para baños galvanoplásticos de zinc y de aleaciones de zinc
JP7002548B2 (ja) * 2016-12-22 2022-01-20 カール・フロイデンベルク・カー・ゲー 金属ピース品の表面に亜鉛含有皮膜を析出させるための水性アルカリ電解液

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US20220411950A1 (en) 2022-12-29
MX2022006443A (es) 2022-08-16
JPWO2021117882A1 (ja) 2021-12-09
CN114787424A (zh) 2022-07-22
WO2021117882A1 (fr) 2021-06-17

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