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WO1999050479A1 - Solution d'electrodeposition - Google Patents

Solution d'electrodeposition Download PDF

Info

Publication number
WO1999050479A1
WO1999050479A1 PCT/GB1999/000913 GB9900913W WO9950479A1 WO 1999050479 A1 WO1999050479 A1 WO 1999050479A1 GB 9900913 W GB9900913 W GB 9900913W WO 9950479 A1 WO9950479 A1 WO 9950479A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
nickel
zinc
compound
silicate
Prior art date
Application number
PCT/GB1999/000913
Other languages
English (en)
Inventor
Ernest Long
Trevor Pearson
Anthony Rowan
Original Assignee
Wm. Canning Limited
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 Wm. Canning Limited filed Critical Wm. Canning Limited
Priority to AU30444/99A priority Critical patent/AU3044499A/en
Publication of WO1999050479A1 publication Critical patent/WO1999050479A1/fr

Links

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 an electroplating solution for depositing a zinc-nickel alloy coating onto a substrate.
  • Electrodeposition of zinc-nickel alloy using an aqueous alkaline plating solution is well known. Much research has been directed towards achieving better deposition in terms of, for example, brightness, absence of pitting, uniformity and efficiency. To this end, plating solutions have been developed which include additives other than the required zinc and nickel salts.
  • US 4889602 discloses a plating bath in which an additive is one of (i) an aliphatic amine, (ii) a polymer of an aliphatic amine or (iii) a hydroxyaliphatic carboxylic acid or salt thereof.
  • US 5417840 discloses a bath containing an additive which is a salt of an aromatic heterocyclic nitrogen containing compound.
  • US 5405523 and US 5435898 disclose the use of a quaternary ammonium polymer in a zinc-nickel plating bath.
  • the object of the present invention is to provide an electroplating solution which has improved characteristics and which, in use, delivers an improved zinc-nickel electrodeposit onto a substrate.
  • an aqueous alkaline electroplating solution for forming a zinc-nickel coating on a substrate comprising:-
  • a soluble compound having a silicate-based anion the silicate- based anion being present in the solution in a concentration range of 0.1 to 100g/l.
  • the ionic zinc species may include zincate ion.
  • zinc ion is intended to include zincate ion and other ionic zinc species.
  • zinc ions are present in a concentration of 1 to 70 g/l, more preferably, 4 to 35 g/l.
  • zinc ions are provided by the chemical dissolution of zinc oxide or the direct electrochemical dissolution of zinc metal.
  • the nickel is present in the range 0.1 to 50 g/l, more preferably, 0.5 to 20 g/l.
  • the nickel is preferably provided by a salt of nickel, such as the chloride, sulphate, sulphamate, carbonate, hydroxide or acetate salt, combined with at least one complexing agent which renders the nickel soluble at the operating pH of the electrolyte and which is of a suitable stability constant to allow co-deposition of nickel from the solution.
  • a salt of nickel such as the chloride, sulphate, sulphamate, carbonate, hydroxide or acetate salt
  • Suitable complexing agents include compounds of formula (I):-
  • the total concentration of the compound(s) of formula (I) is in the range of 17 to 100 g/l, and more preferably in the range of 20 to 60 g l- Suitable complexing agents also include compounds of formula (II):-
  • R R 4 wherein Ri, R 2 , R 3 and R 4 are each independently selected from C, to C 4 alkyl and hydroxyalkyl, provided that at least one of R R 2 , R 3 and R 4 is hydroxyalkyl.
  • the total concentration of the compound(s) of formula (II) is in the range of 1 to 50 g/l.
  • the silicate-based anion is selected from the group consisting of silicate, metasilicate, sesquisilicate, orthosilicate and polysilicate, which may be used singly or in combination.
  • the cation is sodium and/or potassium.
  • the preferred concentration range for the silicate-based species is 0.5 to 50 g/l, preferably 2 to 20 g/l.
  • Suitable alkaline electrolytes include NaOH, KOH, Na 2 C0 3 and K 2 C0 3 , which may be used singly or in combination so as to give a minimum solution pH of 1 1.
  • the electrolyte(s) may be present in a concentration of 50 to 250 g/l, more preferably, 80 to 200 g/l (based on the anhydrous salt).
  • the solution may also contain compounds of the following types; thiourea or substituted thiourea, such as methyl thiourea and allyl thiourea, and heterocyclic thio compounds, such as 2,5- dimercapto-1 ,3,4-thiadiazole, 2-mercapto-5-amino-1 ,3,4-thiadiazole.
  • thiourea or substituted thiourea such as methyl thiourea and allyl thiourea
  • heterocyclic thio compounds such as 2,5- dimercapto-1 ,3,4-thiadiazole, 2-mercapto-5-amino-1 ,3,4-thiadiazole.
  • the preferred concentration range of these compounds is 0.001 to 1.0 g/l. 4
  • the solution also contains a quaternary moiety of formula (III):
  • the solution may also include product(s) of the reaction between epichlorohydrin and an aliphatic amine, and/or product(s) of the reaction between epichlorohydrin and imidazole, preferably in a concentration of 0.1 to 20 g/l.
  • Aromatic aldehydes may be included in the solution, preferably in a concentration range of 0.01 to 2 g/l.
  • Suitable aldehydes include 4- hydroxy-3-methoxybenzaldehyde, 1 ,3-benzodioxole-5-carboxy-aldehyde, veratraldehyde, anisaldehyde, p-tolualdehyde, benzaldehyde, o- chlorobenzaldehyde, 2,3-dimethoxybenzaldehyde, salicylaldehyde and cinnamaldehyde.
  • sodium sulphite adducts of any of the above aldehydes may be included in the solution.
  • the present invention also resides in:-
  • the electroplating solutions of the present invention exhibit significant improvements in terms of tolerances to changes in electrolyte composition, such as salt build up (e.g. carbonate, sulphate and sulphamate) and metal contamination. They also allow the use of wide operating temperatures and current density ranges. Also, they give advantages in terms of the plating rates achievable in both rack and barrel applications as compared to the prior art.
  • salt build up e.g. carbonate, sulphate and sulphamate
  • the resultant deposit shows excellent adhesion to the substrate, and is fully bright over a very wide current density range with no deposit pitting evident.
  • the deposit also exhibits excellent post-plate deformation characteristics.
  • aqueous electroplating solution having the following composition was prepared by dissolving 120g of sodium hydroxide in 300 ml of water. To this hot caustic solution 12.5g of ZnO was added. Once the ZnO had fully dissolved, a further 400 ml of water was added and the solution allowed to cool. 8 g of NiS0 4 .6H 2 0 was then dissolved in 50 ml of water and to this 30 g of a polyethylene imine (mol. wt. 1500) and 20 g of 6
  • N,N,N',N' tetrakis hydroxyisopropyl ethylenediamine was added.
  • the complexed nickel sulphate was then added to the zinc and sodium hydroxide base solution and water added to give 1 litre final volume.
  • the resulting hull cell panel was fully bright from a distance on the test panel corresponding to a primary current density of 3 A/dm 2 to the high current density (hcd) edge of the hull cell panel.
  • the nickel concentration in the deposit was 12 to 14%.
  • a hull cell test (1A/10 min, 30°C, mild air agitation) was carried out on an electroplating solution having a composition identical to that in Example 3 above, but also containing 0.10 g/l of thiourea.
  • the resulting hull cell panel was fully bright from a distance corresponding to a primary current density of 0.05 A/dm 2 (cf. 0.1 A/dm 2 in Example 3) and contained 12 to 13% nickel in the electrodeposit across the panel.
  • the above polymer can be prepared by reacting 1 ,3-bis[3- dimethylamino)propyl] urea and bis(2-chloroethyl) ether in water.
  • the resulting hull cell panel was fully bright across the full current density range and contained 12 to 13% nickel in the electrodeposit across the panel. 8
  • a hull cell test (1 A/10 min, 30°C, mild air agitation) was carried out on an electroplating solution of an identical composition to that in Example 6 above, but also contained 0.05 g/l of veratraldehyde.
  • the resulting hull cell panel was fully bright across the full current density range and contained 12 to 13% nickel in the electrodeposit across the panel.
  • a piece of steel tubing was plated in an electroplating solution having an identical composition to that in Example 6.
  • the tube was plated at an average current density of 2 A/dm 2 to a thickness of 30 ⁇ m.
  • the plating rate was 30 ⁇ m/hr.
  • the tube was then bent through an angle of 180°. No deposit "tinselling" or evidence of poor adhesion was evident.
  • An electroplating solution having an identical composition to that of Example 6 was saturated with sodium carbonate. A bright deposit was still obtained from the electroplating solution. The deposition rate was only reduced by 20%.

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)

Abstract

On décrit une solution d'électrodéposition qu'on utilise dans un procédé de dépôt électrolytique pour former un alliage de zinc et de nickel sur un substrat. Cette solution d'électrodéposition comprend : I) des ions de zinc; ii) une source de nickel soluble permettant un dépôt simultané de nickel; iii) au moins un électrolyte alcalin; et iv) un composé soluble qui comprend un anion à base de silicate présent dans la solution dans une concentration de 0,1 à 100g/l.
PCT/GB1999/000913 1998-03-27 1999-03-23 Solution d'electrodeposition WO1999050479A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU30444/99A AU3044499A (en) 1998-03-27 1999-03-23 Electroplating solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9806539.4 1998-03-27
GBGB9806539.4A GB9806539D0 (en) 1998-03-27 1998-03-27 Electroplating solution

Publications (1)

Publication Number Publication Date
WO1999050479A1 true WO1999050479A1 (fr) 1999-10-07

Family

ID=10829343

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/000913 WO1999050479A1 (fr) 1998-03-27 1999-03-23 Solution d'electrodeposition

Country Status (4)

Country Link
AR (1) AR014781A1 (fr)
AU (1) AU3044499A (fr)
GB (1) GB9806539D0 (fr)
WO (1) WO1999050479A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131478A (ja) * 1999-11-10 2001-05-15 Nippon Hyomen Kagaku Kk 表面処理剤
EP2357268A1 (fr) * 2008-11-11 2011-08-17 Yuken Industry Co., Ltd. Bain de zingage à base de zincate
US20120138473A1 (en) * 2010-09-09 2012-06-07 Yuken Industry Co., Ltd. Zinc plating bath additive and alkaline non-cyanide zinc plating bath
CN110129841A (zh) * 2019-06-17 2019-08-16 广东东硕科技有限公司 整平剂及包含其的电镀液
US20210230762A1 (en) * 2017-10-03 2021-07-29 Xerion Advanced Battery Corp. Electroplating transition metal oxides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856637A (en) * 1973-07-09 1974-12-24 Lea Ronaf Inc Methods of electroplating zinc and cyanide free or low cyanide zinc plating baths therefor
US5405523A (en) * 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856637A (en) * 1973-07-09 1974-12-24 Lea Ronaf Inc Methods of electroplating zinc and cyanide free or low cyanide zinc plating baths therefor
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
US5405523A (en) * 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
H. GEDULD: "Zinc Plating", 1988, FINISHING PUBLICATIONS, TEDDINGTON, MIDDLESEX,ENGLAND, XP002114501 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1099780A2 (fr) 1999-11-10 2001-05-16 Nihon Hyomen Kagaku Kabushiki Kaisha Agent de traitement de surface
EP1099780A3 (fr) * 1999-11-10 2002-08-07 Nihon Hyomen Kagaku Kabushiki Kaisha Agent de traitement de surface
US6500886B1 (en) 1999-11-10 2002-12-31 Nihon Hyomen Kagaku Kabushiki Kaisha Surface treating agent
US7030183B2 (en) 1999-11-10 2006-04-18 Nihon Hyomen Kagaku Kabushiki Kaisha Surface treating method and surface treating agent
JP2001131478A (ja) * 1999-11-10 2001-05-15 Nippon Hyomen Kagaku Kk 表面処理剤
EP2357268A4 (fr) * 2008-11-11 2012-12-05 Yuken Kogyo Co Ltd Bain de zingage à base de zincate
EP2357268A1 (fr) * 2008-11-11 2011-08-17 Yuken Industry Co., Ltd. Bain de zingage à base de zincate
US20110210007A1 (en) * 2008-11-11 2011-09-01 Yuken Industry Co., Ltd. Zincate zinc plating bath
JP5419021B2 (ja) * 2008-11-11 2014-02-19 ユケン工業株式会社 ジンケート型亜鉛めっき浴
EP2489762A1 (fr) * 2010-09-09 2012-08-22 Yuken Industry Co., Ltd. Additif pour bains de zingage et bains de zingage alcalins sans cyanure
EP2489762A4 (fr) * 2010-09-09 2012-12-05 Yuken Kogyo Co Ltd Additif pour bains de zingage et bains de zingage alcalins sans cyanure
US20120138473A1 (en) * 2010-09-09 2012-06-07 Yuken Industry Co., Ltd. Zinc plating bath additive and alkaline non-cyanide zinc plating bath
US20210230762A1 (en) * 2017-10-03 2021-07-29 Xerion Advanced Battery Corp. Electroplating transition metal oxides
US11492719B2 (en) * 2017-10-03 2022-11-08 Xerion Advanced Battery Corp. Electroplating transition metal oxides
US20230313404A1 (en) * 2017-10-03 2023-10-05 Xerion Advanced Battery Corp. Electroplating transition metal oxides
US11859304B2 (en) * 2017-10-03 2024-01-02 Xerion Advanced Battery Corp. Electroplating transition metal oxides
CN110129841A (zh) * 2019-06-17 2019-08-16 广东东硕科技有限公司 整平剂及包含其的电镀液
CN110129841B (zh) * 2019-06-17 2021-04-27 广东东硕科技有限公司 整平剂及包含其的电镀液

Also Published As

Publication number Publication date
AR014781A1 (es) 2001-03-28
GB9806539D0 (en) 1998-05-27
AU3044499A (en) 1999-10-18

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