EP0153369B1 - Nickelage non galvanique d'aluminium - Google Patents
Nickelage non galvanique d'aluminium Download PDFInfo
- Publication number
- EP0153369B1 EP0153369B1 EP84903142A EP84903142A EP0153369B1 EP 0153369 B1 EP0153369 B1 EP 0153369B1 EP 84903142 A EP84903142 A EP 84903142A EP 84903142 A EP84903142 A EP 84903142A EP 0153369 B1 EP0153369 B1 EP 0153369B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- plating
- bath
- metal
- coating
- 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
Links
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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
Definitions
- the invention relates generally to a method for the electroless plating of aluminium and its alloys.
- Electroless nickel plating is a process which is very important in the metal finishing industry and which is widely employed for many metal substrates, including steel, copper, nickel, aluminium and alloys thereof.
- Plating metals such as aluminium and its alloys presents special problems to electroplaters, however, because, for one, they have surface oxide coatings which require special pre-plating operations to condition the surface for plating.
- the present invention relates to the electroless metal plating of such a metal substrate which has been conditioned for plating by depositing a barrier coating on its surface.
- the description which follows will be primarily directed for convenience to electroless nickel plating of zinc coated aluminium alloy surfaces.
- the aluminium parts are first cleaned to remove organic surface contamination, followed by etching to elimiate solid impurities and alloying constituents from the surface, desmutting to remove the oxide film, and coating with a barrier layer of zinc to prevent re-oxidation of the cleaned surface.
- the parts are usually rinsed after each of the above steps and are now ready for electroless nickel plating.
- the electroless nickel plating bath used to plate zincated aluminium has a relatively short bath life when compared to baths used to plate many other metal alloys such as plain steel.
- a bath which would normally be useful for, as an example, about ten turnovers for steel may be useful on barrier coated aluminium for only about five turnovers. After this it must be discarded and replaced because the nickel deposits on the aluminium start to be blistered.
- a turnover may be defined as the period during which the quantity of nickel metal that has been plated out is equal to the quantity of nickel in the bath as made up. For example, for a bath initially containing about 6 g/l nickel, the bath would usually be replenished with nickel salts back to 6 g/l as the nickel is consumed during plating. The cumulative replenishment of 6 g/l nickel represents one turnover.
- Zyering is a commercially important process for the pretreatment of aluminium surfaces because it is a relatively simple process requiring only immersion of the aluminium part in alkaline solution containing zincate ions.
- the amount of zinc deposited is actually very small and depends on the time and type of immersion bath used, the aluminium alloy, temperature of the solution and the pretreatment process; thicknesses up to about 0.1 microns are usually employed.
- U.S. Patent No. 3,666,529 to Wright et al. discloses a method of conditioning aluminium surfaces basically comprising etching the aluminium with an acidic nickel chloride solution to expose the aluminium crystals and deposit a nickel coating, removing the nickel coating with HNO3, activating with an alkaline solution containing hypophosphite ions and then electrolessly plating an alkaline strike coat of nickel at 85 to 90°C, followed by electroless nickel deposition to the desired nickel thickness.
- U.S. Patent No. 3,672,964 to Bellis et al. discloses pretreating the aluminium surfaces with an aqueous solution of hydrofluoric acid and a material which is displaced by the aluminium and which is active to the electroless plating nickel, thereafter plating the treated aluminium surface with an electroless nickel bath which is at a pH of 6-7 and contains an amine borane and a monovalent or divalent sulfur compound.
- the electroless nickel plating of aluminium which has been pretreated with a zinc coating may be improved by employing multiple plating baths under controlled operating conditions.
- the process comprises applying a thin second barrier coating of nickel on the zincated surface from an electroless nickel bath, followed by the use of another nickel bath to plate the surface to the desired thickness and physical characteristics.
- the process thus employs at least two nickel plating baths, the first of which is used to apply a thin second barrier coating of nickel on the zincated surface, with the second bath or baths, comprising the primary bath or baths being used to plate the final nickel coating.
- the process is not limited to nickel plating and also may be applied to tin- as well as zinc-coated aluminium substrates.
- the invention provides a process for plating a zinc or tin coated aluminium substrate by applying a metal plating to the desired thickness on to said zinc or tin coating from an electroless plating bath, the bath being replenished as needed to maintain the desired metal concentration, characterised in that the life of the bath is increased by plating a thin coating comprising the same metal on the zinc or tin coated substrate from another electroless metal plating bath prior to plating to the desired thickness with the primary bath, said thin coating being thinner than said subsequent plating and wherein both electroless metal plating baths contain a source of ions of said metal and a reducing agent to produce the metal ions.
- the primary bath has a pH of about 2 to 7 and said another bath has a pH of about 2 to 12.
- the process of the invention has resulted in an almost doubled turnover life in the primary bath as compared to the prior art process of using a single bath to plate the zincated aluminium to the desired thickness.
- the first bath will last extensively before reaching its normal turnover limit even though it is being used to apply a second barrier coating directly onto a zinc surface, a process decidedly different from the prior art of plating to the desired thickness where the zincated surface is only in contact with the plating solution for a relatively short time.
- the result using the process of the invention is that the amount of work able to be processed through, e.g. two baths, in sequence, is substantially greater (approximately double) than if the baths were used separately.
- the aluminium part to be electrolessly nickel plated is, as discussed hereinabove, pretreated and provided with a barrier coating of zinc or tin, using known techniques and procedures. Small amounts of metals, usually less than 10%, may be co-deposited with the barrier coating metal for purposes such as to modify the deposit properties of coatings thereon, among others. Many metals may be used such as cobalt, nickel, copper and iron.
- Electroless nickel plating compositions for applying the nickel coatings are well known in the art and plating processes and compositions are described in numerous publications.
- compositions for depositing electroless nickel are described in U.S. Patent Nos. 2,690,401; 2,690,402; 2,762,723; 2,935,425; 2,929,742; and 3,338,726.
- Other useful compositions for depositing nickel and its alloys are disclosed in the 35th Annual Edition of the Metal Finishing Guidebook for 1967, Metal band plastics publications, Inc., Westwood, N.J., pages 483-486. Each of the foregoing publications is included herein by reference.
- electroless nickel deposition solutions comprise at least four ingredients dissolved in a solvent, typically water. They are (1) a source of the nickel ions, (2) a reducing agent such as a hypophosphite or an amine borane, (3) an acid or hydroxide pH adjustor to provide required pH and (4) a complexing agent for metal ions sufficient to prevent their precipitation in solution.
- a solvent typically water.
- suitable complexing agents for electroless nickel solutions are described in the above noted publications. In some formulations, the complexing agents are helpful but not a necessity. It will be appreciated by those skilled in the art that the nickel, or other metal being applied, is usually in the form of an alloy with the other materials present in the bath.
- the deposit will contain nickel and phosphorus.
- the deposit will contain nickel and boron.
- nickel includes the other elements normally deposited therewith.
- the nickel ion may be provided by the use of any soluble salt such as nickel sulfate, nickel chloride, nickel acetate and mixtures thereof.
- concentration of the nickel in solution may vary widely and is about 0.1 to 100 g/l, preferably about 2 to 50 g/l, e.g., 2 to 10 g/l.
- the reducing agent is usually the hypophosphite ion supplied to the bath by any suitable source such as sodium, potassium, ammonium and nickel hypophosphite.
- suitable source such as sodium, potassium, ammonium and nickel hypophosphite.
- Other reducing agents such as amine boranes, borohydrides and hydrazine may also suitably be employed.
- concentration of the reducing agent is generally in excess of the amount sufficient to reduce the nickel in the bath.
- the baths may be acid, neutral or alkaline and the acid or alkaline pH adjustor may be selected from a wide range of materials such as ammonium hydroxide, sodium hydroxide, hydrochloric acid and the like.
- the pH of the bath may range from about 2 to 11.5, with a range of 7 to 12, e.g., 9 to 11 being preferred for the first bath, used to deposit the thinner coating (alternatively referred to hereinafter as the second barrier coating), and a range of 2 to 7, e.g., 4 to 6, being preferred for the primary bath used to deposit the final layer of nickel.
- the complexing agent may be selected from a wide variety of materials containing anions such as acetate, citrate, glycollate, pyrophosphate and the like, and mixtures thereof being suitable. Ranges for the complexing agent, based on the anion, may vary widely, for example, about 0 to 300 g/l, preferably about 5 to 50 g/l.
- the electroless nickel plating baths may also contain other ingredients known in the art such as buffering agents, bath stabilizers, rate promoters, brighteners, etc.
- a suitable bath may be formed by dissolving the ingredients in water and adjusting the pH to the desired range.
- the zinc barrier coated aluminium part may be plated with the second barrier coating by electroless nickel plating, by immersing the part in an electroless nickel bath to a thickness adequate to provide a suitable barrier coating for blister-free deposits on the final nickel plate, e.g., up to about 0.1 mil, or higher, with 0.005 to 0.08 mils, e.g., 0.01 to 0.05, being preferred.
- An immersion time of 15 seconds to 15 minutes usually provides the desired coating, depending on bath parameters.
- a temperature range of about 25° to boiling, e.g., 100°C, may be employed, with a range of about 30° to 95°C being preferred.
- the next step in the procedure is to complete the nickel plating to the desired thickness and physical characteristics by immersing the nickel part in another electroless nickel plating bath which is maintained over a temperature range of about 30° to 100°C., e.g., boiling, preferably 80° to 95°C.
- a thickness up to 5 mils, or higher may be employed, with a range of about 0.1 to 2 mils used for most applications.
- the rate of plating may be influenced by many factors including (1) pH of the plating solution, (2) concentration of reductant, (3) temperature of plating bath, (4) concentration of soluble nickel, (5) ratio of volume of bath cm.3/area plated cm.2, (6) presence of soluble fluoride salts (rate promoter) and (7) presence of wetting agent and/or agitation, and that the above parameters are only provided to give general guidance for practising the invention; the invention residing in the use of multiple baths as hereinbefore described to provide an enhanced plating process.
- aluminium panels 21 ⁇ 2 X 4 were alkaline cleaned, water rinsed, acid etched, water rinsed, desmutted and water rinsed. The panels were then zincated at room temperature for 30 seconds using an aqueous solution containing 100 g/l Zn0, 500 g/l NaOH, 1 g/l FeCl3 and 10 g/l Rochelle salt. The panels were water rinsed and a number of the panels plated in an electroless nickel plating bath sold by Enthone, Incorporated under the name ENPLATE NI-431 by immersion in the bath, which was maintained at about 90°C, for about 30 minutes. A coating of about 0.4 mils was obtained on each panel.
- the nickel and hypophosphite concentration were replenished when the concentration fell to about 4 g/l nickel. A total of about 5 turnovers were obtained before the nickel plating started to blister. It is at this point that the bath normally cannot be further used to plate zincated aluminium and must be discarded.
- a zincated aluminium panel prepared as above was plated with a thin second barrier coating of nickel (about 0.02 mil) in the following electroless nickel plating bath for 3 minutes at 40°C: Nickel Sulfamate 24 g/l Tetra Potassium Pyrophosphate 60 g/l Sodium Hypophosphite 27 g/l NH4OH to a pH of 10
- the example demonstrates that the life of an electroless nickel plating bath used to plate zincated aluminium may be increased if the zincated aluminium has a thin second barrier nickel coating before immersion in the bath.
- a zincated aluminium panel as described above was plated with a thin second barrier coating of nickel (about 0.02 mil) for 5 minutes at 65°C in an electroless plating bath containing the following ingredients and adjusted to pH 7.5 with NH4OH: NiSO4 ⁇ 6 H2O 4 g/l CoSO4 ⁇ 7 H2O 28 g/l Na Citrate ⁇ 2 H2O 75 g/l Ammonium Hydroxide 9.4 g/l Na Hypophosphite 28 g/l NH4Cl 42 g/l
- Example I When the panel was immersed in the plating bath of Example I (having 5 turnovers), it received a blister-free nickel deposit. A zincated panel with no thin nickel coating was immersed in the same bath, and the deposit was blistered.
- Example II was repeated using ENPLATE NI-431 sold by Enthone, Incorporated to electrolessly plate the thin nickel second barrier coating with the same results being obtained, to wit, the second barrier coated panels receiving blister-free deposits and the zinc coated panels receiving blistered deposits.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Claims (11)
- Procédé pour le placage d'un substrat d'aluminium revêtu de zinc ou d'étain par application d'un dépôt métallique ayant l'épaisseur désirée sur ce revêtement de zinc ou d'étain à partir d'un bain de dépôt chimique, le bain étant complété en fonction des besoins pour maintenir la concentration en métal désirée, caractérisé en ce que la durée de vie du bain est augmentée par dépôt d'un revêtement mince comprenant le même métal sur le substrat revêtu de zinc ou d'étain dans un autre bain de dépôt métallique chimique avant placage à l'épaisseur désirée avec le bain principal, ce revêtement mince étant plus mince que ce dépôt ultérieur, et dans lequel les deux bains de dépôt métallique chimiques contiennent une source d'ions de ce métal et un agent réducteur pour produire les ions métalliques.
- Procédé suivant la revendication 1, dans lequel le revêtement métallique mince formé sur le revêtement de zinc ou d'étain a une épaisseur allant jusqu'à environ 2,5 µm (0,1 mil).
- Procédé suivant la revendication 2, dans lequel le revêtement métallique mince formé sur le revêtement de zinc ou d'étain a une épaisseur d'environ 0,126 à 2,02 µm (0,005 à 0,08 mil).
- Procédé suivant les revendications 1, 2 ou 3, dans lequel le placage métallique est choisi parmi le cobalt, le cuivre, le nickel et leurs alliages.
- Procédé suivant la revendication 4, dans lequel le métal est le nickel.
- Procédé suivant la revendication 1, dans lequel une surface d'aluminium revêtue de zinc est nickelée, ce bain principal a un pH d'environ 2 à 7 et cet autre bain a un pH d'environ 2 à 12.
- Procédé suivant la revendication 6, dans lequel le premier revêtement de nickel déposé sur la surface revêtue de zinc a une épaisseur allant jusqu'à environ 2,5 µm (0,1 mil).
- Procédé suivant les revendications 6 ou 7, dans lequel le bain utilisé pour déposer le premier revêtement de nickel contient un agent réducteur de type hypophosphite.
- Procédé suivant les revendications 6, 7 ou 8, dans lequel le bain de nickelage chimique principal contient un agent réducteur de type hypophosphite.
- Procédé suivant les revendications 6, 7 ou 8, dans lequel le bain de nickelage chimique principal contient un agent réducteur de type amine borane.
- Procédé suivant l'une quelconque des revendications 6 à 10, dans lequel le bain utilisé pour déposer le premier revêtement de nickel a un pH d'environ 7 à 12.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52535883A | 1983-08-22 | 1983-08-22 | |
US525358 | 1983-08-22 | ||
HK98105637A HK1006860A1 (en) | 1983-08-22 | 1998-06-18 | Electroless nickel plating of aluminum |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0153369A1 EP0153369A1 (fr) | 1985-09-04 |
EP0153369A4 EP0153369A4 (fr) | 1986-02-13 |
EP0153369B1 true EP0153369B1 (fr) | 1993-10-13 |
Family
ID=26316726
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84903142A Expired - Lifetime EP0153369B1 (fr) | 1983-08-22 | 1984-08-08 | Nickelage non galvanique d'aluminium |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0153369B1 (fr) |
JP (1) | JPS60502057A (fr) |
AU (1) | AU558946B2 (fr) |
BR (1) | BR8407027A (fr) |
CA (1) | CA1220101A (fr) |
DE (1) | DE3486228T2 (fr) |
HK (1) | HK1006860A1 (fr) |
MX (1) | MX167978B (fr) |
WO (1) | WO1985001070A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5476688A (en) * | 1988-08-29 | 1995-12-19 | Ostolski; Marian J. | Process for the preparation of noble metal coated non-noble metal substrates, coated materials produced in accordance therewith and compositions utilizing the coated materials |
JP6411279B2 (ja) * | 2015-05-11 | 2018-10-24 | 東京エレクトロン株式会社 | めっき処理方法および記憶媒体 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US366529A (en) * | 1887-07-12 | James timms | ||
JPS5345787A (en) * | 1976-10-08 | 1978-04-24 | Shiguma Ruutein Narodoni Podon | Method of working nonncircular functional hole of drawing die |
US4169171A (en) * | 1977-11-07 | 1979-09-25 | Harold Narcus | Bright electroless plating process and plated articles produced thereby |
JPS6015706B2 (ja) * | 1977-12-19 | 1985-04-20 | 株式会社東芝 | 半田付け用AlおよびAl合金の表面処理法 |
US4346128A (en) * | 1980-03-31 | 1982-08-24 | The Boeing Company | Tank process for plating aluminum substrates including porous aluminum castings |
US4358923A (en) * | 1980-04-10 | 1982-11-16 | Surface Technology, Inc. | Composite coatings for open-end machinery parts |
SU926064A1 (ru) * | 1980-07-15 | 1982-05-07 | Алтайский Сельскохозяйственный Институт | Водный раствор дл подготовки металлической поверхности перед химическим никелированием |
-
1984
- 1984-08-08 AU AU32178/84A patent/AU558946B2/en not_active Ceased
- 1984-08-08 DE DE84903142T patent/DE3486228T2/de not_active Expired - Lifetime
- 1984-08-08 WO PCT/US1984/001253 patent/WO1985001070A1/fr active IP Right Grant
- 1984-08-08 JP JP59503212A patent/JPS60502057A/ja active Granted
- 1984-08-08 BR BR8407027A patent/BR8407027A/pt not_active IP Right Cessation
- 1984-08-08 EP EP84903142A patent/EP0153369B1/fr not_active Expired - Lifetime
- 1984-08-17 CA CA000461286A patent/CA1220101A/fr not_active Expired
- 1984-08-21 MX MX202448A patent/MX167978B/es unknown
-
1998
- 1998-06-18 HK HK98105637A patent/HK1006860A1/xx not_active IP Right Cessation
Non-Patent Citations (3)
Title |
---|
HANDBUCH DER GALVANOTECHNIK, vol. II, 1966, Carl Hansen Verlag; pp. 740-741# * |
METAL FINISHING ABSTRACTS, vol. 22, no. 2, March/April 1980, Hampton Hill; p. 105, abstract A; & JP-A-54 84835 (Tokyo Shibaura Electric K.K.) 19-12-1977 * |
METALS HANDBOOK, 9th ed., 1982, vol. 5; pp. 220-221# * |
Also Published As
Publication number | Publication date |
---|---|
DE3486228D1 (de) | 1993-11-18 |
BR8407027A (pt) | 1985-07-30 |
DE3486228T2 (de) | 1994-04-14 |
JPS60502057A (ja) | 1985-11-28 |
MX167978B (es) | 1993-04-26 |
EP0153369A1 (fr) | 1985-09-04 |
HK1006860A1 (en) | 1999-03-19 |
EP0153369A4 (fr) | 1986-02-13 |
WO1985001070A1 (fr) | 1985-03-14 |
CA1220101A (fr) | 1987-04-07 |
AU3217884A (en) | 1985-03-29 |
AU558946B2 (en) | 1987-02-12 |
JPH0319302B2 (fr) | 1991-03-14 |
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