EP0153369A1 - Electroless nickel plating of aluminum. - Google Patents
Electroless nickel plating of aluminum.Info
- Publication number
- EP0153369A1 EP0153369A1 EP84903142A EP84903142A EP0153369A1 EP 0153369 A1 EP0153369 A1 EP 0153369A1 EP 84903142 A EP84903142 A EP 84903142A EP 84903142 A EP84903142 A EP 84903142A EP 0153369 A1 EP0153369 A1 EP 0153369A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- aluminum
- plating
- bath
- barrier 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.)
- Granted
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 nickel plating of aluminum 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, aluminum and alloys thereof.
- Plating metals such as aluminum, magnesium and their alloys present special problems to electroplaters, how ⁇ ever, becuase, for one, they have surface oxide coatings which require special pre-plating operations to condition the surface for plating.
- the present invention is applicable to the electroless plating of such metal sub ⁇ strates with metals such as nickel, cobalt and nickel- cobalt alloys, the description which follows will be primarily directed for convenience to the electroless nickel plating of aluminum and aluminum alloys which have been conditioned for plating by depositing a zinc coating on its surface.
- aluminum parts are first cleaned to re ⁇ move organic surface contamination, followed by etching to eliminate solid impurities and alloying constituents from the surface, desmutting to remove the oxide film, and coating with a barrier layer such as zinc or tin 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 aluminum 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 fo'r steel may be useful on barrier coated aluminum for only about five turnovers. After this it must be discarded and replaced becuase the nickel deposits on the aluminum 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/1 nickel, the bath would usually be replenished with nickel salts back to 6 g/1 as the nickel is consumed during plating. The cumulative replenishment of 6 g/1 nickel represents one turnover.
- Zyering is a commercially important process to pretreat aluminum surfaces because it is a realtively simple process requiring only immersion of the aluminum part in alkaline solution containing zincate ions.
- the amount of zinc deposited is actually very small and de ⁇ pends on the time and type of immersion bath used, the aluminum alloy, temperature of the solution and the pre- treatment process; thickness 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 aluminum surfaces basically com ⁇ prising etching the aluminum with an acidic nickel chlo- ride solution to expose the aluminum crystals and deposit a nickel coating, removing the nickel coating with UNO.,, activating with an alkaline, solution containing hypophos- phite ions and then electrolessly plating an alkaline strike coat of nickel at 85 to 90°C, followed by electro- less nickel deposition to the desired nickel thickness.
- U.S. Patent No. 3,672,964 to Bellis et al. discloses pretreating the aluminum surfaces with an aqueous solution of hydrofluoric acid and a material which is displaced by the aluminum and which is active to the electroless plating nickel, thereafter plating the treated aluminum surface with an electroless nickel bath which is at a pH of 6-7 and contains an a ine borane and a monovalent or divalent sulfur compound.
- the process comprises apply ⁇ ing a thin second barrier coating of nickel on the zinca ⁇ ted surface from a nickel bath, e.g., electroless, fol ⁇ lowed by the use of another nickel bath to plate the surface to the desired thickness and physical character ⁇ istics.
- 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, being used to plate the final nickel coating.
- the process has resulted in an almost doubled turnover life in the second bath as compared to the prior art process of using a single bath to plate the zincated aluminum 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 aluminum part to be electrolessly nickel plated is, as discussed hereinabove, pretreated and provided with a barrier coating such as zinc, or other metals such as.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 apply ⁇ ing the nickel coatings are well known in the art and plating processes and compositions are described in numerous publications. For example, compositions for depositing electroless nickel are described in U.S.
- Other useful compositions for depositing nickel and its alloys are disclosed in the 35th Annual Edition of the Metal Finishing Guidebook for 1967, Metal and plastics publications. Inc., Westwood,
- 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 solu- ion.
- 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 ap ⁇ preciated 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 phosphorous. Similarly, if an amine borane is employed, the deposit will contain nickel and boron. Thus, use of the term 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 .1 to 100 g/1, preferably about 2 to 50 g/1, e.g., 2 to 10 g/1.
- the reducing agent is usually the hypophosphite ion supplied to the bath by any suitable source such as so ⁇ dium, potassium, ammonium and nickel hypophosphite.
- suitable source such as so ⁇ dium, potassium, ammonium and nickel hypophosphite.
- Other reducing agents such as amine boranes, borohydrides and hydrazine may also suitably be employed.
- the concentra ⁇ tion 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 hy ⁇ droxide, 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 bath used to deposit the second barrier coating and a range of 2 to 7, e.g., 4 to 6, being preferred for the bath used to de ⁇ posit 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 mix ⁇ tures thereof being suitable. Ranges for the complexing agent, based on the anion, may vary widely, for example, about 0 to 300 g/1, preferably about 5 to 50 g/1.
- the electroless nickel plating baths may also con- tain 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 aluminum 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 bar ⁇ rier 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 fac ⁇ tors including (1) pH of the plating solution, (2) con ⁇ centration of reductant, (3) temperature of plating bath,
- EXAMPLE I Aluminum Association Number 3003 aluminum panels 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/1 ZnO, 500 g/1 NaOH, 1 g/1 FeCl- and 10 g/1 Rochelle salt. The panels were water rinsed and a number of the panels plated in an electroless nickel plating bath sold by Enthone, In- corporated 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/i 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 aluminum and must be discarded.
- a zincated aluminum panel prepared as above was plated with a thin second barrier coating of nickel
- the bath was still useful at this point to plate on the second barrier coated panels but the plating rate was very slow, as is usual when a bath has reached about 9-10 turnovers.
- the example demonstrates that the life of an electro ⁇ less nickel plating bath used to plate zincated aluminum may be increased if the zincated aluminum has a thin second barrier nickel coating before immersion in the bath.
- EXAMPLE II A zincated aluminum 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 H 4 OH:
- 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.
Landscapes
- 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)
- Processes Of Treating Macromolecular Substances (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Procédé pour améliorer le nickelage non galvanique d'aluminium qui a été prétraité avec un revêtement barrière comme du zinc, en utilisant de multiples bains de placage sous conditions de fonctionnement regulées.Method for improving the non-galvanic nickel plating of aluminum which has been pretreated with a barrier coating such as zinc, using multiple plating baths under controlled operating conditions.
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52535883A | 1983-08-22 | 1983-08-22 | |
US525358 | 1990-05-17 | ||
HK98105637A HK1006860A1 (en) | 1983-08-22 | 1998-06-18 | Electroless nickel plating of aluminum |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0153369A1 true EP0153369A1 (en) | 1985-09-04 |
EP0153369A4 EP0153369A4 (en) | 1986-02-13 |
EP0153369B1 EP0153369B1 (en) | 1993-10-13 |
Family
ID=26316726
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84903142A Expired - Lifetime EP0153369B1 (en) | 1983-08-22 | 1984-08-08 | Electroless nickel plating of aluminum |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0153369B1 (en) |
JP (1) | JPS60502057A (en) |
AU (1) | AU558946B2 (en) |
BR (1) | BR8407027A (en) |
CA (1) | CA1220101A (en) |
DE (1) | DE3486228T2 (en) |
HK (1) | HK1006860A1 (en) |
MX (1) | MX167978B (en) |
WO (1) | WO1985001070A1 (en) |
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 (en) * | 2015-05-11 | 2018-10-24 | 東京エレクトロン株式会社 | Plating process and storage medium |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5484835A (en) * | 1977-12-19 | 1979-07-06 | Toshiba Corp | Surface treatment of al and al alloy for soldering |
US4358923A (en) * | 1980-04-10 | 1982-11-16 | Surface Technology, Inc. | Composite coatings for open-end machinery parts |
Family Cites Families (5)
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 |
US4346128A (en) * | 1980-03-31 | 1982-08-24 | The Boeing Company | Tank process for plating aluminum substrates including porous aluminum castings |
SU926064A1 (en) * | 1980-07-15 | 1982-05-07 | Алтайский Сельскохозяйственный Институт | Aqueous solution for preparing metal surface to chemical nickel plating |
-
1984
- 1984-08-08 DE DE84903142T patent/DE3486228T2/en not_active Expired - Lifetime
- 1984-08-08 JP JP59503212A patent/JPS60502057A/en active Granted
- 1984-08-08 BR BR8407027A patent/BR8407027A/en not_active IP Right Cessation
- 1984-08-08 WO PCT/US1984/001253 patent/WO1985001070A1/en active IP Right Grant
- 1984-08-08 EP EP84903142A patent/EP0153369B1/en not_active Expired - Lifetime
- 1984-08-08 AU AU32178/84A patent/AU558946B2/en not_active Ceased
- 1984-08-17 CA CA000461286A patent/CA1220101A/en not_active Expired
- 1984-08-21 MX MX202448A patent/MX167978B/en unknown
-
1998
- 1998-06-18 HK HK98105637A patent/HK1006860A1/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5484835A (en) * | 1977-12-19 | 1979-07-06 | Toshiba Corp | Surface treatment of al and al alloy for soldering |
US4358923A (en) * | 1980-04-10 | 1982-11-16 | Surface Technology, Inc. | Composite coatings for open-end machinery parts |
Non-Patent Citations (5)
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 * |
METAL FINISHING ABSTRACTS; vol. 22, no. 2, March/April 1980, page 105, abstract A, Hampton Hill; & JP-A-54 084 835 (TOKYO SHIBAURA ELECTRIC K.K.) 06-07-1979 * |
METALS HANDBOOK, 9th ed., 1982, vol. 5; pp. 220-221# * |
See also references of WO8501070A1 * |
Also Published As
Publication number | Publication date |
---|---|
JPH0319302B2 (en) | 1991-03-14 |
DE3486228T2 (en) | 1994-04-14 |
DE3486228D1 (en) | 1993-11-18 |
EP0153369A4 (en) | 1986-02-13 |
EP0153369B1 (en) | 1993-10-13 |
CA1220101A (en) | 1987-04-07 |
HK1006860A1 (en) | 1999-03-19 |
AU3217884A (en) | 1985-03-29 |
JPS60502057A (en) | 1985-11-28 |
AU558946B2 (en) | 1987-02-12 |
MX167978B (en) | 1993-04-26 |
BR8407027A (en) | 1985-07-30 |
WO1985001070A1 (en) | 1985-03-14 |
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