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Plating Process For Electroless

1. A process is described for electrolessly plating nickel onto zinc die castings to provide corrosion resistance and wearability. 2. The key steps are depositing an electrolytic zinc layer, followed by one or more electroless nickel layers using alkaline or acidic baths. 3. It is preferred that the electroless nickel baths contain antimony ions to improve bath stability and adhesion of the plated layers.
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0% found this document useful (0 votes)
118 views5 pages

Plating Process For Electroless

1. A process is described for electrolessly plating nickel onto zinc die castings to provide corrosion resistance and wearability. 2. The key steps are depositing an electrolytic zinc layer, followed by one or more electroless nickel layers using alkaline or acidic baths. 3. It is preferred that the electroless nickel baths contain antimony ions to improve bath stability and adhesion of the plated layers.
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© © All Rights Reserved
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US005578187A
United States Patent (19) 11) Patent Number: 5,578,187
Zitko et al. 45 Date of Patent: Nov. 26, 1996
(54) PLATING PROCESS FOR ELECTROLESS 4,730,022 3/1988 Willis ...................................... 524/800
NICKEL ON ZINC DE CASTINGS 4,792,038 12/1988 Cooper .................................... 206/180
4,904,354 2/1990 Stavitsky et al. . ... 204/40
(75) Inventors: Mark W. Zitko, Meriden; John H. 5,182,006 1/1993 Haydu et al. ......... 205/213
Commander, Old Saybrook; Victor J. 5,194,140 3/1993 Dobrovolskies et al. 205/245
Waldman, Milford, all of Conn. 5,435,898 7/1995 Commander et al. .... ... 205/245
5,437,887 8/1995 Yarkosky et al. ....................... 427/1.31
(73) Assignee: Enthone-Omi, Inc., West Haven, Conn. OTHER PUBLICATIONS
(21) Appl. No.: 545,354 Caplus: 1982: 481,714.
Caplus: 1988: 635, 259.
22 Filed: Oct. 19, 1995 Metal Finishing, 63rd Guidebook and Directory Issue, Jan.
51 int. Cl. ................................... C2SD 5/00 1995, vol. 93, No. 1A, p. 402 May 7, 1986.
(52) U.S. Cl. ................... ... 205/191; 427/405; 427/438 Primary Examiner-Kathryn Gorgos
58 Field of Search ............................. 205/191; 427/405, Assistant Examiner-Kishor Mayekar
427/438 Attorney, Agent, or Firm-DeLio & Peterson
(57) ABSTRACT
(56 References Cited
U.S. PATENT DOCUMENTS
A process is provided for plating zinc die cast substrates with
an electroless nickel coating comprising depositing an elec
2,690,401 9/1954 Gutzeit et al. ............................ 117/47 trolytic zinc layer on the substrate followed by depositing a
2,690,402 9/1954 Crehan ........... ... 117/47 first electroless nickel layer on the electrolytic zinc layer
2,762,723 9/1956 Talmey et al. .......................... 117/130 using a first alkaline electroless nickel bath and then depos
2,884,344 4/1959 Ramirez .................................. 117/130 iting a finish electroless nickel layer on the first electroless
2,929,742 3/1960 Minjer et al. ........................... 117/130 nickel layer using an acidic electroless nickel bath. In a
2,935,425 5/1960 Gutzeit et al. .......................... 117/130 preferred embodiment, a second electroless nickel layer is
3,338,726 8/1967 Berzins ....................................... 106/1 deposited on the first electroless nickel layer using a second
3,853,718 12/1974 Creutz ............ ... 204/55 alkaline electroless nickel bath. It is preferred that at least
3,869,358 3/1975 Nobel et al. ... 204/55
3,884,774 5/1975 Kessler ............... ... 204/55 one and preferably all of the electroless nickel baths contain
3,930,081 12/1975 Shinomiya et al. ... ... 427/421 an effective amount of antimony ions to enhance bath
4,113,583 9/1978 Oshima et al. .... 204/55 stability and metal to metal adhesion. Mechanical cleaning
4,169,771 10/1979 Creutz et al. ... ... 204/55 of the zinc die casting before plating is preferred.
4,229,267 10/1980 Steinecker ...... ... 204/55
4,567,066 1/1986 Schultz et al. .......................... 427/305 7 Claims, No Drawings
5,578,187
1. 2
PLATING PROCESS FOR ELECTROLESS depositing a zinc or zinc alloy layer on the zinc die cast
NICKEL ON ZINC DE CASTINGS substrate using a zinc electroplating bath, preferably an
alkaline zinc bath;
depositing a first electroless nickel layer on the zinc layer
BACKGROUND OF THE INVENTION 5
using a first alkaline electroless nickel plating bath; and
1. Field of the Invention depositing a finish electroless nickel layer on the first
The present invention relates to a process for depositing electroless nickel layer using an acidic electroless
electroless nickel on zinc die cast substrates and the products nickel plating bath.
made from the process, and more particularly, to a process 10 A preferred embodiment utilizes an additional step of
comprising a series of metal electroplating and electroless depositing a second electroless nickel layer on the first
nickel plating steps to provide a plurality of different metal electroless nickel layer using, preferably, a different second
layers on the zinc die cast substrate and in a preferred alkaline electroless nickel plating bath. In highly preferred
embodiment to the use of antimony in one or more of the embodiments, at least one and preferably all of the electro
electroless nickel plating baths. 15 less nickel plating baths contain an effective amount of
2. Description of Related Art antimony ions to provide enhanced bath stability and adhe
sive plated layers.
Zinc die castings are used to make a variety of industrial It is also preferred to clean or rough finish the castings
and consumer products because of their low cost and ease of before zinc electroplating with a highly preferred method
fabrication. The zinc die castings however, are not aestheti 20
being mechanical cleaning by tumbling the castings in a
cally pleasing and/or do not have the properties required for barrel by themselves or with ceramic or other particles
most products such as corrosion resistance or wearability. preferably in a fluid medium.
Accordingly, most zinc die cast products have a finish The zinc die cast articles having an electroless nickel
coating depending on the particular application or decorative coating prepared by using the process of the invention
effect required. comprise a zinc die cast substrate, a layer of electrolytic zinc
25
Electroless nickel has been used extensively to plate zinc or zinc alloy on the zinc die cast substrate, a first layer of
die cast parts with a finished coating because of its many electroless nickel deposited on the electrolytic zinc layer
desired properties such as brightness, corrosion resistance, from a first alkaline electroless nickel bath and a finish layer
wearability and the like. Electroless nickel is not typically of electroless nickel deposited on the first layer of electroless
used for the direct plating of the zinc die casting, however, 30 nickel deposited from an acidic electroless nickel bath. A
because of bath contamination and lack of adhesion between preferred embodiment comprises a second layer of electro
the zinc die casting and the electroless layer resulting in less nickel deposited on the first layer of electroless nickel
blistering and peeling of the electroless nickel layer. Pro which second layer is preferably deposited from a different
cesses have been developed to electrolessly nickel plate Zinc second alkaline electroless nickel plating bath than the first
die castings and one process utilizes an electrolytic copper 35 bath used to plate the first electroless nickel layer. It is highly
strike coating on the zinc die casting followed by electroless preferred that at least one and preferably all of the electroless
nickel plating to produce the final coating. The electrolytic nickel baths contain an effective amount of antimony ions to
copper layer provides an adhesive coating for the electroless enhance bath stability and metal to metal adhesion.
nickel layer and is likewise adhesive to the zinc die casting. DESCRIPTION OF THE PREFERRED
The use of electrolytic copper in industry is being sharply 40 EMBODIMENT(S)
curtailed, however, because commercial electrolytic copper
baths utilize cyanides which are toxic and environmentally Zinc die castings used for industrial and consumer prod
undesirable. Additionally, the use of barrel plating is becom ucts are very well known and are made using conventional
ing more important then rack plating for many applications casting techniques. Any Zinc or zinc alloy die cast part can
and new electroless nickel plating processes for zinc die 45 be used in the process of the invention to produce the articles
castings must be versatile and useful for all types of plating of the invention. Two typical zinc die casting alloys as in
processes including barrel plating, rack plating and immer ASTM B86 are shown in the following table:
sion processes.
Bearing in mind the problems and deficiencies of the prior ELEMENT ALLOY 3 ALLOY 5
art, it is therefore an object of the present invention to 50
provide a process for plating zinc die castings with electro Aluminum
Copper
3.904.30%
0.25 max. 76
3.90-430%
075-1.25%
less nickel. It is a further object of the present invention to Magnesium 0.02-0.05% 0.03-0.06%
provide a process for plating zinc die castings with electro Iron 0.075 Inax % 0.075 max. 26
less nickel using any electroless nickel plating process such Lead 0.004 max. 96 0.004 IIlax. 26
as rack, barrel and immersion plating processes. 55 Cadmium 0.003 max. 9 0.003 Ilax. 96
Tin 0.002 max. 9% 0.002 IIlax. 90
Another object is to produce electrolessly nickel plated Zinc Remainder Remainder
Zinc die casting products.
Still other objects and advantages of the invention will in In a highly preferred embodiment, the zinc die castings
part be obvious and will in part be apparent from the 60 are mechanically cleaned using a process such as "Harper
specification.
ization” which is a mechanical cleaning performed by
tumbling the castings with a ceramic media and fluid in a
SUMMARY OF THE INVENTION barrel. The fluid may be any suitable aqueous or non
aqueous fluid which is substantially noncorrosive and non
It has now been discovered that the objects and advan 65 reactive with the castings.
tages of the present invention for plating zinc die castings The mechanical cleaning removes scale, burs, flash, for
with an electroless nickel coating comprises: eign material and other undesirable protrusions or adherents,
5,578,187
3 4
and sometimes discoloration, from metal parts in a tumbling may range up to 200 amperes per square foot (ASF) or more
barrel. Cleaning is accomplished by impact between the with a preferred range being about 1 to 50. A plating
parts and their rubbing together, preferably in an admixture thickness of up to about 1 mill or higher usually 0.1 to 0.3
of ceramics, abrasive materials, sawdust, leather cuttings, mils may be plated although higher or lower thicknesses
and various other materials to suit conditions. Working 5 may be employed for certain applications.
conditions within the tumbling barrel sometimes are varied Electroless nickel baths are also very well known in the
to produce higher impact between the parts, with resultant industry and any electroless nickel bath may be used in the
surface hardening. A revolving barrel-like container in process of the invention. Other electroless baths may also be
which the castings are placed is generally used. used such as Ni-Co, Co, and the like but for convenience, the
It has been found that mechanical cleaning provides a 10 following description will be directed to electroless nickel
finished plated product having enhanced adhesive metal plating baths. Broadly stated, the electroless nickel bath
layer characteristics and the products made using the plating contains 1) a source of metal ions, 2) a reducing agent such
steps of the invention together with mechanical cleaning are as hypophosphite or amine borane, 3) an acid or hydroxide
an important feature of the invention. pH adjuster to provide the required pH and 4) a complexing
The zinc die castings are also preferably cleaned to 15 agent for metal ions sufficient to prevent their precipitation
remove grease and other dirt thereon. Typical cleaners are in the solution. Compositions for depositing electroless
acidic, alkaline or neutral and include sodium hydroxide, nickel are described in U.S. Pat. Nos. 2,690,401; 2,690,402;
sodium pyroborate, sodium metasilicate, sodium polyphos 2,762,723; 2,935,425; 2,929,742; and 3,338,726. Other use
phate and sodium carbonate, together with surfactants and ful compositions for depositing nickel and its alloys are
complexing agents and are used both by immersion tech 20 disclosed in the 63rd Guidebook and Directory Issue of The
niques and electrolytic techniques. Organic solvents may Metal Finishing for January 1995, Volume 93, Number 1A,
also be used alone or in admixture with the above chemicals. Elsevier Science, Inc., page 402. The foregoing publications
The mechanical cleaning and chemical cleaning steps are included herein by reference.
may generally be performed in any order. The nickel ion may be provided by the use of any soluble
The chemically and/or mechanically cleaned zinc die 25 salt such as nickel sulfate, nickel chloride, nickel acetate,
castings are then preferably etched and then provided with nickel sulfamate and mixtures thereof. The concentration of
an electrolytic strike coating of zinc or zinc alloy. The the nickel in solution may vary widely and is about 0.1 to
etchant may be any suitable material and is preferably 100 g/l, preferably about 2 to 50 g/l, e.g., 2 to 10 g/l.
acidic, e.g., HSO4. Any zinc electroplating bath may be The reducing agent is usually the hypophosphite ion
used and a number of patents have been issued over the 30 supplied to the bath by any suitable source such as sodium,
years disclosing such baths including: U.S. Pat. Nos. 3,853, potassium, ammonium and nickel hypophosphite. Other
718; 3,869,358; 3,884,774; 4,113,583; 4,169,771; 4,229, reducing agents such as amine boranes, borohydrides and
267; 4,730,022; 4,792,038; 5,182,006; 5,194,140; and hydrazine may also suitably be employed. The concentration
5,435,898. The disclosure of these patents are hereby incor of the reducing agent is generally in excess of the amount
porated by reference. 35 sufficient to reduce the nickel in the bath.
The preferred zinc electroplating bath is alkaline and The baths will be acid or alkaline depending on the plating
contains a zinc compound and an alkali hydroxide. The zinc step being performed. The acid or alkaline pH adjuster may
salt may be any soluble salt and is usually zinc oxide and the be selected from a wide range of materials such as ammo
base sodium hydroxide and the predominant zinc species in nium hydroxide, sodium hydroxide, hydrochloric acid and
40
the bath at high pH ranges is believed to be the zincate ion. the like. The pH of the acid bath usually ranges from about
The zinc bath may also contain zinc alloy ingredients such 2 to 5.5, preferably 4.5 to 5.5 and the alkaline bath from
as nickel, cobalt and iron and combinations thereof to about 8-14, preferably 8-11.
provide alloys of zinc and nickel; zinc and cobalt; zinc, The complexing agent may be selected from a wide
nickel and cobalt, Zinc and iron; and zinc, iron and cobalt. 45 variety of materials such as lactic acid, malic acid and those
The composition of the zinc electroplating bath is gener containing anions such as acetate, citrate, glycolate, pyro
ally about 5 to 25 g/l and up 200 g/l, e.g., 100 g/l of the zinc phosphate and the like, with mixtures thereof being suitable.
compound and about 75 g/l to 500 g/l of the alkali hydrox Ranges for the complexing agent, based on the anion, may
ide. A preferred zinc electroplating bath comprises about 7.5 vary widely, for example, about 1 to 300 g/l, preferably
to 15 g/l zinc and 100 to 135 g/l sodium hydroxide. 50
about 5 to 50 g/l.
A chelating agent is normally employed in the bath in an The electroless nickel plating baths may also contain
effective amount to maintain the metals in the bath in other ingredients known in the art such as buffering agents,
solution. The chelating agent used herein should complex bath stabilizers, rate promoters, brighteners, etc.
the metal ions to an electrodepositable extent in a strong It has been found that the use of antimony ions in the
alkalinity of a pH of above 13 and thus permit their stable 55 electroless nickel plating baths provide enhanced bath sta
dissolution. Levels of about 1-150 g/l or more may be bility and metal adhesion properties. Amounts of about 10 to
employed and suitable chelating agents includes citrates, 500 ppm preferably 30 to 60 ppm may be employed. The
tartrates, gluconates and glycolates, amino alcohols, poly antimony may be supplied to the bath in any suitable form
amines, aminocarboxylic acid salts, polyhydroxy alcohols, such as antimony potassium tartrate and antimony trifluo
sorbitol and thioureas. The plating bath may also contain 60 ride.
additives of the type conventionally employed in alkaline The use of antimony in electroless nickel plating baths is
Zinc electroplating baths and includes such materials as described in U.S. Pat. No. 2,884,344 which relates to
brightening agents, grain refiners, and the like. electroless nickel plating on metal surfaces. The patent
The zinc die casting may be electroplated over a wide shows the need for two or more elements selected from
range of temperatures of about 10° to 100° C., typically from 65 arsenic, antimony and bismuth to accelerate the plating
20° to 50° C. preferably 25° to 32° C. for 5 to 30 minutes, process and to stabilize the bath against catalytic decompo
preferably 10 to 20 minutes. The current desities employed sition. U.S. Pat. No. 5,437,887 is directed to making alumi
5,578,187
5 6
num memory disks and utilizes antimony or cadmium in electroplated using a bath containing 11.25 g/l zinc and 105
electroless nickel phosphorous baths to enhance the reten g/l NaOH. The bath had a pH of 14 and the castings were
tion of the original magnetic properties of the plating after barrel plated at 10 amps per square foot (ASF) for 15
exposure of the disks to elevated temperatures. U.S. Pat. No. minutes at 20° C. A thickness of about 0.1 mil was plated.
3,930,081 is directed to forming a coating on a zinc surface After a cold water rinse, the castings were barrel plated at
with an acidic displacement solution (not an electroless 90° C. for 30 minutes in a first electroless commercial
nickel plating bath) containing nickel, cobalt or iron and a alkaline nickel plating bath using sodium hypophosphite as
desensitizing ion selected from antimony, tin, copper, lead,
germanium, vanadium, arsenic and tungsten. the reducer and having a pH of 9. The bath contained 40 ppm
antimony.
A suitable electroless nickel plating bath may be formed 10
by dissolving the ingredients in water and adjusting the pH After a cold water rinse, the nickel plated castings were
to the desired range. barrel plated under the same conditions as the first electro
The zinc coated zinc die casting is plated with an alkaline less nickel plating in a second different electroless nickel
electroless nickel bath with a strike coating or to any desired plating bath having the same composition as the first elec
thickness. Preferably, the part is immersed in the bath to 15 troless nickel bath. Both nickel platings had a thickness of
plate a thin nickel coating adequate to provide a suitable about 0.1 mil.
base for the thick deposits of the final nickel plate using a The plated castings were then rinsed with cold water and
different acidic electroless nickel bath. Thicknesses may barrel plated in a bright electroless commercial nickel plat
range up to about 1 mill or higher, typically 0.1 to 0.3 mils. 20 ing bath having a pH of 5.2 at 85°C. for 30 minutes. The
An immersion time of 5 to 60 minutes, preferably 10 to 30 bath contained 40 ppm antimony. The nickel plating had a
minutes usually provides the desired coating, depending on thickness of about 0.3 mil.
bath parameters. A temperature range of about 25 C. to The plated parts were bright and had excellent adhesion
boiling, e.g., 100° C., may be employed, with a range of (no blistering or delamination) after heating at 350°F. for 30
about 80° to 95° C. being preferred. 25 minutes.
In a preferred embodiment, a second electroless nickel While the present invention has been particularly
layer is deposited on the first electroless nickel layer using described, in conjunction with a specific preferred embodi
preferably a different second alkaline electroless nickel bath. ment, it is evident that many alternatives, modifications and
Similar thicknesses and plating times for the second elec variations will be apparent to those skilled in the art in light
troless nickel layer may be used as for the first electroless 30 of the foregoing description. It is therefore contemplated that
nickel layer. the appended claims will embrace any such alternatives,
The next step is to complete the nickel plating to the modifications and variations as falling within the true scope
desired thickness and finish physical characteristics by and spirit of the present invention.
immersing the nickel coated part in an acidic electroless Thus, having described the invention, what is claimed is:
nickel plating bath which is maintained over a temperature 35 1. A process for plating a zinc die casting with an
range of about 30°C. to 100°C., e.g., boiling, preferably 80 electroless nickel coating comprising:
C. to 95° C. A thickness up to 5 mils. or higher may be mechanically cleaning the zinc die casting;
employed, with a range of about 0.1 to 2 mils e.g. 0.3-0.5 depositing a zinc or zinc alloy layer on the casting using
mils being used for most applications. An immersion time of a zinc electroplating bath having a pH greater than
30 to 60 minutes is typically used. It is preferred to rinse the 40 about 13;
electrolessly coated substrates between plating steps.
It will be appreciated by those skilled in the art that the depositing a first electroless nickel layer on the zinc
rate of electroless plating may be influenced by many factors electroplated layer using a first alkaline electroless
including (1) pH of the plating solution, (2) concentration of nickel bath containing antimony ions in an effective
reductant, (3) temperature of the plating bath, (4) concen 45 amount to provide enhanced bath stability and metal
tration of soluble nickel, (5) ratio of the volume of bath to adhesion properties; and
the area plated, (6) presence of soluble fluoride salts (rate depositing a finish electroless nickel layer on the electro
promoters) and (7) presence of wetting agent and/or agita less nickel layer thereof using an acid electroless nickel
tion, and that the above parameters are only provided to give bath.
general guidance for practicing the invention; the invention 50 2. The process of claim 1 further comprising depositing a
residing in the use of a series of electrolytic zinc and second electroless nickel layer on the first electroless nickel
electroless nickel plating steps as herein before described to layer using a second alkaline electroless nickel bath con
provide a zinc die casting having enhanced metal adhesion taining antimony ions in an effective amount to provide
and other properties. enhanced bath stability and metal adhesion properties.
The composition and process of the present invention will 55 3. The process of claim 1 wherein the zinc die casting is
now be more fully illustrated by the following specific mechanically cleaned before being plated by tumbling the
examples which are illustrative and in no way limitative and castings together.
wherein all parts and percentages are by weight and tem 4. The process of claim 3 wherein the tumbling is per
peratures in degrees centigrade unless otherwise noted. formed in a barrel with fluid and ceramic media.
60 5. The process of claim 1 wherein the zinc die castings are
EXAMPLE plated in each of the plating steps by barrel plating.
6. The process of claim 2 wherein the zinc die castings are
Mechanically cleaned (Harperized) and chemically plated in each of the plating steps by barrel plating.
cleaned zinc die castings about 1X2X2 inch of Alloy 3 supra 7. The process of claim3 wherein the zinc die castings are
were plated using the following process. The castings were 65 plated in each of the plating steps by barrel plating.
first etched in an acidic etch solution for 2 minutes at 25 C.
After rinsing with water the etched castings were zinc ck k k :: *k
UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,578,187
DATED : November 26, 1996
INVENTOR(S) : Mark W. Zitko, et. al.
it is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
Corrected as shown below:

Title page, item (73), the correction should read:--ENTHONE-OMI, INC

Signed and Sealed this


Eleventh Day of March, 1997

(a teen
BRUCE LEHMAN

Attesting Officer Commissioner of Patents and Trademarks

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