United States Patent Office 3,152,009

Patented Oct. 6, 1964

2
provision of an electroless nickel plating procedure where
3,152,009 by hydrogen fluoride, nickel salts other than nickel chlo
ELECTROLESS NICKEL, PLATING ride or sulfate, a compatible hypophosphite ion, an organic
Herbert K. De Long, Midland, Mich., assignor to The acid salt and optionally potassium or ammonium fluoride
Dow Chemical Company, Midland, Mich., a corpo are mixed in an aqueous solution, and used to treat a cata
ration of Delaware
No Drawing. Coatiauation of application Ser. No. lytic basis metal surface, such as, iron, aluminum, brass
725,510, Apr. 1, 1958. This application May 7, 1962, or magnesiu in metal surfaces, at a pH between 3.5 and
Ser. No. 195,405 7.0 and at a temperature between 90 and 212 degrees
7 Claims. (C. 117-130) Fahrenheit thereby to yield a hard, adherent, semi-bright,
10 nickel plate on the metal. Other objects will become ap
This invention relates to the deposition of nickel by parent hereinafter.
chemical reduction as opposed to electrolytic deposition The foregoing and additional objects have been accom
and is more particularly concerned with a bath therefor plished by the provision of an electroless nickel plating
and a method for the electroless deposition of nickel on bath comprising nickel ions, fluoride ions, and hypophos
magnesium, aluminum, iron and brass and other cata 5 phite ions in water. This bath also must contain at a maxi
lytic basis metals. mu;in only trace quantities of chloride ion and sulfate
This application is a continuation of my prior-filed ap ion. It has been found that such a bath will plate mag
plication Serial No. 725,510, filed April 1, 1958, now nesium without attack of the magnesium. In order to
abandoned, which was a continuation-in-part of applica maintain the nickel in solution, a pH for the bath below
tion Serial No. 663,871 filed June 6, 1957, now aban 20 7.0 is required and to prevent excessive attack of the metal
doned. to be plated, a pH below about 3.5 is usually avoided.
In United States Patent 2,532,283, Brenner, there is de Preferably, the pH is maintained between 5.0 and 6.8
scribed a method of nickel plating by chemical reduction. and the most desirable pH is 6.5 for most uses. Con
This patented process uses nickel chloride or nickel sulfate trol of the pH may be accomplished by adding ammoni
in combination with a hypophosphite to accomplish dep 25 um hydroxide, hydrogen fluoride, or other acidic or basic
osition of nickel on a metallic surface without the ap materials compatible with the bath. Preferably, a water
plication of an electric current. This process has var soluble organic acid salt is employed as buffering agent
iously been called electroless or chemical nickel plating. to maintain pH control. Representative salts of organic
However, when magnesium is placed in the Brenner bath, acids which may be employed as buffers include, for ex
substantial etching of the magnesium and foaming oc 30 ample, Sodium citrate, sodium succinate, sodium tartrate,
curs as the acid solution attacks the metal, or else, the Sodium phthalate, sodium lactate, potassium citrate, etc.
magnesium dissolves in the solution and replaces the that is, a Soluble Salt which affects the pH so as to main
nickel therein. Thus, the Brenner bath has not been suit tain the solution in the desired pH range. The presence
able for the deposition of nickel on magnesium. of the fluoride ion is usually accomplished by the addition
Another United States Patent 2,694,019, Gutzeit, shows 35 of a 50 percent aqueous solution of hydrogen fluoride,
the feasibility of using fluoride concentrations below 0.12 however, fluoride Salts may be employed, such as, for ex
mole per liter, but indicates that greater concentrations of ample, sodium, potassium, ammonium, nickel, etc. fluo
fiuoride ion decrease the plating rate and adversely affects rides. By the addition of fluoride salts where hydrogen
the stability of the bath. This patent, however, shows
40
fluoride is also employed, some mass action repression
only the use of nickel chloride as the source of nickel of the hydrogen fluoride is obtained, thereby affording
ions. When magnesium is placed in the Gutzeit bath, a Some pH control. When hydrofluoric acid is used as a
similar result is obtained as is obtained with the Bren 50 percent aqueous solution, quantities from 5.7 cc. per
ner bath, i.e., etching and foaming of the magnesium sur liter to 98 cc. per liter may be employed to obtain a
face.
45
final bath concentration between .15 and 2.5 moles per
Where the use of magnesium metal is desired because liter of fluoride. Preferably the mole per liter concen
of its structural advantages including strength and reduced tration of fluoride employed is from .15 to .75 and de
weight, but because its wearability or resistance to corro sirably at .32 mole per liter.
sion does not meet the requirements of a particular ap The concentration of the nickel ion in the final bath
plication, coating with a nickel surface would be desira 50 may be varied from .04 to 1.4 moles per liter, but is
ble. This nickel coating would increase the corrosion preferably present in concentrations from .08 to .32,
resistance and wearability of the magnesium base material from .04 to .16 mole per liter also being satisfactory and
without appreciably affecting its structural and weight desirably a concentration of .08 mole per liter is used.
advantages. Representative applications where the proc Unexpectedly, it has been found that nickel chloride and
ess can be utilized to increase wear resistance and resist 55 nickel Sulfate may not be used in the bath and process of
ance to corrosion of various base metals include printing the present invention as the source of nickel ions. When
plates, aircraft tubing, fluid couplings, internal combustion these materials are employed, extensive gassing of mag
engine parts, electronic equipment parts having complex nesium occurs. Therefore, the use of nickel chloride or
shapes, etc. Other applications are also possible, par
ticularly those shapes difficulty plateable by conventional nickel sulfate is not contemplated within the scope of this
electrolyte methods. Another use of the nickel surface is 60 invention and are specifically excluded herefrom. While
as a base for subsequent coatings of copper, chromium, basic nickelous carbonate is usually employed to obtain
tin, nickel, zinc, cadmium, silver, gold, etc., using con the nickel ion concentration, other soluble nickel salts
ventional baths and procedures. which will furnish the nickel ion to the final bath, such
It is, therefore, a principal object of the present inven 65
as, for example, nickel carbonate, nickel cyanide, nickel
tion to provide an electroless nickel plating bath suitable fluoride, nickel acid fluoride, nickel hydroxide, nickel
for use on magnesium. Another object of the present in Oxalate, nickel oxide, nickel phosphide, nickel hypophos
vention is to provide an electroless nickel plating pro phate, etc. may be used. A water-soluble salt of a
cedure applicable to magnesium and which results in a hypophosphite is employed such that the resulting gram
nickel plate which is continuous, hard, semi-bright, has 70 ion concentration of hypophosphite ion is between .04
good adhesion, and which can be buffed to a mirror-like and 2.6 moles per liter, preferably .04 to .55 mole per
surface. A further object of the present invention is the liter and desirably .18 mole per liter. To achieve a con
 3,152,009
3 4.
centration of hypophosphite ion of .18 mole per liter, 20 10.8551 grams or a weight gain of .1833 gram. The plat
grams per liter of NaH2POHO are employed. ing rate for thickness was 0.0006 inch per hour of a con
When a bath of the above composition has been pre tinuous, hard, semi-bright metallic in color, nickel plate
pared, it may be used to treat a catalytic metal surface having a good adhesion to the magnesium surface. There
which has been cleaned to remove any oxide, oil, or was no evidence of chemical attack on the basis metal.
other surface contamination which might be present. If Example 2
such surface contaminations are allowed to remain, a
firmly adhered nickel plate is not usually obtained. Ei To show that increased plating rates may be obtained
ther brushing with a steel brush, sand blasting, or the from increased fluoride concentrations, the following baths
use of pickling and surface activating pre-treatments may O
were prepared and the procedure of Example 1 repeated
be employed. The surface activation and cleaning tech with the following results:
niques are conventional and are used in a conventional
manner to provide a relatively clean surface for the (a)
deposition of the nickel. The article to be plated after
surface treatment is immersed in a bath such as herein 5 HF (70%) ---------------------------cc./I-- 5
before described while a bath is maintained at a tempera 2NiCo3+3Ni(OH)2.4H2O --------------gm./l.-- 10
ture from 90 to 212 degrees Fahrenheit, preferably from NaH2PO2H2O -----------------------gm./I.- 20
160 to 212 degrees Fahrenheit, and desirably at 170 to Na3CH5O' 2H2O sm - n man mm - - - - - - - - - - gm./l.-- 10
180 degrees Fahrenheit. The surfaces to be plated are Temperature ---------------------------- F - 175
immersed in the bath at the pre-selected temperature for 20
pH ---------------------------------------- 6.5
a period of time from 3 minutes to a number of hours Rate, 0.0001' per hour.
depending upon the particular characteristics of the plate (b)
desired. Thereafter, the article is separated from the
bath, washed to remove any bath residue, and, if desired, HF (70%) ----------------------------cc./l-- 5
buffed to give a hard, bright, adherent, nickel plate having 25
2NiCO3-3Ni(OH)2.4H2O -------------gm./l.-- 10
thicknesses up to and above three thousandths of an inch. NaH2POHO a is a Purw vow n w man men m - - - - - - - - gm./l.-- 20
While the bath of the present invention is particularly Na3CH5O'2H2O - - --- - - -- - --- -- - -- - - - gm./l.-- 10
suited for magnesium, it may be used on other catalytic NH4HF2 -----------------------------gm./l-- 5
basis metal, such as, for example, iron, aluminum, brass, Temperature --------------------------- F 175
etc. surfaces with facility. The bath of the present in pH ---------------------------------------- 6.5
vention appears to be more stable than the prior art Rate, 0.0005'' per hour.
baths by virtue of the absence of substantial precipitation (c)
as is found in prior art baths after use.
The following examples are given to illustrate the HF (70%) --------------------------cc./-- 5
process and bath of the present invention but are not to 2NiCO33Ni(OH)2.4H2O --------------gin./l-- 10
be construed as limiting the bath or process thereto. NaH2PO2H2O -----------------------gm./l-- 20
Comparative Prior Art Na3C5H5O2H2O --- -- - - - - - - - - -- - - - - - - gm./l.-- 10

A Mg base alloy having a nominal composition of NHHF m r - an as a - norm on ru respo e - - - - - - - - - - gm./ll- 10

3 percent aluminum, 1 percent zinc, balance magnesium, 40 Temperature --------------------------- F 175

panel whose dimensions were 1 inch by 2 inches by 0.040 pH ---------------------------------------- 6.5
inch were immersed in a conventional nickel chloride Rate, 0.0008' per hour.
electroless nickel solution of the following composition: (d)
(U.S. Patent 2,532,283-Brenner).
HF (70%) ----------------------------cc./ll- 5
NiCl26H2O ------------------grams/liter.-- 30 2NiCO3'3Ni(OH)2.4H2O --------------gm./l-- 10
NaH2POHO - - - - - - - - - as a -- --- - -do---- 10 NaH2PO2H2O -----------------------gm./I-- 20
NH4Cl ----------------------------do---- 50 NaCHO-2HO - - - -- - - - - - - - -- - - - - - - -gm./1-- 10

Na3CH5O'5H2O, sodium citrate ------ do---- 100 NH4HF2 -----------------------------gm./1-- 15

pH------------------------------------- 8.4 50 Temperature --------------------------- F. 175
Temperature -----------degrees Fahrenheit-- 170-180 pH ---------------------------------------- 6.5
Rate, 0.001' per hour.
The original weight of the panel was 10.7814 grams and (e)
after 1 minute immersion time it weighed 10.3937 grams,
giving a weight loss in grams/minute of .38777. This 55 HF (70%) ----------------------------cc./1-- 5
panel gassed very profusely in the above solution caus 2NiCO3Ni(OH)2.4H2O --------------gm./l-- 10
ing considerable foam, and it was difficult to keep the NaH2POHO ara - - --- - - - - - - - --- -- - - - - - gm./l.-- 20

panel immersed in the solution. The panel, after the 1 Na3CH5O 2HO - - - - - - - -a - - - - - - - - - - -gm./1.-- 10

minute immersion was badly pitted by the chemical NH4HF2 -----------------------------gm./-- 20

attack. 60 Temperature --------------------------- F. 175
Example 1 pH ---------------------------------------- 6.5
A similar panel to that used above was immersed in Rate, .0010' per hour.
an acid fluoride electroless nickel bath of the following (f)
composition:
HF (70%) ---------------------------cc./I-- 5
HF (50 percent) --------------milliliters/liter- 7 2NiCO33Ni(OH)2.4H2O --------------gm./-- 10
2NiCO3Ni(OH)2.4H2O ----------grams/liter-- 10 NaH2PO2H2O -----------------------gm./1-- 20
NaH2PO2H2O ------------------------do---- 20 NaCH5O2H2O a - no run uu u m or mum - - - - - - - - - - - gm./l.-- 10

NaCHO".5H2O - - - -- - - -- - - --- --- - -- m --do---- 10 NH4HF2 -----------------------------gm./ll- 25

KF ----------------------------------do---- 10 70 Temperature --------------------------- F 175
pH ---------------------------------------- 6.5 pH ---------------------------------------- 6.5
Temperature --------------degrees Fahrenheit-- 175 Rate, .0012'' per hour.
The original weight of the panel was 10.6718 grams and with all of the above baths, a bright, nickel deposit hav
the weight of the panel after 30 minutes immersion was 75 ing good adhesion was obtained.
 3,152,009
5 6
Example 3 Example 4
Other examples of baths which have been used to give Many types of magnesium alloys have been plated uti
bright and adherent electroless nickel deposits are: lizing the baths of the present invention including:
Sand cast -------------------------------- EK30
(a) Sand cast -------------------------------- EZ33
Sand cast -------------------------------- AZ92
NiF2'4H2O --------------------------gm./1-- 14 Sand cast -------------------------------- AZ63
NaH2PO2H2O -----------------------gm./1-- 20 Sand
Na3CshsO7.5H2O ----------------------gm./l.-- 10 O Sand cast --------------------------------
cast --------------------------------
HZ32
HK3
KF ---------------------------------gm./-- 10 Sand cast -------------------------------- AZ81
Tempellature --------------------------- F 175 Extrusions ------------------------------- ZK60
pH ---------------------------------------- 6.8 Extrusions ------------------------------- AZ80A
Rate, 0.0009' per hour. Extrusions ------------------------------- AZ61A
(b) 5 Die cast ---------------------------------- AZ91A.
Sheet ------------------------------------ AZ31A
HF (50%) ---------------------------cc./l.-- 7
2NiCO33Ni(OH)2.4H2O --------------gm./1-- 10 Sheet ------------------------------------
Sheet M1A
------------------------------------ ZE10
NaH2PO-HO

Na3CHO 5H2
----

- ww
- -- -

- - - -
Sheet ------------------------------------ HK31
- - - --- - -- - -

- - - - - www a - - - - we -
- - - -gm./l.--

gm./l.--
20

10
20 Sheet ------------------------------------ HM21
KF----------------------------------gm./l-- 10
Temperature --------------------------- F 175 While the invention has been particularly described
pH ---------------------------------------- 6.5 with respect to magnesium and the magnesium base alloys,
Rate, 0.0009' per hour. it is to be understood that the bath and process of the
(c) 25 present invention are applicable to other catalytic basis
metals including, for example, iron, aluminum, aluminum
HF (50%) ---------------------------cc./l-- 7 base alloys, brass, etc.
NiCOs --------------------------------g./l-- 10 The term "magnesium” used herein and in the ap
NaH2PO-H2O -- - -- - -- - - - -- -- - - - -- - - - - - g./l-- 20 pended claims means magnesium and the magnesium base
Na3CH5O 5HO - a -- - - - - - - - - -a ad - - - - - - - - - g/l.-- 10 30 alloys in which the magnesium content exceeds 75 per
KF -----------------------------------g./l-- 10 cent by weight. s
Temperature --------------------------- F. 175 Various modifications may be made in the bath and
pH ---------------------------------------- 6.5 method of the present invention without departing from
Rate, 0.0010' per hour. the spirit or scope thereof and it is to be understood that
(d) I limit myself only as defined in the appended claims.
I claim:
HF (50%) ---------------------------cc./l-- 7 1. A process for electroless nickel plating which com
2NiCO33Ni(OH)2.4H2O ---------------g/1-- 10 prises;
NaH2POHO - -- -- - -- - - - - -- -- - -- - -- - - -g/l-- 20 immersing a magnesium based metal article in an
Na3C5H5O. 2HO - - -- - - - - -- - - - - - -- - -- - - -g/l.-- 10 40 aqueous solution maintained at a temperature of
KF -----------------------------------g/l.-- 10 from about 90 to about 212 F., said aqueous solu
Temperature --------------------------- F 175 tion consisting essentially of from about 0.15 to
pH ---------------------------------------- 6.5 about 2.5 moles fluoride ion per liter of said aque
Rate, 0.0008' per hour. ous solution, from about 0.04 to about 1.4 moles
(e) 45 nickel ion per liter of said aqueous solution and from
about 0.04 to about 2.6 moles hypophosphite ion per
HF (70%) --------------------------cc./1-- 5 liter of said aqueous solution, said solution containing
2NiCO33Ni(OH)2.4H2O ----------------g/l.-- 10 at a maximum only trace quantities of chloride
NaH2POHO - -- - - - --- - - - - -- - - -- - - - - - -g/l.-- 20 and sulfate ions and being buffered to a pH between
Na3CshsO2H2O ----------------------g./l-- 10 50 about 3.7 and 7.0.
NH4HF2 -------------------------------g./ll- 10 2. A process for electroless nickel plating which com
Temperature --------------------------- ° F 175 prises;
PH---------------------------------------- 6.5 (1) immersing a magnesium based metal article in an
Rate, 0.0008' per hour. aqueous solution maintained at a temperature of
55 from about 90 to about 212 F., said aqueous solu
(f) tion consisting essentially of from about 0.15 to
about 2.5 moles fluoride ion per liter of said aqueous
HF (70%) ---------------------------cc./l-- 5 solution, from about 0.04 to about 1.4 moles nickel
2NiCO33Ni(OH)2.4H2O ----------------g./l-- 10 ion per liter of said aqueous solution and from about
NaH2PO-H2O - --- - -- - - - - -- - -- -- - - - - -g/l.-- 20
60 0.04 to about 2.6 moles hypophosphite ion per liter
Na3CHsO. o 2H2O -- a- - - - - - - - --- - - - -- - - - - - g./I-- 10
of Said aqueous solution, said solution containing at
KF -----------------------------------g./I-- 20 a maximum only trace quantities of chloride and
Temperature --------------------------- ° F 175 sulfate ions and being buffered to a pH between about
PH---------------------------------------- 6.5 3.7 and 7.0,
Rate, 0.0010' per hour. 65 (2) maintaining the article in said solution for at least
(g) 3 minutes, and
(3) separating the nickel plated article from said
HF (70%) ---------------------------cc./1-- 5 solution.
2NiCO33Ni(OH)2.4H2O ----------------g/l-- 10 3. A process for electroless nickel plating which com
NaH2PO2H2O -------------------------g./l-- 20 O prises;
Na3CsHsO2H2O ----------------------g./l-- 10 (1) immersing a magnesium based metal article in an
NH4HF2 ------------------------------g./-- 20 aqueous solution maintained at a temperature of
Temperature --------------------------- F 175 from about 90 to about 212 F., said aqueous solu
PH---------------------------------------- 6.5 tion consisting essentially of from about 0.15 to
Rate, 0.0010' per hour. 75 about 2.5 moles fluoride ion per liter of said aqueous
 3,152,009
7 8
solution, from about 0.04 to about 1.4 moles nickel (1) immersing a magnesium based metal article in an
ion per liter of said aqueous solution and from about aqueous solution maintained at a temperature of
0.04 to about 2.6 moles hypophosphite ion per liter from about 160 to about 212 F., said aqueous solu
of said aqueous solution, said solution containing at tion consisting essentially of about 0.32 mole fluoride
a maximum only trace quantities of chloride and 5 ion per liter of said aqueous solution, about 0.08
sulfate ions and being buffered to a pH between about mole nickel ion per liter of said aqueous solution,
3.7 and 7.0, said nickel ion being furnished substantially from
(2) maintaining the article in said solution for at least nickel carbonate and about 0.18 mole hypophosphite
3 minutes, and ion per liter of said aqueous solution, said solution
(3) separating the nickel plated article from said solu- 10 containing at a maximum only trace quantities of
tion, and chloride and sulfate ions and being buffered to a
(4) washing the nickel plated article to remove bath pH of about 6.5, -
residue therefrom. - - (2) maintaining the article in said solution for a period
4. A process for electroless nickel plating, which com of time of from about 3 minutes to a number of
prises; - - - - 5 hours, and
(1) immersing a magnesium based metal article in an (3) separating the resulting nickel plated article from
aqueous solution maintained at a temperature of said solution. -
from about 90 to about 212 F., said aqueous solu 6. A bath for nickel plating by chemical reduction of
tion consisting essentially of from about 0.15 to magnesium and its alloys consisting essentially of an
about 0.75 mole fluoride ion per liter of said aque- 20 aqueous solution of a nickel salt and a hypophosphite and
ous solution, from about 0.08 to about 0.32 mole a fluoride, wherein the nickel ion is furnished essentially
nickel ion per liter of said aqueous solution and from nickel carbonate and wherein the concentration of
from about 0.04 to about 0.55 mole hypophosphite nickel is .04 to 1.4 moles per liter, of hypophosphite ion
ion per liter of said aqueous solution, said nickel 25 is .04 to 2.6 moles per liter, and of fluoride ion is .15 to
ion being obtained from a nickel compound selected 2.5 moles per liter, buffered to a pH between 3.5 to 7.0.
from the group consisting of basic nickelous car 7. A bath for nickel plating by chemical reduction of
bonate, nickel carbonate, nickel cyanide, nickel fluo magnesium and its alloys consisting essentially of an
ride, nickel acid fluoride, nickel hydroxide, nickel aqueous solution of a nickel salt and a hypophosphite
oxalate, nickel oxide, nickel phosphide and nickel 30 and a fluoride, wherein the nickel ion is furnished essen
hypophosphate, said solution containing at a maxi tially from basic nickel carbonate corresponding to the
mum only trace quantities of chloride and sulfate empirical formula 2NiCO33Ni(OH)2.4H2O and wherein
ions and being buffered to a pH between about 5.0 the concentration of nickel is .04 to 1.4 moles per liter,
and 6.8, of hypophosphite ion is .04 to 2.6 moles per liter, and of
(2) maintaining the article in said solution for a period fluoride ion is .15 to 2.5 moles per liter, buffered to a pH
between 3.5 to 7.0.
of time of from about 3 minutes to a number of
hours, and References. Cited in the file of this patent
(3) separating the resulting nickel plated articles from
said solution. UNITED STATES PATENTS
5. A process for electroless nickel plating which com- 40 2,694,019 Gutzeit ---------------- Nov. 9, 1954
prises; 2,916,401. Puls ------------------ Dec. 8, 1959