Patented Oct.

28, 1947 2,429,970

UNITED STATES PATENT OFFICE
2,429,970
SILVER PLATING
Christian J. Wernlund and James R. Macon,
Niagara Falls, N. Y., assignors to E. I. du Pont
de Nemours & Company, Wilmington, Del, a
corporation of Delaware
No Drawing. Application January 1, 1944,
Serial No. 51,841
5 Claims. (C. 204-46)
1. 2
This invention relates to Silver plating and more to 12 ounces per gallon of free cyanide. Various
particularly, to the electrodeposition of bright other practices common in electroplating silver
silver deposits from Silver cyanide plating baths. from cyanide baths are generally applicable to our
Without the use of brightening agents, silver invention.
cyanide plating baths produce dull or matte In practicing our invention we may add from
type silver deposits. Heretofore carbon disulfide 0.01 to about 1 ounce per gallon of the addi
has been used to some extent as a brightening tion agent. Preferably, the addition agent is first
agent in Silver plating baths. However, the dissolved in a small amount of alkali metal hy
brightening effect of this addition agent is ef droxide or in a small amount of the electroplating
fective Only OVer a relatively narrow range of O solution and the appropriate amount of this SO
Current densities and it has not been entirely suit lition is added to the plating bath. The bath is
able for the electrodeposition at relatively high then operated in the conventional manner to elec
current densities for a variety of purposes. trodeposit Silver.
An object of this bath is to provide a novel We have found that by means of our addition
process for the electrodeposition of bright silver 5 agents good, bright deposits of silver may be ob-,
electrodeposits. A further object is to provide a tained with still electrodes at current densities
brightening agent for silver cyanide plating baths as high as 30 amperes per square foot at both
the anode and cathode, and with moving elec
which is effective over a relatively wide current trodes
density range and at relatively high current den or With bath agitation to cause the elec
Sities. Further objects will be apparent from the 20 trolyte to flow past the electrodes, at current den
sities as high as 100 amperes per square foot at
following description of the invention. the anode and up to 50 amperes per square foot at
We have discovered that excellent bright de
posits of silver can be obtained over a wide range the Cathode. With a bath such as that set forth
of current densities by electrolysis of silver cy above, operated at a bath temperature of 21 to
anide Solutions to which have been added small 25 43 C., we are able to electrodeposit 0.001 inch of
amounts of certain organic sulfur compounds, to Silver at a current density of 37 amperes per
wit: 2-mercaptobenzothiazole, 2-mercaptothi Square foot at the Cathode in a period of about
azole, 2-mercaptothiazoline, thioacetanilide and 10 minutes. The electrodeposit is hard, dense
trimercaptocyanuric acid. Our novel addition and mirror bright. The brightness of the elec
agents may be utilized in any conventional silver 30 trodeposit and the high speed with which it is
Cyanide plating bath, that is, a bath containing a deposited make the process especially attractive
double cyanide of Silver and an alkali metal cy for many present day industrial uses.
anide, With or Without the further addition of The following examples further illustrate our
alkali metal hydroxide, carbonate or other addi
tives common in silver cyanide plating solutions. 35 in Vention:
The following is an example of a silver cyanide | Eacample 1
plating bath to which our invention can be ap
plied, it being understood that this formula is Silver was electroplated from the following so
given merely by way of example and that the in 40 lution maintained at a temperature of 27° C.,
Wention is in noWise restricted thereto: to which was added 2-mercaptobenzothiazole:
Ounces per gallon
Silver cyanide------------------------------ 10 Ounces per gallon
Potassium cyanide ------------------------- 16 AgCN ---------------------------------- 10
Potassium hydroxide ----------------------- 45 KCN ----------- a - -- - - - - - win m ------...-e we ... m. 17

KOH----------------------------------- 0.25
Silver plating baths made with potassium cy
anide are generally preferred in practicing our in Bright electrodeposits were obtained at the
Vention, but our novel brightening agents are Cathode current densities indicated below:
likewise effective in baths made with sodium cy 50
anide or With the cyanide of the other alkali
metals, cesium, rubidium and lithium. We may 2-Mercaptoben
20thiazole Current
also use electrolytes containing ions of two or
Concentration Bright Density
Range
more of the alkali metals, in any desired propor
tion. We may use a high concentration of free 02. per gal. Amps per sq. ft.
Cyanide, e. g., 10 to 14 ounces per gallon, or sub 0,040 5 to 30
stantially no free cyanide. In general, an in 0.054
0.067
4 to 60
5 to over 70
crease in free cyanide concentration results in a 0.134 6 to over 70
corresponding Widening of the current density
bright range. Usually we prefer to use about 6 60
 2,429,970
3 4
Eacample 2 Eacd.imple 6
The procedure of Example 1 was carried out Silver was electroplated from the solution of
using the following solution: Example 5, except that trimercaptocyanuric acid
Ounces per gallon 5 Was added as brightener. At a bath tempera
AgCN ----------------------------------- 10.0 ture of 32° C. and at the cathode current densi
NaCN ----------------------------------- 12.7 ties indicated below, bright electrodeposits were
KOH------------------------------------ 4.0 obtained:
The following results where obtained: 10
2-Mercaptoben- Cathode Current
20thiazole Density Trimercapto-
cyanuric Acid Current Density
Concentration Bright Range Concentration Bright Range
02. per gal. Amps. per sq.ft. O2. per gal. 47mps. per sq. ft.
6.
0.268
E;
8 to over 70
15 0.03 18 to 40
0.027 18 to 45
0.054 5 to 45
Eacample 3
Silver was electroplated from the following so- 20
lution maintained at a temperature of 32° C., to We claim:
which was added 2-mercaptothiazole: 1. A process for producing bright silver elec
Ounces per gallon trodeposits which comprises electrolyzing a sil
AgCN ----------------------------------- O ver-alkali metal cyanide solution containing an
KCN ------------------------------------ 10 25 Organic Sulfur compound selected from the group
consisting of 2-mercaptobenzothiazole, 2-mer
Bright electrodeposits were obtained at the captothiazole, 2-mercaptothiazoline, thioacetan
cathode current densities indicated below: ilide and trimercaptocyanuric acid in an amount
Sufficient to brighten the deposit within the
2-Mercapto- Current Density 30 range of 0.01 to 1 ounce per gallon.
thiazole
Concentration Bright Range 2. A process for producing bright silver elec
trodeposits which comprises electrolyzing a sil
Oz. per gal. 4mps. per Sq. ft. ver-alkali metal cyanide solution Containing 2
0.03 10 to 13 mercaptobenzothiazole in an amount sufficient to
0.027 5 to 10 35 brighten the deposit within the range of 0.01 to
0,040 5 to 7
0.067 5 to 7 1 ounce per gallon.
3. A process for producing bright silver elec
Eacample 4 trodeposits which comprises electrolyzing a sil
Silver was electroplated from the following so- 40 ver-alkali
acetanilide
metal cyanide solution containing thio
in an amount sufficient to brighten
lution, maintained at a temperature of 33 C., to the deposit within the rangew of 0.01 to 1 ounce
which was added 2-mercaptothiazoline: per gallon.
Ounces per gallon 4. A process for producing bright silver elec
AgCN ----------------------------------- 1945 trodeposits which comprises electrolyzing a sil
KCN ------------------------------------ O Ver-alkali metal cyanide solution containing tri
KOH------------------------------------ 4. mercaptocyanuric acid in an amount sufficient
Bright electrodeposits were obtained at the to brighten the deposit within the range of 0.01 to
cathode current densities indicated below: 1 ounce per gallon.
50 5. A process for producing bright silver elec
trodeposits which comprises electrolyzing a sil
2-Mercapto-
-
thiazoline
Current IDensity
Bright Range ver-potassium cyanide solution containing 2
Concentration mercaptobenzothiazole in an amount sufficient
to brighten the deposit within the range of 0.01
O2. per gal.
0.03
Amps. per sq. ft.
25 to 30
55 to 0.5 ounce per gallon.
0.027 30 to 55
0.054 30 to 60 CHRISTIAN J. WERNLUND.
JAMES R. MACON.
Eacample 5
Silver was electroplated from the following so- 60 REFERENCES, CTED
lution, to which was added thioacetanilide: The following references are of record in the
Ounces per gallon file of this patent:
AgCN ----------------------------------- 10
KCN ------------------------------------ 10 65 UNITED STATES PATENTS
Bright electrodeposits Were obtained at the Number Name Date
Cathode Current densities indicated below: 1857,507 Heckman et al. ----- May 10, 1932
2,110,792 Egeberg et al. -------- Mar. 8, 1938
Thioacetanilide Current Destiny
Concentration Bright Range 70 OTHER REFERENCES
O2. per gal. Aimps. per sq. ft. Transactions of the Electrochemical Society,
0.027 50 to over 70
0.054 to 45 vol. 74, pages 211-227 (1938).
75