SILVER PLATING
by Alan Blair
AT&T Bell Labs, Murray Hill, N. J.
The majority of silver-plating solutions in use today are remarkably similar to those
patented by the Elkington brothers in 1840. Even in these environmentally aware days,
cyanide-based silver-plating solutions offer the most consistent deposit quality at the lowest
cost.
Silver anodes dissolve readily in electrolytes containing free cyanide and the consumption
of brighteners or grain refiners is generally low, making these processes very economical to
operate in spite of waste treatment costs. High-speed silver-plating solutions that employ
insoluble anodes are well established, and, even though these contain no free cyanide,
potassium silver cyanide remains the source of the metal. Truly cyanide-free silver-plating
solutions have been sought after for many years. Several formulations are workable and are
described below.
CYANIDE SYSTEMS
A typical, traditional silver-plating solution suitable for rack work would be as follows:
Silver as KAg(CN), 15-40 g/L (2.0-5.5 oz/gal)
Potassium cyanide (free), 12-120 g/L (1.616 ozfgal)
Potassium carbonate (min), 15 g/L (2 oz/gal)
Temperature, 20-30°C (70-85°F)
Current density, 0.5-4.0 A/dm2 (5-40 A/ft*)
Barrel plating usually results in much greater drag-out losses and lower current density
during operation so lower metal concentrations are desirable. A typical formula would be:
Silver as KAg(CN), 5-20 g/L (0.7-2.5 oz/gal)
Potassium cyanide (free), 25-75 g/L (3.3-10.0 oz/gal)
Potassium carbonate (min), 15 g/L (2 oz/gal)
Temperature, 15-25°C (60-SOoF)
Current density, 0.1-0.7 A/dm* (l-7.5 A/ft*)
The formulas above will produce dull, chalk-white deposits that are very soft (less than
100 Knoop). Additions of grain refiners or brighteners will modify deposits causing them to
become lustrous to fully bright.
Examples of these additives are certain organic compounds, which usually contain sulfur
in their molecule, and complexed forms of a group VA or VIA element such as selenium,
bismuth, or antimony. Deposits become harder as brightness increases; the usual hardness
range will be between 100 and 200 Knoop. Antimony and selenium will produce harder
deposits than most organic compounds, although the latter generally have better electrical
properties.
Carbonate is an oxidation product of cyanide, so additions are not needed after the initial
solution makeup. This oxidation occurs slowly even when the solution is not in use, and when
the potassium carbonate concentration has reached 120 g/L (16 oz/gal) deposits can become
dull or rough. Removal of carbonate can be accomplished by freezing-out or precipitation with
calcium or barium salts.
Silver is a relatively noble metal, and as such will form immersion deposits on the
surfaces of less noble metals that are immersed in its solution. This tends to happen even when
the base metal enters the silver solution “hot” or “live,” that is, with a voltage already
290
applied. The inevitable result of this phenomenon is poor adhesion of subsequent deposits. To
minimize this effect, it is essential to employ a silver strike coating prior to the main deposit.
A typical silver strike would be as follows:
Silver as KAg(CN), 3.5-5 g/L (0.5-0.7 ozfgal)
Potassium cyanide (free), St&100 g/L (IO-13 o&al)
Potassium carbonate (min), 15 g/L (2 ozfgal)
Temperature, 15-25°C (60-SOoF)
Current density, 0.5-1.0 A/dm* (S-10 A/ft*)
It is not necessary to rinse between such a strike and a cyanide-based silver-plating
solution. Silver strike thickness is tvuicallv 0.05-0.25 urn (0.000002-0.000010 in.).
Anode purity is of paramount*importance since typical impurities, such as copper, iron,
bismuth, lead, antimony, sulfur, selenium, tellurium, and platinum-group metals will cause
solution contamination and may lead to anode filming, which inhibits proper dissolution of the
silver. Silver anodes are produced by rolling, casting, or extruding the metal. Care should be
taken to ensure adequate annealing has taken place after fabrication. The object of annealing
is to obtain correct grain size so that the anodes do not shed during dissolution. (Shedding
means that small particles break away from the anode, and these can cause roughness in the
silver deposit.)
Insufficient concentration of free cyanide and insufficient anode area will cause anodes to
shed or dissolve improperly. Cyanide concentration should be analyzed regularly and additions
of potassium cyanide made as needed. Optimum anode to cathode area ratio is 2: 1; a maximum
anode current density of 1.25 A/dm2 (13.5 A/ft2) is recommended.
HIGH-SPEED SELECTIVE PLATING
Electronic components such as lead frames are usually plated with silver using selective
methods. Silicon chips and aluminum wires can be bonded to the silver by employing
ultrasonic or thermosonic bonding techniques. Silver thickness ranges 1.875 to 5.0. pm
(0.000075~.000200 in.), with deoosition times between 1 and 4 sec.
The small areas to. be plated demand the use of insoluble anodes. Platinized-titanium
mesh and platinum wire are examples of anode materials in common use. Traditional cyanide
silver electrolytes suffer rapid degradation under these conditions, oxidation and polymeriza
tion of the cyanide at the inert anodes being the principal cause. Special solutions were
developed to overcome this situation; these contain essentially no free cyanide but still depend
on potassium silver cyanide as the source of silver. A typical formula is as follows:
Silver as KAg(CN), 40-75 g/L (S-10 oz/gal)
Conducting/buffering salts, 60-120 g/L (S-16 oz/gal)
pH, 8.G9.5
Temperature, 60-7O’C (140-l 60°F)
Current density, 3G380 A/dm* (300-3.500 A/ft*)
Agitation, Jet plating
Anodes, Pt or PtfTi
Conducting salts can be orthophosphates, which are self-buffering, or nitrates, which
require additional buffering from borates or similar compounds. Buffering is important in these
solutions since there is a significant drop in pH at the inert anode during plating due to
destruction of hydroxide ions. Insoluble silver cyanide forms on the anode surface as a result
of cyanide depletion in this locally low pH. Plating current drops off rapidly due to
polarization. The following equations summarize the reactions involved.
40H- + 2H,O + 0 + 4e-
Ag(CN)-, + AgCNj + CN-
292
Other additives include grain refiners, for example, selenium, and anti-immersion
agents. The latter inhibit chemical deposition onto unplated areas of the lead frames. They
are usually based on a mercaptan or similar compound, which will attach itself to the active
base metal surface.
NONCYANIDE SYSTEMS
Many compounds of silver have been investigated as potential metal sources for a
noncyanide plating process. Several authors have subdivided these studies into three groups by
compound type. These groups are (1) simple salts, e.g., nitrate, fluoborate, fluosilicate; (2)
inorganic complexes, e.g., iodide, tbiocyanate, thiosulfate, pyrophosphate. trimetaphosphate;
and (3) organic complexes, e.g., succinimide. lactate, thiourea. The simple salts all appear to
suffer from the same problem: light sensitivity of the materials. Although some smooth
deposits have been obtained from such systems, they are not viable under normal production
conditions.
Of the inorganic complexes considered, three are worth discussing further. These are the
iodide, trimetaphosphate, and thiosulfate solutions.
Iodide Solutions
Several authors report some success with baths that are quite similar. A typical solution
might be as follows:
Silver iodide, 20-45 g/L (2.5-6.0 oz/gal)
Potassium iodide, 300-6CXl g/L (40-80 oz/gal)
HI or HCI, 5-I5 & (0.7-Z ozlgal)
Gelatin (optional), 1-4 giL (0.15-0.55 oz/gal)
Temperature, 25-6O’C (SO-14O”P)
Current density, 0.1-15 A/dm* (1.0-150 A/ft*)
Without exception these authors found iodine in deposits from their particular formula.
This fact, and the relatively high price of the iodide salts, has prevented further use of this type
of solution.
Trimetaphosphate Solution
A process was developed for silver plating magnesium and its alloys; its use on other
metals is not reported.
Silver trimetaphosphate (monobasic), Ag,HPsO,, 345 g/L (0.40-0.60 oz/gal)
Sodium trimetaphosphate (trimer), Na,sP,O,s. 100-160 g/L (13.5-21.5 oz/gal)
Tetrasodium pyrophosphate, Na4P20,, 50-175 g/L (6.7-23.5 o&gal)
Tetrasodium EDTA, 3545 g/L (4.7-6.0 oz/gal)
Sodium fluoride, 3-5 g/L (0.40-0.70 oz/gal)
pH (adjust with triethanolamine or sodium bicarbonate), 7.9-9.5
Temperature, 50-6O’C (120-140°F)
Current density, 0.5-2.5 A/dm2 (5-25 A/ft*)
Thiosulfate Solutions
Thiosulfate-based formulas have proven to be the most successful of any inorganic
complex investigated. Early attempts to plate silver from such a solution resulted in rapid
oxidation of the complex and precipitation of insoluble silver compounds. Additions of sodium
metabisulfite were found to minimize this tendency, and all thiosulfate-based processes now
294
contain this ingredient.
Solution composition can be expressed:
Silver as thiosulfate, 30 g/L (4.0 al/gal)
Sodium thiosulfate, 300-500 g/L (40-70 oz/gal)
Sodium metabisultite, 30-50 g/L (406.7 oz/gal)
pH (adjust with sodium bisulfite or hydroxide), S-10
Temperature, 15-3O’C (60-85“F)
Current density, 0.4-1.0 A/dm2 (4-10 A/ft2)
These electrolytes can be operated with stainless steel or silver anodes; however, the latter
should be bagged.
Problems of poor adhesion can be overcome by using a conventional silver strike or one
in which there is no free cyanide. In either case, rinsing before entry into the thiosulfate
solution is a good practice. A small amount of cyanide drag-in will react with thiosulfate in the
solution to form thiocyanate:
CN- + S20,-2 -+ CNS- + SO,-2
One reported advantage of thiosulfate over cyanide systems is that thickness distribution
is better on complex-shaped objects. However, deposits seem to tarnish in air much quicker
than cyanide-produced ones. Postplating passivation is recommended.
Succinimide Solutions
Several electrolytes based on this organic complex of silver have been patented, two of
which are described below:
Silver as potassium silver disuccinimide, 30 g/L (4.0 oz/gal)
Succinimide. 11.5-55 g/L (1.5-7.4 oz/gal)
Potassium sulfate, 45 g/L (6.0 oz/gal)
pH, 8.5
Temperature, 25°C (77’P)
Current density, 1 A/dm2 (I 0 A/ft2)
Potassium nitrite or nitrate can be substituted for the sulfate and the addition of amines,
such as ethylene diamine or diethylenetriamine, and wetting agents produce bright, stress-free
deposits.
Silver as potassium silver disuccinimide, 24 g/L (3.3 odgal)
Succinimide, 25 g/L (3.4 oz/gal)
Potassium citrate, 50 g/L (6.7 ox/gal)
pH, 7.5-9.0
Temperature, 20-70°C (70-160°F)
Current density, 0.54 A/dm2 (5.5 A/ft2)
Potassium borate may be used in place of potassium citrate.
Tarnish resistance of deposits obtained from these processes is inferior to that of deposits
produced from cyanide electrolytes.
Organic Solvent Solutions
Nonaqueous solvents enable investigation of silver plating from salts that are insoluble in
water. One such system, based on dimethylformamide (DMF), is illustrated below:
Silver chloride, 10 g/L (1.3 ozfgal)
Thiourea, 30 g/L (4.0 oz/gal)
Aluminum chloride, 10 g/L (I .3 ozfgal)
Solvent dimethylformamide, balance
296
Room temperature
Current density, cl.5 A/dm2 (~15 A/ft2)
Milky white silver deposits were obtained from a small volume of this solution over an
extended time period; however, some scale-up problems are inevitable with such a system.
SUMMARY
After more than 150 years, silver plating is still performed using a cyanide electrolyte that
resembles the electrode in the original 1840 patent. Most of the work directed at replacing
cyanide in silver plating has resulted in little more than technical interest. As yet, no
production-proven, noncyanide alternative has been found, although systems based on
thiosulfate and succinimide appear to offer some promise. Both of these systems are
commercially available.
Standards and Guidelines for Electroplated Plastics,
Fourth Edition
by The American Society for Electroplated Plastics
163 pages $60.00
This technical guide has been updated to reflect the latest changes in rhe technology
for electroplating on plastics. It consists of ten chapters covering such topics as the
properties of plateable plastics, part design, mold design, racking, electroless
plating, electroplating, automated processing equipment, and test procedures. A
concise but thorough coverage of the subject.
Send Orders to:
METAL FINISHING
Three University Plaza For faster service, call (201) 487-3700
Hackensack, NJ 0760 1 or FAX your order to (201) 487-3705
All baok orders musr be prepaid. NY, NJ and MA residents add appropriate sales tax. Plea= include SS.00
shipping and handling for delivery of each book via UPS to addresses in the U.S.; $8.00 for each book for Ail
Parcel Post shipment 10 Canada; and $20.00 for each book for Air Parcel Post shipment IO all other countrin
297
