Chapter-2

Silver Electroplating

2.1 Introduction

Silver was first plated at the beginning of the nineteenth century [1]. However,
the earliest patent for silver plating was granted to Elkington [2] • in 1840 and this
signaled the start of the electroplating industry. That bath is basically the one used in
silver plating today, that is, the double silver cyanide with excess free cyanide. Many
other baths have been proposed such as nitrate [3], iodide [4], thiourea [5],
thiocyanate [6], sulfamate [7], and thiosulfate [8]. A recent review summarizing
cyanide-free formulations [9] states that none of the baths listed has been accepted by
industry in preference to the common cyanide solution. A proprietary iodide bath has
been offered publicly.

Early usage of silver plating was for its decorative effect and for a suitable
deposit for tableware and hollow ware, in which cases its resistance to foods, and so
on (with the exception of those of high sulfur content) was the important
consideration. Within the past 40 years, several industrial uses have arisen. Such uses
are for bearings, where silver provides a surface resistant to galling at low loads, for
electronic circuit components, for slip rings, waveguides, and hot gas seals.
Improvements in the plating of silver have historically revolved around bright
deposits by the addition to a conventional bath of brightener and surfactant, and
changes in the amount of free cyanide and silver for increasing plating speed.

2.2 BATH FORMULATIONS

The composition of silver cyanide plating solutions will vary with the type of silver
plate required. Decorative silver is usually plated from baths with lower silver content
than those used for engineering applications where thicker deposits are required. The
higher silver concentrations allow the use of higher current densities and thus more
economic plating speeds. Typical bath compositions are shown in Table 1.
 Silver cyanide forms a complex double cyanide with alkali metal cyanides,
KAg(CN)2. Thus, 1 g of AgCN requires about 0.5 g KCN in addition to the free
cyanide shown in Table 1. The bath is also commonly prepared by dissolving the
calculated amount of potassium cyanide in about half the final volume of deionized
water. After complete dissolution the silver cyanide is added slowly with constant
stirring to form the complex. Other required salts are then added and the solution
brought to operating volume with deionized water. The solution is then filtered,
preferably through activated carbon, before the addition of brighteners. Although
most large volume silver solutions are prepared in this fashion, many baths are
prepared with the readily available potassium silver cyanide. In this case, the bath
ingredients, other than the KAg(CN)2 and brighteners, are dissolved in a spare tank in
water equal to half the final bath volume. This solution is heated to 70°C and
activated carbon in the amount of 1.2 g/1 of bath is added. Stir 1 hr and filter into the
operating tank, make up almost to volume, then add the potassium silver cyanide
directly to the tank with stirring. With this procedure no silver is removed by the
carbon. Finally, add brighteners if desired and dilute to volume.

TABLE 1. TYPICAL BATH COMPOSITIONS

Conventional or Bright High-Speed Silver for

Silver Thicker Deposits
Silver (as metal) 20-45 35-115
Silver cyanide 31-56 44-153
Potassium cyanide (total) 50-78 68-235
Free potassium cyanide 35-50 45-160
Potassium carbonate 15-90 15-90
Potassium nitrate ---- 40-60
Potassium hydroxide ---- 4-30
Current density,
A/dm2 (with agitation) 0.5-1.5 0.5-10.0 0.5-1.5 0.5-10.0
Temperature, °C 20-28 38-50
Brighteners As required As required
Alkali silver cyanide provides the silver necessary for the deposition of silver on the
cathode. The mechanism of silver deposition is moot, but from a practical standpoint,
low silver content and high free cyanide favor improved throwing power, and higher
concentrations permit the use of higher current densities. Consequently, baths low in
silver contents are generally used for 2- to 5- µm deposits. The alkali cyanide
increases the conductivity (Table 2) [10] and the cathode polarization, contributes to
good anode corrosion, and, of course, serves to form the silver complex ion.
Potassium cyanide is used rather than sodium cyanide because of higher solution
conductivity, higher solubility of the resultant potassium carbonate buildup, and
higher limiting current densities provided. The potassium cyanide baths also offer a
wider operating bright range.

Potassium carbonate adds to the conductivity of the bath and increases anode
and cathode polarizations, which aids in increased throwing power. The
recommended minimum concentration is added initially and the concentration
gradually increases through decomposition of the cyanide. In regular production
practice the concentration of potassium carbonate may rise to 110 g/1 without adverse
effects. Higher concentrations may cause coarse, rough deposits. When the plating
process is properly engineered the carbonate content usually levels off within the
recommended operating range.

Potassium nitrate has been recommended for high-speed plating baths [11].
Additions of 40 to 60 g/1 are said to aid in anode corrosion at higher current densities
and lower free cyanide content.

Hydroxides have been used for promoting anode corrosion for high-speed
plating [11] and stabilizing the bath against cyanide decomposition [12].

Chlorides, formates, acetates, phosphates, borates, and sulfates have been

reported to increase the hardness of the silver as deposited. This was explained as
associated with the use of a carbon disulfide brightener [10].

Addition agents are generally added to the silver bath to produce fine-grained,
smooth deposits and, in the case of decorative silver, mirror-bright deposits. Details of
these additions are discussed separately in the sections on decorative and engineering
applications.
2.3 OPERATING CONDITIONS

The conventional silver plating baths are generally operated at room temperature (21-
27°C) and at current densities of 0.5 to 1.5 A/dm2. Agitation is usually supplied by
cathode-rod motion augmented by solution circulation by means of a pump or
mechanical mixers.

Higher operating temperatures and vigorous agitation are required for

TABLE 2.

THE EFFECT OF INCREASING CONCENTRATION OF ADDED INGREDIENTS

ON THE RESISTIVITY OF A CYANIDE SILVER PLATING SOLUTION

Effect of Potassium Effect of Sodium Cyanide Effect of Potassium Nitrate

Carhimate
Concentration Resistivity Concentration Resistivity Concentration Resistivity
g/1 ohm/cm3 g/1 ohm/cm3 g/1 ohm/cm3
12.9 9.6 7.5 14
75 6.2 30 11 75 9
130 5.0 45 9 120 6.6

high-speed silver plating. Current densities as high as 10 A/dm2 can be used with a
high silver content in a solution operated at 50°C. The limiting current density
depends mainly on the degree of solution flow past the cathode. In other words, under
the recommended plating conditions for high-speed plating, the limiting current
density will depend on the capabilities of the agitation system.

The average silver plating installation includes equipment for continuous or

intermittent solution filtration with arrangements for treatment with activated carbon.
Periodic filtration is required of all silver plating baths, coupled with carbon treatment
when it becomes necessary to remove harmful organic impurities. High-speed baths
for plating bearings, and so on, should be filtered continuously.
2.4MAINTENANCE AND CONTROL

Cyanide silver plating solutions are relatively easy to maintain and control. Anode
and cathode current efficiencies are essentially 100% under normal operating
conditions and, therefore, the solution remains in balance for long periods with
respect to metallic content. Small amounts of impurities of less noble metals present
no serious problem because the silver plates out preferentially. However, as with all
plating baths, good housekeeping habits should be observed to prevent heavy metallic
or organic contamination. The introduction of iron in large amounts through the use of
steel anodes or dragin from the strike solutions can cause off-color granular deposits
and interfere with bright plating solutions. Iron can be removed by cooling the
solution to 3°C and filtering off the precipitated ferrocyanide [13].

Solution control is based on routine chemical analysis and appearance of the

plate. Standard analytical procedures [14-16] are used for control of silver, free
cyanide, carbonate, hydroxide, and nitrates if present. Frequency of analysis depends
on the work schedules and can be determined only by experience. Carbonate
formation [17], cyanide decomposition [18], dragin from strike solutions, and dragout
from the plating bath are the main causes for change in composition.

Sodium carbonate in excess of 60 g/1 can be removed by cooling the solution

to 3°C. Potassium carbonate, which is used in most silver electroplating installations,
cannot be removed by freezing out because of its high solubility. The carbonate can
be precipitated by the addition of calcium nitrate, or calcium or barium hydroxide. For
solutions containing nitrate or hydroxide the use of calcium compounds is most
economical. One gram of potassium carbonate will be removed by about 1.2 g of
calcium nitrate or 0.5 g of calcium hydroxide. Barium cyanide is more generally
suitable becausethe soluble end product is potassium cyanide. One gram of potassium
carbonate will be precipitated by 1.4 g of barium cyanide. However, the high cost of
this chemical has limited its use. Filtration following this treatment is mandatory. The
effect of added nitrate, hydroxide, or cyanide resulting from these reactions must be
taken into consideration. Moreover, if the carbonate is high, no attempt to reduce it
drastically should' be made because the barium or calcium carbonate is voluminous
and difficult to filter out.
 The main cause of roughness of electrodeposited silver under normal
operating conditons is the presence of suspended solid particles in the plating bath.
Periodic or continuous filtration is essential for this reason. Continuous filtration is
especially valuable in high-speed plating of thick deposits. Care must be exercised to
avoid the introduction of air through the filtering system because of its undesirable
effect in promoting pitting of the silver plate. Occasional treatment with activated
carbon may be necessary to remove harmful organic contaminants. Brighteners
removed by the carbon are replaced after the treatment.

Brighteners can be controlled by Hull cell tests under the direction of an

experienced operator or as recommended by suppliers of proprietary brightener
additives.

2.5ANODES

Silver anodes are usually supplied with a purity of 99.97% or higher. Two grades of
anode silver are generally available, a regular grade and a high-quality grade. For the
best plating results the high-quality-grade anodes should be used. These anodes are
made from selected melts and are recommended by the anode suppliers for optimum
performance in the plating bath. Impurities in silver anodes can cause the formation of
black film and flaking which result in plate roughness. Anodes are supplied in the
form of bar, balls, shot, and special shapes, as required.

Development of films and blackening of silver anodes sometimes occur in

plating solutions. Assuming that high-quality silver anodes are used, the "black
anodes" can be caused by low free cyanide in the plating bath, too low pH, a high
anode current density, high iron content, or the presence of sulfur compounds or
impurities such as organic decomposition products from brighteners in the bath [19].
The ratio of anode to cathode area should not be less than 1-1 to avoid films due to
anode polarization. The addition of nitrate and hydroxide to high-speed plating baths
aids in preventing "black anodes" due to high-current-density conditions.

The use of high-quality anodes is important not only to prevent black film
formation due to anode impurities but also to avoid flaking or shedding ofanode
particles into the solution during dissolution. The first indication of flaking may be the
appearance of roughness on the work caused by adherence of fine silver particles. An
investigation of the cause of particle separation [20, 21] has contributed to the
production of high-quality anodes. In critical conditions it is common practice to bag
the anodes or anode assemblies (steel baskets containing silver balls or chips) with
woven synthetic fabrics such as polypropylene, polyethylene, or other alkali-resist-ant
materials. All fabric coverings should be free of sizing that will cause contamination
of the solution. Fabric suppliers should be informed of the solution temperature and
brighteners used. The weave of the fabric should not restrict solution flow to cause
anode polarization. The fabric selected should be approved by the vendor of bright
plating solutions.

2.6 MATERIALS OF CONSTRUCTION

Plating equipment is generally the same as that used in other cyanide plating
systems. Steel tanks should be lined with rubber, neoprene, or plastics inert to highly
alkaline solutions. The supplier of new equipment (tanks, or pumps and filter systems)
should be apprised of the bath composition, temperature, and brighteners that will be
used. Rigid polyvinyl chloride (PVC), polypropylene, and reinforced polyester tanks
are frequently used.

Unlined steel or stainless steel tanks are unsatisfactory for the silver plating
solutions because of the possibility of stray currents which may lead to nonuniform
current distribution and plating of nonadherent silver deposits on the tank wall that
may become a source of roughness on the plated part.

Anode hooks and rack contacts should be stainless steel. Standard coated racks
recommended by the supplier are satisfactory. Stainless steel or plastic lined filter
systems are generally employed.

2.7PREPARATION OF BASIS METAL

The preliminary treatments of cleaning and etching of any metal before silver
plating follow standard procedures, except that a silver strike is required. Because
most basis metals are less noble than silver (including gold in the cyanide system),
they will precipitate silver by immersion from the regular silver plating baths and
result in poorly adherent deposits. The strike baths contain low metal concentration
and high free cyanide. This composition lowers the tendency for electrochemical
displacement by the basis metal and provides a low-efficiency hydrogen activation
process. The established procedure for steel is to use a double strike, first in a
solutioncontaining a lower silver content and some copper cyanide, and second in a
conventional strike solution. The second strike solution is also used as the first strike
bath for copper and copper alloys, nickel or nickel-silver, etc.

1. Strike bath No. 1 for steel

Silver cyanide 1.5-2.5 g/1
Copper cyanide 10-15 g/1
Potassium cyanide 75-90 g/1
Temperature 22-30°C
Current density 1.5-2.0 A/dm2
Voltage 4-6

2. Strike for nickel and nonferrous metals, also second strike for steel
Silver cyanide 1.5-5 g/1
Potassium cyanide 75-90 g/1
Temperature 22-30°C
Current density 1.5-2.0 A/dm2

The strike also serves to cover work made up of more than one metal, such as
soldered parts and assemblies. The required time is 8 to 25 sec for bright decorative
silver plating, and 15 to 35 sec for thicker deposits.

As an added precaution to prevent loss of adhesion due to electrochemical

displacement, the work is made cathodic before immersion it the strike and plating
solutions. On automatic plating lines where this procedure is not practical, use the
strike sequence for steel for all metals. When there is little danger of dragin from a
contaminated strike solution, the rinse between the strike and plating solution can be
omitted.

A recommended practice for plating adherent thick deposits of silver on steel is

reviewed in the engineering section of this chapter, as are special practices for
decorative work.
2.8DECORATIVE SILVER PLATING

Most of the decorative silver plating applications concern electroplating small

household items, such as hollow ware, flatware, jewelry, and the like. Because of the
variety of such items, the types of basis metal may be diverse and often the item to be
plated is a combination of two or three metals joined by solder.

Replating silvered items is even more of a chore, because usually the silver is
stripped and then repairs are made, often with several solder compositions. For items
having basis metals of copper, high or low brass, lead alloys, or Britannia metal (high
tin alloy), plus solder, the initial soakcleaner should be a relatively low pH alkaline
cleaner formulated for removal of buffing soils. Time of such soaking may be up to
10 min, if required, but shorter times are preferable. This is followed by a mild
cathodic electrolytic alkaline cleaner at 2.0 to 2.5 A/dm2, after which comes an acid
dip in hydrochloric (10%), fluoboric (10%) for lead alloy and soldered items, or a
proprietary acid solution. Following these operations a thin strike of either copper or
nickel is recommended to obtain the coverage on solder seams or lead alloy parts. If
the alloy is high in tin, use a nickel fluoborate strike. The parts are now given a silver
strike in the following bath:

Free potassium cyanide 75-90 g/1

Silver 1.25 g/1

The strike should be operated at or slightly below room temperature, at 1 to 2

A/dm2 and for 20 sec. Silver plate immediately after striking. The best baths for this
type of plating are the proprietary bright ones at 0.5 to 1 A/dm2. Since silver plating is
approximately 100% efficient, the time required to obtain a thickness of 5 pm at 1
A/dm2 is 7 min 24 sec or 37 min for 25 pm. The proprietary bright baths minimize the
buffing of the final plate, which not only saves metal but also assures a more uniform
thickness on finished items. Rinsing following plating should provide for dragout
recovery. Some proprietary plating baths leave a water-break surface after plating.
This may increase water spotting in the final drying step, so many platers use a film
breakdown step in the rinse line or return to the soak cleaner, and acid dip before the
final rinsing. The preparation of nickel-brass (nickel-silver used for flatware) is done
in a manner similar to that described previously, except that more alkaline soak
cleaners and elctrolytic cleaners are used. A nickel strike is optional, but a Wood's
nickel strike followed by a brief Watts plate will assure adhesion. For very heavy
silver on leaded nickel-brass a fluoborate nickel strike has made it possible to
eliminate a pimpling effect which occurred using an antimony-hardened bright silver.

Brass is handled much the same as nickel-brass flatware, except that the silver
deposit is normally only about 5 pm. Consequently, it is common to plate 5- to 15µm
of a leveling bright nickel before the silver plate.

Preparation of steel is described thoroughly in the section on engineering

applications. Stainless steel represents a special case, where the first plating step
should be a Wood's nickel strike of at least 3-min duration at 4 to 6 A/dm2, except
when the silver deposit is thin. When the silver deposit is only 2 to 3 pm, the
possibility of pores can accelerate corrosion when a more base metal undercoat, such
as nickel, is interposed. In such cases, a strike in a highly acid (pH 2.1) gold bath is
recommended. The platiiig of beryllium copper requires proper surface preparation
and adouble silver strike. The composition of the second strike should be

Free potassium cyanide 70 g/1

Silver 2.5 g/1

Conventional solutions containing a carbon disulfide or thiosulfate brightener

are used for plating flatware. These baths should be operated at 1.5 to 2.0 A/dm2.
Since the surface may be oxidized before final finishing and flatware can be buffed
easily (liquid, greaseless), high brightness is not required. Special plating applications
may dictate the use of high-speed solutions with thiosulfate brightener and an elevated
temperature (32-37°C).

For many years, until the 1950s, two brightening agents were widely used in
silver plating. Carbon disulfide [22] in cyanide solutions was, and still is, used for
decorative baths. The other was thiosulfate which is still used in high-speed and
flatware baths. Neither brightener gives mirror-bright deposits, but the resulting plate
requires much less buffing. Excessive amounts of carbon disulfide brightener can
cause lowered throwing power, poor deposit distribution, black spots, pinholes, and
areas of no plate and even extreme roughness. Excess brightener can be removed by
an activated carbon treatment.
 Many addition agents have been proposed, such as gums [23], sugars,
unsaturated alcohols [24], and sulfonated aliphatic acids [25]. Most of these agents are
sulfur-bearing organic compounds or reaction products of sulfur and organic
compounds.

Fully bright silver plating on a consistent basis became possible with the
development of a ketone-carbon disulfide reaction product [26], a modification of
Weiner's [27] selenite [28, 29] bath, and the development of antimony polyalcohol
addition agents [30, 31]. Such full bright baths give mirror-bright deposits over a
reasonable current density range for decorative plating. Certain of these bright baths
are claimed to give better scratch resistance and thus' greater hardness. Use of all
should result in lowered postplating finishing costs, in most applications other than
flatware. The combination of full bright systems with accompanying bath characteris-
tics yields better deposit distribution, much better throwing power, and slightly less
tendency to tarnish. All mirror-bright solutions are proprietary, thus full information
should be obtained from the vendor. These solutions normally require a moderate
silver concentration and relatively high free cyanide. As is true of most other plating
solutions, failure to maintain sufficient anode area can produce conditions which will
cause these mirror-bright systems to fail. Good control is required.

There has been much discussion, especially in Europe, with respect to the
relation of hardness and resistance to wear. The alloy (Sb) hardened silverhas an
essentially permanent hardness, as high as 200 kg/mm2 (Vickers), while the selenite
and ketone-carbon disulfide silver deposits are in the 120-kg/mm2 range. Originally,
it was thought that the very hard deposits would wear longer, but this was not borne
‘out by tests, admittedly often confusing, because wearability, like solderability, is
difficult to measure. It is now pretty well agreed that very high hardnesses are
undesirable. However, it is claimed [32] that silver processes providing hardnesses of
130 to 150 kg/mm2 (Vickers) of the permanent type are preferable. The controversy
has not been particularly recognized by platers of flatware on this side of the Atlantic,
who generally use thiosulfate- or CS2-brightened baths at a higher current density
than employed for consistent full bright processes, but they do buff (often with liquid
compounds) and find the wearability as good as or better than that of antimony-
hardened silver deposits.
2.9SPECIFICATIONS FOR FLATWARE

General standards applying to the plating of flatware and hollow ware have
existed for many years. Flatware is generally specified with regard to the numer of
troy ounces of silver per gross (144) of teaspoons as follows:

Federal specification plate 280 g or 9 tr oz/gross

Quadruple plate 250 g or Ekr oz/gross

Triple plate 187 g or 6 tr oz/gross

Double plate 124 g or 4 tr oz/gross

Par plate 62 g or 2 tr oz/gross

Since the area of an average teaspoon is about 52 cm2, the thickness of

quadruple plate would be about 32 Am. Equivalent thicknesses are provided on the
other basic items of tableware (place fork, dessert or place spoon, knife, tablespoon).
The items getting occasional usage are generally given commensurately less silver.

In the case of hollow ware, the specifications for plating are less definitive.
They are generally as follows:

Federal specifications plate 32.5 mg/cm2 (20dwt/ft2)

Hotel plate 16.8-25.1 mg/cm2 (10-15 dwt/ft2)

Commercial plate 2.4-6.8 mg/cm2 (2-4 dwt/ft2)

In the plating of silver, the system of weights for the metal remains today that
of the troy scale of weights (a dwt is a pennyweight, or one-twentieth of a troy ounce).
Federal specification RR-T-451a covers in detail the standard thickness for the plating
of tableware and hollow ware.

2.9 BEARINGS AND RELATED INDUSTRIAL PRODUCTS

The excellent mechanical properties of silver, as reported by the National

Bureau of Standards [33], suggested its use as bearing material and led to the
development of high-speed plating of silver on steel-backed sleeve bearings. Since
this time silver has been widely used as an intermediate material for heavy-duty
bearings and to prevent galling or seizing of metal surfaces under light loads.
Antigalling applications include silverplated threads on stainless steel bolts, on
titanium compressor blades [34], and as a sealing medium for hot gas seals [35].
Aerospace material specification 2410E [36] covers this type of application.

Primary requirements of electroplated silver for heavy-duty bearing use are

adhesion, ductility, and soundness of deposits for thicknesses up to 1.5 mm. The
development of high-speed silver plating was directed toward these requirements by
Mathers and Gilbertson [37], who reported on the adhesion of thick silver deposits on
steel. Later investigations of Simon and Lumley [38] pointed to the use of vigorous
agitation for high-current-density silver plating. Further advancements were made
during World War II with the development of high-speed silver plating of aircraft
bearings [39-41].

The adhesion of silver to the steel backing for bearing use is of prime
importance. The preplate procedure recommended by Hart and Heussner [4] is as
follows: Degrease, anodic alkaline clean, anodic sulfuric acid etch, followed by an
activating 1.2 N hydrochloric acid dip. A nickel strike is interposed between the steel
and the conventional silver strike used before plating the silver deposit. The nickel
strike provides a higher degree of adhesion and greater reliability than plating silver
directly on steel. A low-pH (2.0-2.0) Watts-type nickel bath was recommended by
Schaefer [11] for this procedure.

When thick deposits of silver with mechanical strength are required for a
bearing material or electroforms, the rapid plating process becomes practical. Higher
plating speeds are made possible by increasing the agitation, raising the temperature,
adjusting the solution composition, and carefully controlling the symmetry between
anode and cathode. Filtration of the bath is important to prevent roughness caused by
dirt or anode particles adhering to the cathode. Continuous filtration and bagging of
anodes are mandatory if high-quality, thick deposits are to be produced.

Wide variations in solution compositions and operating conditions for high-

speed silver plating have been proposed. Typical compositions are as follows:

A[11] B[42]
Silver cyanide 45-50 g/1 75-
110 g/1

Potassium cyanide (free) 45-50 g/1 50-

90 g/1

Potassium hydroxide 10-14 g/I 0-

30 g/1

Potassium carbonate 45-80 g/1 15

g/1 (min)

Potassium nitrate 40-60 g/1

0

Brightener as required

Temperature, °C 42-45 38-49

The functions of the nitrate and hydroxide anions are not completely
understood. Both aid in anode corrosion and the hydroxide aids in stabilizing the bath
against cyanide decomposition [12].

Agitation and electrode positioning are usually determined empirically for a

practical plating rate of 5 to 10 A/dm2. Rapid agitation is accomplished by a
combination of cathode motion or rotation and pumping of solution past the cathode
surface. The elctrodeposition cell should be designed to maintain uniform agitation.
When moderate agitation and lower current densities (1.0-2.0 A/dm2) are used in the
presence of thiosulfate as the brightener, the solution temperature should be kept at
28°C maximum to avoid nodular roughness.

The brightener commonly used for these high-speed baths is ammonium

thiosulfate. The brightener gives the desired metallurgical properties with practical
solution control. Suggested rates of addition are 0.02 to 0.05 g/1 every 24 hr [11]. On
starting the bath after a shutdown period, 0.02 g/1 is added. Continuous or more
frequent additions may be beneficial. Potassium thiosulfate is preferred by Orr [43].

Silver plate for bearings or other antigalling use often requires a heat treatment
or anneal to meet hardness specifications or to improve adhesion. The problems
associated with the proper annealing procedure carry over to silver plate subjected to
high-temperature engineering applications. Oxygen rapidly diffuses through silver at
high temperatures and, in the case of silver plate, will oxidize the underlying metal,
causing blistering of the deposit. Typical heat-treating specifications over 204°C
require the heating and cooling medium to be a neutral or reducing atmosphere.

Federal specification QQ-S-365a (Amendment 2, February 24, 1967) requires

"copper-alloy-basis metal articles on which a nickel undercoat is not used and other
basis metals whereon a copper undercoat is employed should not be used for
continuous service in excess of 150°C. Adhesion of the silver plating is adversely
affected because diffusion forms a weak silver-copper eutectic at the basis metal-
coating interface."

When silver plate is used for low load bearing or antigalling surfaces, the
thickness required is usually 7.5 min or less. Deposits in this thickness rangeare plated
from conventional silver plating baths, since higher throwing power may be desired
and plating speed is not critical. Laboratory studies [44] have shown that
superimposing alternating current, or the periodic reversal of direct current, raises the
limiting current density of a highspeed bath operated at 20 to 25°C without the use of
agitation. Current densities as high as 1.5 A/dm2 can be used with improved plate
distribution while maintaining plate quality and structure.

Silver deposits 25 to 38 ism thick are used for pressure-activated hot gas seals
in rocket engine systems [35, 45]. The seals are fabricated from heat-treated INCO
718 alloy. The mating surfaces are Hastelloy C flanges. The seals operate at high
temperatures in an oxidizing atmosphere and the silver plate is permeable to oxygen.
The underlying metal is plated with 1.3 1.4m of gold after proper surface preparation
and then baked under vacuum to diffuse the gold into the basis metal before silver
plating. This diffused gold-INCO 718 interface resists oxidation and subsequent
blistering of the silver during high-temperature operation. After this diffusion layer is
formed and silver is plated, a heat treatment in an argon atmosphere is used to soften
the silver, producing optimum sealing properties and adhesion of the silver plate. An
overlay of 0.13 to 0.25µm of rhodium prevents sticking of the silver plated materials
to the mating Hastelloy C surfaces.
 An application of plating silver on an iron-nickel alloy for glass-to-metal seal
arrangement included a thin coating of indium over the silver plate to resist diffusion
of oxygen at high temperatures [46].

A unique four-step process for electroplating aluminum bus bar was

developed by Westinghouse Electric Corporation [47]. Ultrasonic irradia-tion was
used in the zincate immersion solution, as well as the silver plating solution. This
method resulted in a process that produced better adhesion and a silver coating equal
to or better than conventional processes. The effect of ultrasonic agitation, coupled
with a flowing solution in the cell, increased the limiting current density.

2.10 ELECTRICAL CONTACTS AND ELECTRONIC CIRCUITS

Silver plate has been and is used in the electrical and electronic industries
because of its outstanding electrical conductivity. The conductivity of the deposit will
vary according to the silver process employed. In ,eneral, the specific resistivity will
be in the range 0.017 to 0.024 ohm-mm /m (1.8-2.4 microhm-cm) as compared to
0.0162, 0.0178, and 0.029 for high-purity solid silver, copper, and aluminum,
respectively.

Krusenstjern and co-workers [48] report that sulfur- and selenium-con-taining

electrolytes yield deposits with 85 to 90% of the conductivity of pure silver.
Antimony-brightened deposits, however, have a conductivity of 10 to 25% that of
pure silver. A bath without addition agents gave specificconductivities of 0.0167 to
0.0196 ohm-mm2/m. Consequently, metallic brightening agents should be avoided for
high-conductivity applications.

Deposits 7.5 µ m thick are used on plug and socket contacts; thicker deposits
(500 m m or more) are used on slip rings and heavy-duty switch gear [49].

The major drawback of silver on contacts is its tendency to form sulfide films
which significantly increase contact resistance. For light-pressure, low-voltage
contacts, overlays of gold or rhodium are used [50, 51]. It has been reported [52] that
silver-plated contacts overplated with 4 Am of gold still had a large amount of
porosity. Harding [50] found that 10 /AM of gold was necessary over silver.
Consequently, there has been a strong trend not to use silver for the more sensitive
electronic circuit contacts, although Mil-G.45204-B, Amendment 2, still permits a
silver strike and underplate. The formation of sulfide films on heavy-duty switches is
less important because the heavy contact pressure and high voltage break through the
tarnish.

Silver plate is widely used in the production of waveguides for radar use
because radio frequency conductivity is directly related to electrical conductivity. The
use of periodic reverse (PR) current was proposed for this application when it was
shown that the conductivity of silver plated with PR current is higher than that plated
by conventional methods [53]. The bath used for PR plating of waveguides is a
moderate, high-speed formulation (40 g/1 silver cyanide, 40 g/1 potassium cyanide)
with 9-sec cathodic at 1.9 A/din2, 4-sec anodic at 1.2 A/dm2. This PR silver yielded
99% conductivity based on the International Annealed Copper Standard; direct
current yielded 94%. Brighteners that affect electrical resistivity should be avoided in
waveguide applications. The technique for plating these devices has been described
by Foster and Eddy [54].

Another reason for the use of silver for plating the complex forms encountered
in waveguide design is the relatively high throwing power of the silver cyanide
plating solution. Comparative throwing power values have been reviewed by Foulke
and Johnson [55]. Silver is not used extensively in the printed circuit industry because
of what is known as "silver migration." It has been shown that under a positive direct-
current potential within a damp resin component, silver will "migrate" across
insulating paths and, on drying, silver metal will be found in the body of the
insulation, producing low-resistant leakage paths [56]. Silver plating should not be
used when circuit boards are to meet Mil-Standard 275B or Mil-P-55110.

2.11 POSTPLATE TREATMENTS

The formation of tarnish films on silver, varying in color from light brown to
black, presents the most serious problem to the silver plating industry.Whereas silver
is practically unaffected by oxygen, it tarnishes readily in the presence of sulfur-
containing media. Since urban atmospheres normally contain traces of sulfur
compounds, protection from tarnish becomes very important for decorative and
electrical applications. Apart from the poor appearance, the sulfide film diminishes
the solderability and increases contact resistance of silver-plated electrical
components.
 Since the early days of silver plating many methods have been proposed for
the prevention of tarnishing, by the use of both alloying elements and surface
treatment. Alloying the silver with tin, indium, cadmium, or palladium has not been
successful because of change of color on aging, lower electrical conductivity, and
difficulty in obtaining uniform deposits. Surface treatments for retarding silver
tarnishing include deposition of more noble metals over the silver plate, passivation
treatments, and the application of clear waxes or lacquers. The organic coatings are
not suitable for electrical contacts or cutlery but find some use in decorative
applications. Care in the selection of these coatings is necessary to make sure there is
no yellowing with age. Overlays of gold or rhodium are commonly used to deter
silver sulfide formation. A rhodium plate 0.31 to 1.3 /AM thick has been used to a
large extent as a protective coating for jewelry and silver contacts. Gold overlays also
offer protection for silver-plated electrical contacts. However, Harding [50] reports
that many instances of tarnishing have occurred through pores in a 7- Am overlay of
gold. The creep of sulfide tarnish on gold-plated silver contacts has also been
discussed by Antler [51].

Thick overlays of gold, on the other hand, can be very useful. If, for example,
25 Am of a highly conductive corrosion-resistant metal is required, it would be more
economical to plate 15 Am of silver with an overlay of 10 Am of gold, than one 25-
Am layer of gold.

Chromate passivating treatments have been developed which are quite

effective in protecting silver plate from tarnishing [57, 58]. The best protection is
afforded by films which are developed with the aid of direct current or a galvanic
couple (Al—Ag or Ag—Zn). The work is made cathodic at about 2 A/dm2 or in
contact with aluminum or zinc for 1 to 5 min in the following solutions:

Potassium dichromate 25-50 g/l

Potassium carbonate 25-50 g/1

Potassium hydroxide 25-50 g/1

It is operated at 22 to 30°C using stainless steel anodes. Although corrosion of

the silver is not permanently prevented, a worthwhile improvement in tarnish
resistance is achieved with minimum effects on contact resistance and solderability.
However, when a low contact resistance is critical, tests should be carried out to
ascertain whether this treatment impairs electrical properties.

The packaging of silver-plated parts is very important for temporary

prevention of tarnish. Paper products in contact with the parts should be free of sulfur
compounds and, preferably, be impregnated with antitarnish chemicals. Transparent
plastic bags are especially suitable as a protective package.

An accelerated tarnish test has been used by Goldie [59] and Dettner [60] to
evaluate postplate treatments for silver. The test consists of immersion of the treated
sample in 2% potassium polysulfide solution at 20 to 25°C. A properly passivated
silver part must withstand a 15- to 30-min dip without breakdown of the passivated
surface. Dettner reviews the various methods of tarnish prevention and accelerated
tests. The Silver Institute reported a number of antitarnish methods [61], including the
use of mercaptans [62-65].

2.12 ANALYSIS AND TESTS

The Hull cell is used for brightness control .Often the amount of silver is
specified in terms of weight per piece. Large items are often weighed before and after
plating. Grab samples of a number of smaller pieces are stripped and the weight per
piece found by the weigh-strip-weigh method. For Britannia metal, make anodic in
sodium cyanide solution; for nickel-silver, brass, or copper, use a solution containing
19 parts sulfuric acid and one part nitric acid, both concentrated.

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