SILVER AND SILVER ALLOYS

Vol 22

SILVER AND SILVER ALLOYS

Silver [7440-22-4], Ag (at no. 47), is a white, lustrous, soft, malleable metal having the highest known electrical and thermal conductivities. It is the most highly reflective
of all the metals in the visible spectrum and second only to gold in the long-wave infrared. Along with its colorful neighbors copper and gold in the Periodic Table
Group II (IB) metals, silver occurs naturally in metallic form and thus was among the earliest metals used by humans. Silver is widely used for jewelry, tableware,
holloware, and coinage. Its advantageous chemical and physical properties find extensive application in photography (qv), electrical and electronic components (see
ELECTRICAL CONNECTORS; ELECTRONIC MATERIALS), solders and brazing alloys (qv), catalysts, clinical treatment, mirrors, high performance journal bearings, and
sanitation.

Properties
Some properties of silver are summarized in Table 1. The solar energy transmittance and neutron-absorption characteristics of silver are shown in Figures 1 and 2,
respectively. Thermal properties are given in Table 2. Other properties are given in References 1,3, and 4.

Table 1. Properties of Silver

Parameter
atomic mass, amu
a
melting point , C
electron structure
b
isotopic abundance , %
106.9051
108.9048
atomic diameter, pm
ionic radius, pm
crystal structure
lattice spacing, a0, at 20C, pm

Value
107.8682
961.93
[Kr] 4d10 5s1
51.84
48.16
2883
126

Reference
1
1
1
1
1
1

fcc, Fm3m
0.4078 nm

1
1

ionization potentials, eV
Ag ! Ag + + e
Ag + ! Ag 2+ + e
Ag 2+ ! Ag 3+ + e

electrochemical potential , V
density, at 20C, g/cm3
annealed
hard drawn
at 0 K
boiling point, C
e
recrystallization temperature , C
f
tensile strength, 5-mm dia wire, MPa
annealed at 600C
50% cold worked
elongation, 5-mm dia wire, % in 5.08 cm
at 20C, annealed at 600C
50% cold worked

7.574
21.960
36.10
0.798

1
1
1
1

10.492
10.43
10.63
2187
20200

1
3
1
4

125186
290

3
3

4350
35

0:00422 108
1:467 108
2:875 108
8:415 108
17:30 108

6
6
6
6
6

106
104
102

1
101
102
2530

7
7
7
7
7
7
5

131.5
97.33
51.1

1
1
1

91.3
26.929.7

1
5

0.364

electrical resistivity , , /m
20 K
273.15 K (=0 C )
500 K
1235.08 K, solid
h
1235.08 K, liquid
i
vapor pressure, Pa
684C
828C
1028C
1330C
1543C
1825C
j
hardness, Brinell, kg/mm2
k
elastic constants, 0C, GPa
C11
C12
C44
l

elastic properties
k
Young's modulus at 20C, GPa
k
modulus of rigidity at 20C, GPa
Poisson's ratio, at 293 K
annealed

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SILVER AND SILVER ALLOYS

hard drawn
viscosity, molten, at 1043C, mPas(=cP)
thermal neutron capture cross section, m2
Fermi energy, eV
Fermi surface, spherical
work function, electrons
thermionic, eV
photoelectric, eV
a

Electron volts, 1 eV = 1:602 1019 J .

For the equation, Ag + + e ! Ag.

necks at < 111 >

3.094.31
3.674.81

4
4

To convert MPa to psi, multiply by 145.

Total electrical resistivity of 99.999% pure or purer bulk silver. Impurities increase resistivity.

5.52

4
8
1
1

Depends on amount of dissolved oxygen and trace elements in solid solution in silver, plus cold work.

63 1028

See also Ref. 2.

0.39
3.697

A partial pressure of 20 kPa (2.9 psi) O2 results in a freezing point of ca 950C.

Vol 22

Liquid 99.95% pure or purer.

To convert Pa to mm Hg, multiply by 0.0075.

At 20C, annealed at 600C.
To convert GPa to psi, multiply by 145,000.
1 Pascal = 10 dyne=cm 2 = 1:45 104 lbf=in:2 .

Fig. 1. Solar energy transmittance through glass and glass having sputtered silver coatings, where A corresponds to clear float glass; B, to LoE, one layer of sputtered
silver in stack of oxides (prevents tarnishing and eliminates internal reflections) deposited on one interior surface of two layers of glass (an inert gas (argon) is placed
between panes); C, to LoE1, same as B except silver and oxide layer thicknesses selected to provide lower solar energy minimum transmission; and D, LoE2, similar to
B except that two separated layers of sputtered silver located in stack of oxides (9). Courtesy of Cardinal IG.

Fig. 2. Total neutron cross sections of silver (

) and cadmium ( { { { ) (10). To convert pm2 to barns, multiply by 104 .

Table 2. Thermal Properties of Silver

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SILVER AND SILVER ALLOYS

Vol 22

Parameter
a
thermal conductivity at 0C, W=(mK)
linear coefficient of thermal expansion,

Value
418.7

Reference
3

m=(mK)

av 0100C
at 500C
b
specific heat, mean, J=(kgK)
solid at 0C
at 100C
at 527C
at 961C
liquid at 9612227C
b
latent heat of fusion, J/g
b
latent heat of vaporization, kJ/g
bc
heat capacity, Cp, at 0800C, J=(g C) ,
thermal electromotive force vs NBS Pt 27 (NBS Standard), mV
at 100C
300C
500C
700C
a
b
c

19:68 106
20:61 106

234
238
282
297
310
104.2
2.636

3
3
3
3
3
4

Cp = 0:2320 + 0:06035 104 t 0:67896 108 t2

+0:76
+3:20
+6:50
+10:80

5
5
5
5

1 W=(mK) = 2:39 103 cal=(scm C) = 0:578 (Btuin.)=(hft 2 F) .

To convert J to cal, divide by 4.184.

Temperature, t, in C.

In the electromotive force series of the elements, silver is less noble than only Pd, Hg, Pt, and Au. All provide high corrosion resistance. Silver cannot form
oxides under ambient conditions. Its highly reactive character, however, results in the formation of black sulfides on exposure to sulfur-containing atmospheres.
Silver has the highest (97%) visual light reflection and is second only to gold in its reflectance of long-wave infrared radiation (Ag 92%, Au 97%). Transparent
coatings of silver sputtered onto window glass, ie, low E-glass, are the most reflective coatings for thermal insulating windows (see Fig. 1).
Laser stimulation of a silver surface results in a reflected signal over a million times stronger than that of other metals. Called laser-enhanced Raman
spectroscopy, this procedure is useful in catalysis. The large neutron cross section of silver (see Fig. 2), makes this element useful as a thermal neutron flux monitor for
reactor surveillance programs (see NUCLEAR REACTORS).
The fatigue resistance of silver in bearings is superior to that of all other materials, which accounts for its use in diesel locomotive crankshafts (see BEARING
MATERIALS). A flash leadtin overplating is applied to trap or collect particles that would otherwise score the hard surface of silver. Silver is widely used to prevent galling
in bearings, acting as a dry film lubricant owing to its tendency toward interplanar shear. Silver is also widely used to prevent seizing of bearings experiencing long idle
periods. On start-up, the low shear strength of silver permits instant response.
Oxidation States. The common oxidation state of silver is +1, ie, Ag + , as found in AgCl, which is used with Mg in sea- or freshwater-activated batteries
(qv); AgNO3, the initial material for photographic materials, medical compounds, catalysts, etc; and silver oxide, Ag2O, an electrode in batteries (see SILVER COMPOUNDS).
Few Ag 2+ compounds are known. The aqua ion [Ag(H 2 O)4 ]2+ , which has one unpaired electron, is obtained from an HClO4 or HNO3 solution by oxidation of Ag +
with ozone or by dissolution of AgO in acid. The potentials for the Ag 2+ =Ag + couple, +2:00 V in 4 M HClO4 and +1:93 in 4 M HNO3, show that Ag 2+ is a powerful
oxidizing agent.
Silver in the +3 oxidation state, including silver peroxide, ie, black oxide, marketed as AgO, is obtained by the action of the vigorous oxidizing agent S2O28 on
Ag2O or other Ag compounds. X-ray and neutron diffraction analyses show the nominal AgO unit cell to be Ag2OAg2O3. Both Ag+ and Ag3+ are present. Another
compound of potentially important commercial value is Ag4O4, which has a unit cell of two Ag + and two Ag 3+ ions. Its preparation is as follows:
4 AgNO 3 + 2 Na 2 S 2 O 8 + 8 NaOH ! Ag 4 O 4 + 4 Na 2 SO 4 + 4 NaNO 3 + 4 H 2 O
Tetrasilver tetroxide is a powerful oxidizer for sanitizing swimming pools, hot tubs, and industrial cooling system waters (see WATER, TREATMENT OF SWIMMING
This oxide is slightly soluble and its dissociation into silver ions is enhanced by the addition of the oxidizer K2S2O8. Bivalent and trivalent silver
disinfectants have been shown to be from 50 to 200 times more effective as sanitizers than monovalent silver compounds.
Trivalent complexes of biguanide and periodate are also prepared commercially for water sanitation. The trivalent silver periodate, for example, is prepared by
the action of potassium periodate and potassium hydroxide on Ag4O4:

POOLS, SPAS, AND HOT TUBS).

Ag 4 O 4 + 6 KOH + 4 KIO 4 ! 2 K 5 H 2 [Ag(IO 6 ) 2 ] + Ag 2 O + H 2 O

Oxygen Reactivity. Silver is second only to gold as the element having the weakest interaction with oxygen, providing silver with its superior sparking and
combustion resistance. Silver must be oxidized chemically or electrolytically to form Ag2O. Thermodynamically, silver exists only in the metallic state above 200C.
Solid silver is more permeable by oxygen than any other metal. Oxygen moves freely within the metallic silver lattice, not leaving the surface until two oxygen
atoms connect to form O2. This occurs at 300 C . Below this temperature silver is an efficient catalyst for gaseous oxidative chemical reactions. Silver is also an
extremely efficient catalyst for aqueous oxidative sanitation.
Oxygen migrates through silver in the atomic state, its rate of diffusion increasing with rising temperature. An instrument using this effect provides a stream of
pure atomic oxygen in vacuo through a ca 0.25-m silver membrane, operating at ca 350450C with oxygen pressure behind the membrane. A flux of low energy
electrons is aimed at the membrane to strike off the atoms of oxygen as they reach the outer surface of the silver.
Molten silver dissolves nearly 10 times its own volume of oxygen, ie, 0.32 wt % above its melting point, and ejects much but not all of the 2 violently as it
solidifies. There appears to be no lower temperature limit at which oxygen does not dissolve in silver.
Ordinary silver bullion processed in air may contain ca 200 ppm oxygen. Commercial silver bullion prepared under nitrogen may contain as little as 25 ppm
oxygen. During casting some oxygen may be introduced to convert base metal impurities into oxides. Because these oxides do not enter into the solid solution, they
have no effect on the annealing and recrystallization temperature of the silver critical to the silversmith.
Ignition Suppression. The formation of the weak silver oxide produces such little heat (14 J/g (3.3 cal/g)) that silver does not sustain combustion even
when ignited. Thus silver finds important use as a spark suppressor in oxygen-rich systems such as in the space shuttle, where solid silver parts are used in the high

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SILVER AND SILVER ALLOYS

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pressure liquid oxygen pumps and wherever sparks might be generated by rubbing or friction.
Catalysis. The mechanism of hydrogen abstraction from alcohols to form aldehydes (qv) over silver has been elucidated (11). Silver is the principal catalyst
for the production of formaldehyde (qv), the U.S. production of which was 4 106 metric tons in 1993. The catalytic oxidation of ethylene (qv) to ethylene oxide (qv)
is unique to silver. The U.S. production of ethylene oxide was 2:9 106 metric tons in 1993. Silver is an effective oxidative catalyst because it breaks oxygen molecules
into atoms, adsorbing those atoms lightly on the surface and providing sites for the oxidation of oncoming chemical compounds or bacteria. The silver itself remains
chemically inactive.
Sanitation. The power of silver to inactivate bacteria was confirmed in 1893. The exact biological mechanism(s), however, remain to be clearly identified.
Considerable research demonstrates the effective sanitation of swimming pools, hot tubs, and cooling towers by electrically generated silver and copper ions (12). When
silver is plated on alumina particles in an aqueous medium, the very weak (ca 2934 J/mol (78 kcal/mol)) bond silver forms with oxygen results in powerful oxidation
power providing a 99% bacteria kill in a single pass and a 100% kill in ozone-charged water.
Hydrogen and Nitrogen. Silver dissolves about 0.02 mL of hydrogen per mL of Ag0 at 600C, and 0.05 mL at 900C. Nitrogen, insoluble in silver, is a
suitable atmosphere for casting and melting silver to avoid oxygen absorption.
Dissolution of Silver. Silver is dissolved by oxidizing acids and alkali metal cyanide solutions in the presence of oxygen. The latter method is the principal
technique for dissolving silver from ore. Silver has extensive solubility in mercury (qv) and low melting metals such as sodium, potassium, and their mixtures. Cyanide
solutions of silver are used for electroplating and electroforming. The silver is deposited at the cathode either as pure crystals or as layers on a mandrel.
A dissolution reaction with KCN is as follows:
4 Ag + 8 KCN + O 2 + 2 H 2 O ! 4 KAg(CN) 2 + 4 KOH
Nitric acid dissolves silver at all concentrations. This is the principal chemical reaction for the dissolution of silver into the soluble nitrate, which is the chemical
intermediate for the production of electroplated ware, catalysts, battery plates, pharmaceuticals, mirrors, and silver halides for photographic materials. Nitric acid
removes silver from the residual pellet in the gold fire assay.
Tarnish. No passivation treatment to prevent silver from tarnishing exists. Sulfides in the atmosphere react to form Ag2S. The rate of tarnishing increases
with the proportion of copper in the alloy, the latter forming a black Cu2S deposit. Increasing humidity hastens tarnish formation. As the tarnish film thickens, the rate
of tarnish formation is reduced. Tarnishing can be reduced in storage by the use of sulfur-free paper or paper impregnated with copper or cadmium acetate which
preferentially absorbs H2S.
A list of a wide variety of compounds and their reaction with silver is available (13).

Occurrence
The American cordillera extending from Alaska to Bolivia has been the most productive source of silver wherever it is associated with Tertiary age intrusive volcanic
rocks, mostly concentrated by hydrothermal action. The largest producing mine in the cordillera is at Potosi, Bolivia, where the total silver output since the 1500s is
estimated at over 31,000 metric tons.
Mexico, the world's leading producer of silver since the Spanish conquest, obtains virtually its entire silver production from leadzinc mines in the central
cordillera. Mexico retained its dominance in silver production until the discovery of the Comstock Lode in Nevada in 1859. Discoveries in Colorado, Arizona, and
Montana placed the United States as the world's top silver producer from 1871 until 1900. As these mines played out, Mexico's vast resources returned it to its former
position of dominance.
The most important body of primary silver ore in the United States in the 1990s is located in Silver Valley, the Coeur d'Alene Mining District of Shoshone
County, Idaho, which produces >200 t=yr of silver. The main ore mineral is tetrahedrite [12054-35-2], associated with sulfides of lead, copper, iron, and zinc.
In the Commonwealth of Independent States (CIS, formerly the USSR), nearly 50% of the CIS production comes from Kazakhstan. Silver is produced from the
leadzinc mines at Ostkamen, Shymkent, and Leninogorsk (ca 1000 t) and also in Russia's Far East, where it is a by-product of the tin deposits near Khabarovsk, and of
the copper and gold deposits in the Ural Mountains.
Canada's most productive district is in the Canadian shield at Cobalt, Ontario. Nearly 97% of the silver values in this pre-Cambrian age ore were found as great
slabs of nearly pure silver. One slab was 474 kg. The huge open-pit Kidd Creek Mine has had an annual output of over 80 t of silver.
Some 60 silver minerals are known. The most important economically are argentite [1332-04-3], Ag2S; cerargyrite [14358-96-4], AgCl; polybasite [53810-31-4],
Ag16Sb2S11; proustite [15152-58-4], Ag3AsS3; pyrargyrite [15123-77-0], Ag3SbS3; stephanite [1302-12-1], Ag5SbS4; tetrahedrite, Cu3(AsSb)S3; and the tellurides. Silver is
commonly associated with gold (see GOLD AND GOLD COMPOUNDS), copper (qv), lead (qv), and zinc (see ZINC AND ZINC ALLOYS) ores.
Resources. World resources of silver are estimated to be about half a million tons. However, only about 250,000 metric tons are considered economically
recoverable reserves. These are associated with ores of copper, gold, lead, and zinc, and extraction depends on the economic recovery of those metals. Canada and the
CIS vie for the greatest reserves of silver in the ground.

Mining and Processing

Silver utensils dating to ca 3000 BC attest to the antiquity of silver production. By ca 1000 BC the argentiferous lead ores at Mount Laurium, Greece, were smelted, ie,
melted in a furnace, and followed by cupellation, ie, blowing air across the pool of metal to oxidize the base metals into slag. An estimated 8000 t of silver produced
from the mines at Laurium greatly contributed to the wealth of Athens. Studies of Greenland ice and lake sediments throughout northern Europe show lead levels
hundreds of times higher than natural, beginning ca 500 BC. This serves as evidence of early large-scale silver smelting by the Greeks and Romans.
The discovery of aqua regia by the Arab alchemist Jabir Ibn Hayyan (AD 720813) provided a new extraction technology. Amalgamation of silver in ores with
mercury was extensively used during the late fifteenth century by the Spaniards in Mexico and Bolivia. In 1861 the complex ores of the Comstock Lode, Nevada, were
ground together with mercury, salt, copper sulfate, and sulfuric acid, and then steam-heated to recover the silver.
The chlorination process, introduced in Europe in 1843, roasted ore with chlorides, followed by a hot brine leach and subsequent precipitation of the silver on
copper. In 1887 it was discovered that gold and silver can be recovered by sodium cyanide, and this process displaced the dangerous chlorination process. By 1907 the
cyanide process, where a cyanide solution is mixed with zinc dust to precipitate the silver, was universally in use.
In the 1980s, zinc precipitation was replaced by a method involving the passing of the solution over activated carbon to adsorb the precious metals, which are
then stripped from the charcoal by a hot caustic solution. Electrowinning removes the precious metals from this solution, depositing them on the cathode. One benefit
of this process is that the filtration or deareation steps of the zinc precipitation are not required. Thus the environmental hazard of the zinc salts is eliminated.
Heap leaching, ie, spraying of sodium cyanide solution over roughly crushed ores heaped on an impervious pad, has become the most economical way of
recovering precious metal values from very low grade ores. Recoveries are lower, however, ca 70%, for heap leaching; ca 85% for milling and cyanidization.

Production and Consumption

Mine Production of Silver. World production of silver by region is given in Table 3. Some 900,000 metric tons are estimated to have been mined since
early times. By the year 1500 world mine production was about 50 t/yr. In 1992 world production exceeded 14,900 metric tons. Following the breakup of the Soviet
Union, previously undisclosed data showed that the USSR led world silver production during 19791980 at about 1550 metric tons. During the early 1990s the

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production in this region exceeded 2000 t/yr.

Table 3. Silver Mine Production,

a,b

Region
Africa
Asia
Europe
North America
Central and South America
Oceania
c
CIS
d
Total
a
b
c
d

1985

1990

496
678
1,762
4,573
2,618
1,088
1,960
13,312

1994

570
524
1,728
5,858
3,118
1,182
2,239
15,992

564
597
1,594
4,443
3,168
1,077
1,499
13,817

Ref. 14.
To convert metric tons to millions of troy ounces, divide by 31.1.
Formerly USSR.
Includes China and North Korea.

U.S. silver production from 1985 to 1994 averaged 1588 t/yr. Less than one quarter of this output comes from silver mine districts, however. About half is as
by-product of gold mines; about one quarter comes from copper and leadzinc mines. The silver production in Mexico from 1985 to 1994 averaged 2256 t/yr, and
Peru, at the southern extremity of the cordillera, where silver is a by-product of copper and leadzinc mines, averaged 1810 t/yr.
Consumption. World consumption of silver in 1994, including the use of scrap, was about 23,300 t. Industrial and decorative uses consumed 8,690 t;
jewelry and silverware, 6,477 t; photography, 6,820 t; and official coins, 1,335 t.
The demand for silver is an indicator of technically advanced products production. In 1950, when the population in the free-market countries was 1.7 billion,
consumption of silver was 2.9 t/106 people. By 1992, the population had increased to 4.2 billion and silver consumption reached 4.2 t/106 people. Fabrication demand
by country is given in Table 4 and by category in Table 5.
ab

Table 4. Fabrication Demand by Country, t ,

Country
United States
Belgium
Canada
France
Germany
Hong Kong
India
Italy
Japan
Mexico
the Netherlands
Peru
South Korea
Thailand
Taiwan
United Kingdom and Ireland
a
b

1985
3,704
510
292
597
1,060
100
759
2,258
292
31

607

1990
3,982
597
186
765
1,681
100
1,315
1,426
3,601
478
86
46
212
750
140
801

1994
4,190
629
70
873
1,616
90
2,834
1,496
3,353
921
96
28
496
905
160
1,043

Ref. 14.
Includes scrap.

Table 5. U.S. Fabrication Demand of Silver, t

Product category
photography
electrical contacts and conductors
batteries
catalysts
sterlingware
jewelry
silverplate
mirrors
miscellaneous
coinage
Total
a

1985
1801
855
78
75
109
180
115
31
448
12
3704

1990
2084
709
93
93
109
62
87
37
425
283
3982

1994
2109
650
106
124
200
165
93
44
444
255
4190

Refs. 14 and 15.

Secondary Silver Recovery. The consumption of silver normally exceeds its mine production; therefore recovery from scrapped products, such as

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electrical gear, coins, and photographic film and solutions, is critical to its supply. In 1994, the silver gleaned from scrap throughout the world was estimated to exceed
4100 t. The overwhelming proportion of this was from photographic material (see RECYCLING, NONFERROUS METALS) (16).

Standards and Specifications

Commodity exchanges require good delivery silver bullion to be 999 parts per 1000 fine silver. Samples of specifications for silver are given in Table 6. Specifications
for silver bullion, brazing alloys, electrical contact alloys, etc, are published by ASTM, the American Welding Society, Japanese Industrial Standards, SAE (Aerospace
Materials Specifications), and the U.S. Department of Defense.

Table 6. Specifications for Silver and Silver Alloys, Wt %

Grade

Designation
Grade 99.90 Re-fined silver

ASTM B413
d
MIL-S-13282b

Grade A silver
f

SAE/UNS P07931 ,
a
b
c
d
e
f
g

sterling silver, silversmith's

grade

Ag
99.90
99.95
92.1093.50

Ag + Cu

99.95
99.98
g

6.507.90

Fe
0.002
0.005

Pb
0.025
0.025

0.05

0.03

Other
Bi 0.001, Cu 0.08
Bi 0.001, Cu 0.10, Se
0.001, Te 0.001
Ca 0.05, Zn 0.06, all
others 0.06

Value is minimum.
Value is maximum.
Ref. 17.
Ref. 18.
For anodes.
Ref. 19.
Cu only.

Assaying and Analysis

The fire assay, the antecedents of which date to ancient Egypt, remains the most reliable method for the accurate quantitative determination of precious metals in any
mixture for concentrations from 5 ppm to 100%. A sample is folded into silver-free lead foil cones, which are placed in bone-ash cupels (cups) and heated to between
1000 and 1200C to oxidize the nonnoble metals. The oxides are then absorbed into a bone-ash cupel (ca 99%) and a shiny, uniformly metallic-colored bead remains.
The bead is brushed clean, rolled flat, and treated with CP grade nitric acid to dissolve the silver. The presence of trace metals in that solution is then determined by
instrumental techniques and the purity of the silver determined by difference.
Chemical analysis methods may be used for assay of silver alloys containing no interfering base metals. Nitric acid dissolution of the silver and precipitation as
AgCl, or the Gay-Lussac-Volhard titration methods are used interchangeably for the higher concentrations of silver. These procedures have been described (4).
Instrumental methods for quantitative determination of silver purity include (1) atomic absorption, which is the fractional decrease in intensity of radiation per
number of atoms per unit area. It is fast, accurate, and economical. Silver detection is highly sensitive and this analysis is widely used for ores and concentrates down to
ca 23% silver. (2) Emission spectroscopy and (3) mass spectrometry (qv) are used to quantitatively assay trace elements in high purity silver. The purity of the silver is
found by subtracting the proportion of the trace elements present. The use of ms assay is a necessity for electronics applications, where 999.99 or five nines fine silver
or better is required. (4) The inductively coupled plasma technique functions on the same principle as emission spectroscopy, but uses solutions put through an
8,00010,000 K plasma of argon. The growing popularity of this method is based on the fast, simple analysis. The usual interpretation of photographic plates is avoided
(see PLASMA TECHNOLOGY). Lastly (5), x-ray fluorescence is simple, rapid, and accurate. This technique leads to identification of elements by their characteristic x-ray
emission. The composition of the sample is obtained by converting the x-ray intensities into metal concentrations. However, each type of sample must be individually
calibrated.

Health and Safety Factors

Silver is one of the very few antimicrobial agents for which epidemiological data extend over millennia of use. Silver metal dissolves in water to the extent of 5 parts per
billion (ppb), making the water sufficiently toxic to kill such organisms as E. coli and B. typhosus. Silver blocks growth of E. coli cells as a result of both surface binding
and intracellular uptake. On the surface of a bacterium, and on fish gills, silver blocks transmission of oxygen, leading to expiration. Silver is not toxic to humans
because it does not react with mammalian cells, and the blood brain barrier blocks the silver from nerve cells of the brain and spinal column, where it would exhibit
toxicity.
The U.S. Environmental Protection Agency, under the Safe Drinking Water Act, set the secondary contaminant level for silver in drinking water at 0.1 mg/L
(20). Secondary contaminants are not considered to be hazardous to health and thus the limits are not federally enforceable.

Silver Alloys
The atomic radius of silver (144 pm) is within about 15% of many elements, permitting solid solutions with Al, Au, Be, Bi, Cu, Cd, Ge, In, Mn, Pb, Pd, Pt, Sb, Sn, Th,
and Zn. These metals form useful brazing, jewelry, and soldering alloys. Copper is the only metal with which silver forms a simple eutectic between two solid solutions
(Fig. 3). Silver has extremely limited solubility in B, C, Co, Cr, Fe, Ge, Ir, Ni, Mg, Mo, Se, Si, Te, Ti, and W. Thus these metals may be brazed by silver alloys without
serious erosion during welding (qv).

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Fig. 3. Silvercopper phase diagram.

Silver's advantageous physical, chemical, electrical, and thermal conductive properties are used in a variety of alloys. For example, (1) a 3.5% Ag, 0.5% Zr copper
alloy provides a high strength, thermally conductive, fatigue-resistant liner of the hottest portion of the space shuttle engine main combustion chamber (see ABLATIVE
MATERIALS). (2) The oldest standard silver jewelry alloy is sterling, 92.5% Ag, 7.5% Cu, which, when heated and rapidly quenched, results in a soft, highly workable,
ductile alloy. Annealing results in extended wear life for silver coins and tableware.
Brazes and Solders. Silver imparts high tensile strength, ductility, thermal conductivity, bactericidal properties, and unusual wettability to most metals for
soldering and brazing alloys. Some 1200 t of silver are used worldwide annually for this application. Alloys of Pb, Sb, and Sn provide low temperature solders
(143320C); Au and Ge provide brazes melting at ca 525C; Cd, Cu, Mn, Ni, P, Sn, and Zn provide high temperature brazes (660970C). A highly ductile 92% Ag,
4% Ti, 1% In alloy provides strong ceramic-to-ceramic joints at 1000C. A 65% Sn, 25% Ag, and 10% Sn alloy provides unique wetting and resistance to thermal
fatigue properties that are critical for the bonding of silicon chips to metallic substrates.

Uses
Coinage. As a store of value, silver metal has been traded since prehistoric times. About 700 BC, trade silver was issued in the form of coins. Because silver is
soft, the coin silver alloy (90 Ag, 10 Cu) was adopted in the United States in 1837 and also by other national governments. Following World War II, burgeoning
industrial demand consumed much of mine production, and with the inflation of national currencies, the decreasing monetary value of silver coins to below that of
their bullion value brought an end to circulating silver coinage. Coinage consumption of silver as of the 1990s is split between commemorative coins, made from
sterling and coin silver alloys, and bullion coins, made of pure silver, such as the Mexican Onza and the U.S. Eagle.
Photography. The introduction into photographic techniques of tabular silver halide crystals in 1983 markedly improved the efficiency of silver halides for
capturing light, decreasing light scattering, and allowing greater adsorption of sensitizing dyes, extending the film's sensitivity to 1400 nm in the infrared. In the best
fine-grain color negative film, a 35-mm frame contains some 25 million image elements. The best digital electronic system contains about two million image elements.
The reaction of light with halides is one of reduction. The silver ion is reduced to silver, and the halogen atoms react with the emulsion, making the process irreversible
(see PHOTOGRAPHY).
Photochromic glass used for sunglasses contains silver, copper, and halogen salts. Sunlight reduces the silver ion to a silver atom, darkening the glass. The
released halogen atoms are trapped by the copper, and on removal of sunlight are recovered by the silver, restoring the glass to colorlessness, a readily reversible
process. The silver crystallites block up to 97% of harmful uv rays.
Electrical Contacts. Silver combines the highest electrical and thermal conductivity and freedom from corrosion with low price. Its high resistance to
arcing and mechanical wear may be increased by combining it with other materials such as graphite and cadmium oxide, which have superior nonsticking and
nonwelding properties, and tin and indium oxides. The low power membrane switch consists of pure silver surfaces on the inside surfaces of two opposing sealed Mylar
sheets that make an electrical contact. This switch finds universal use under the keys of millions of computer keyboards and control panels. Above 800 A, contacts are
made of silver infiltrated into a tungsten matrix to avoid arc welding. On annealing, sputtered silver contacts can provide a resistivity of 109 cm 2 . These are useful
for high temperature superconductor switching. Tarnish has little effect on silver contacts because the film, though dark, is soft and easily wiped off a contact when a
toggle switch is activated.
Silver Thick Films. About half of the silver consumed in the United States for its electrical properties is used by the electronics industry. Of this amount
some 40% is used for the preparation of thick-film pastes in circuit paths and capacitors. These are silk-screened onto ceramic or plastic circuit boards for multilayer
circuit sandwich components.
Electroplating. The use of silver for plating tableware and decorative objects in the United States exceeds 100 t/yr. Silver is normally plated using
potassium cyanide solutions, which exhibit the highest plating current densities. The advent of computer-monitored electroplating has allowed consistent production
line plating of goldsilver alloys.
Electroless Plating. The historic three-part mirror silvering system of AgNO3 and ammonia (to retard precipitation of the silver), a solution of NaOH,
and a reducing solution of invert sugar (later formaldehyde) (ca 1835), has been replaced by a two-solution silvering system of NaOH and ammoniacal AgNO3, mixed
with a glucose solution containing an amine group. This allows electroless plating of mirrors at lower temperatures with better adhesion. Both require glass pretreated
with SnCl2. The new system lends itself to automated production of video compact disks, ornaments, thermos bottles, bottle caps, etc. About 40 t/yr of silver are used
in the United States for manufacturing mirrors.
Magnetron Sputtered Reflective Coatings. Silver atoms sputtered in vacuo onto glass and polyester films entered the domestic window market in 1979
and are primary contenders for energy savings. The invisible silver coatings on ordinary double-pane windows where argon is used as the insulating gas can approach a
96% reflectivity in the long infrared (see Fig. 1). Multilayer polyester films have achieved an R-value of 10.
Sputtered silver mirrors are used for solar energy (qv) collectors and astronomical telescope mirrors. Approximately 3 t/yr of silver are used in the United States

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

SILVER AND SILVER ALLOYS

Vol 22

for low emissivity windows.

Dental Amalgam. Silvermercury dental amalgams have been universally used since the late 1830s. These have proven to be the most successful tooth
filling materials in terms of both bactericidal and physical properties. This includes the ability to be pressed into tooth cavity irregularities and then to expand slightly on
solidification to provide a firm fit. The silver alloys incorporated in the amalgam have varied widely in composition: Ag 2570 wt %, Cu 030 wt %, Sn 030 wt %, and
Zn 01 wt %. The mercury-to-alloy ratio has ranged from 4354% (see DENTAL MATERIALS).
In 1993 the National Institute of Standards and Technology (NIST) announced a mercury-free, silver-coated tin filling material. The silver-coated tin particles are
stripped of oxygen and stored in an oxygen-inhibiting solution until they are packed into the tooth cavity. When this solution is expelled during packing in the cavity by
the dentist, the particles are freed to cold-weld, forming a true metallurgical bond.
Other Uses.

Bearings. Silver is plated in all main-shaft bearings of jet engines because the silver provides a low coefficient of friction and superior fatigue and corrosion
resistance, and has sufficient lubricity to serve as an emergency lubricant in case of oil failure.
Giant Magnetoresistance. Silver and cobalt, although mutually insoluble, may be ground together and fused to exhibit giant magnetoresistance when a
magnetic field is applied. Resistance changes as great as 50% are observed. The Co-rich precipitates in an Ag-rich matrix find use in magnetic-tape read heads, sensing
magnetism devices, etc (see MAGNETIC MATERIALS ).

Economic Aspects
New York Commodity Market (COMEX) prices from 1982 to 1993 are given in Table 7. The economic aspects of silver have been reviewed (14).
a

Table 7. Spot Settlement Price for Silver , $= kg

Year
1982
1985
1990
1994
a

High
363.30
221.51
172.01
185.83

Low
154.64
176.19
126.67
146.93

Average
254.95
197.41
154.97
169.76

Ref. 21.

BIBLIOGRAPHY
"Silver and Silver Alloys" in ECT 1st ed., Vol. 12, pp. 426438, by E. H. Konrad and F. A. Meier (Analysis), The American Platinum Works; in ECT 2nd ed., Vol. 18,
pp. 279294, by C. D. Coxe, Handy & Harman; in ECT 3rd ed., Vol. 21, pp. 115, by G. H. Sistare, Consultant.
1.
D. R. Smith and F. R. Fickett, J. Res. Nat. Inst. Stds. Technol. , (100), 119171 (1995).
2.
D. Strominger, J. M. Hollander, and G. T. Seaborg, Rev. Mod. Phys. 30, 585 (1958).
3.
B. A. Rogers and co-workers, Silver: Its Properties and Industrial Uses, NBS Circular C412, U.S. Government Printing Office, Washington, D.C., 1936.
4.
A. Butts, Silver Economics, Metallurgy, and Use, Van Nostrand Reinhold Co., Inc., New York, 1967. A comprehensive study of silver.
5.
Technical Bulletin, Vol. 10, No. 3, Engelhard Industries, Iselin, N.J., 1970, p. 80. Data on silver.
6.
R. A. Matula, J. Phys. Chem. Ref. Data 8, 4 (1979). American Institute of Physics resistivity tables.
7.
N. Nesmayanov, Vapor Pressure of the Elements, Academic Press, Inc., New York, 1963.
8.
D. J. Hughes and R. B. Schwartz, Neutron Cross Section, USAEC report BNL-325, U.S. Atomic Energy Commission, Washington, D.C., 1958.
9.
Glass Products for Windows and Doors, Cardinal IG, Minnetonka, Minn., 1994, p. 21.
10.
E. Bleuler and G. J. Goldsmith, Experimental Nucleonics, Holt, Reinhart and Winston, Inc., New York, 1952.
11.
H. K. Plummer, Jr., W. L. H. Watkins, and H. S. Gandhi, Appl. Catal. 29, 261283 (1987).
12.
C. P. Gerba and R. B. Thurman, CRC Crit. Rev. Environ. Control 18(4), 295 (1989).
13.
L. Addicks, Silver in Industry, Reinhold Publishing Co., New York, 1940, pp. 368393.
14.
World Silver Survey, 1995, The Silver Institute, Washington, D.C.
15.
World Silver Survey, 1994, The Silver Institute, Washington, D.C.
16.
P. Krause, 1992 World Silver Survey, The Silver Institute, Washington, D.C., p. 73.
17.
Book of Standards, Vol. 2.04, American Society for Testing and Materials, Philadelphia, Pa., 1995.
18.
Silver and Silver Alloys, MIL-S-13282 B, Naval Publications Center, U.S. Department of Defense, Philadelphia, Pa., 1964.
19.
Unified Numbering System, SAE/HS 1086a, SAE, Inc., Warrendale, Pa.
20.
Fed. Reg. 56, 1471 (Jan. 14, 1991).
21.
COMEX, New York, 1995.
General References
World Silver Survey, The Silver Institute, Washington, D.C., 1992, 1995.
T. P. Mohide, Silver, Ontario Ministry of Mineral Resources, Toronto, Canada, 1985.
Mineral Facts and Problems, U.S. Bureau of Mines, Washington, D.C., 1965.
I. E. Wachs and R. J. Madix, Surface Sci. 76, 531 (1978).
M. S. Antleman, in IPMI Proceedings, International Precious Metals Institute, Allentown, Pa., 1992, p. 141.
R. J. Araujo, Contemp. Phys. 21(1), 77 (1980).
M. J. Carey and co-workers, Appl. Phys. Lett. 61(24), 14 (Dec. 1992).
J. W. Ekin and co-workers, Appl. Phys. Lett. 52(4), 331 (1988).
J. G. Hust and A. F. Clark, Cryogenics, 13(6), 325 (June 1973).
J. A. Eisele, A. F. Colombo, and G. E. McClelland, Separ. Sci. Technol. 18(12,13), 19081 (1983).
C. L. Fox and B. W. Rappole, Surg. Gynecol. Obstet. 128, 1021 (May 1969).
The Fire Assay for Gold, The Gold Institute, Washington, D.C., 1985.
C. F. Heinig, Jr., Ozone Sci. Eng., 533546 (Dec. 1993).

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SILVER AND SILVER ALLOYS

Vol 22

F. Habashi, CIM Bull. 80, 108 (Sept. 1987).

C. F. Key, J. G. Austin, and J. W. Bransford, Flammability of Materials in Gaseous Oxygen Environments, NASA TMX-64783, National Aeronautics and Space
Administration, Washington, D.C., Sept. 1973.
Technology Assessment Conference Statement on Effects and Side Effects of Dental Restorative Materials , National Institute of Dental Research, NIH, Bethesda, Md., Aug. 2629,
1991.
M. L. Malhotra and K. Asgar, J. Am. Dental Assn. (96), 444 (Mar. 1978).
R. A. Outlaw and M. R. Davidson, Vacuum Sci. Tech. A (12), 854 (MayJune 1994).
K. W. Nageli, Schweiz. Naturf. Ges. 33, 174 (1893).
Personal communication, D. H. Corrigan, VP, Handy & Harman, Oct. 1994.
Personal communication, P. Krause, President (ret.) Ilford Corp., June 1994.
R. M. Levine, World Silver Survey, The Silver Institute, Washington, D.C., 1994, p. 117.

Samuel F. Etris
The Silver Institute

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)