1992 Review of Extractive Metallurgy
Bismuth-Production, Properties,
and Applications
_ _ _ _ _ _ _ _ _ Funsho K. Ojebuoboh
Bismuth, the most metallic element in
group VA of the periodic table, is primarily
a by-product of lead refining. It is also a by-
product of several ore-dressing operations,
especially high-grade scheelite and wolframite
ores. It is generally recovered by processing
lead electrorefining slimes, Kroll-Betterton
dross, and other process residues which con-
tain bismuth. No matter the source, it is
refined to virgin metal with chlorine. Bis-
muth's unique properties make it attractive
for a plethora ofapplications such as alloying
additives in steel and aluminum, fusible al-
loys, and pharmaceuticals. Recent awareness
of the "green" nature of bismuth in free-
machining steels and similar applications
has made it a potential substitute for metals
deemed less favorable environmentally.
INTRODUCTION
Although the use of bismuth bronze
and bismuth-lead alloys was known in
the Middle Ages, l the occurrence of this
metal was recognized centuries earlier
because of the apparent use of bismuth
compounds as a remedy for stomach
discomfort, wounds, and sores. Bismuth
was first identified as a metal in the 15th
century, but it was more precisely char-
acterized in the 18th century by J. Pott
and T. Bergman.z Bismuth is a lustrous,
silvery white, heavy metal with a ten-
dency to crystallize in coarse grains. In
lead-bismuth alloys being refined for
bismuth recovery, the coarse grains of
bismuth start to appear at levels of -20
wt. % Bi. Despite the metallic appear-
ance, tinges of pink and red characterize
pure bismuth.
Estimates of its occurrence in the
Table I. Physical Properties of Blsmuth13
Property
Atomic Number
Crystal Structure
Stable Isotopes
Atomic Mass
Melting Point
Boiling Point
Heat of Fusion
Heat of Vaporation
Specific Heat (O°C to 270°C, mean)
Coefficient of Linear Expansion
Density at 20°C
Density at 271 °C (liquid)
Volume Expansion on Solidification
Thermal Conductivity at 20°C
Electrical Resistivity at O°C
Thermal Neutron Absorption Cross Section
46
-===========:=1
Earth's crust vary substantially, but av-
erage between 0.1 ppm and 0.2 ppm.
This is roughly the same level of abun-
dance as silver. Like some of the other
minor metals (e.g., arsenic, antimony,
selenium, and tellurium), bismuth is re-
covered from process residues in the
smelting and refining of the base met-
als-copper and lead.
In the periodic table, bismuth is lo-
cated in the boundary region between
metals and nonmetals. As expected from
the period it occupies, it has the stron-
gest metallic characteristics of its group,
but it is also characterized by a low
melting point (271°C). Its chemistry is
notable forseveral anomalous or extreme
properties:
• It expands on solidification. (This
behavior is carried over to some
bismuth alloys.)
• Its thermal conductivity is the lowest
of any metal in the solid state at
ambienttemperatures. (Its electrical
conductivity is also quite low for a
metal.)
• It is the most diamagnetic metal.
Tables I and II summarize various
material properties.
Bismuth is supplied commercially in
the form of 99.99% pure ingots, arsenic-
free needles primarily for pharmaceuti-
cal applications, and pellets for steel and
foundry applications. It may also be
supplied as bismuth-lead alloy ingots.
RAW
MATERIALS
Bismuth occurs naturally in the forms
of native bismuth, bismuthinite or bis-
Value
83
Rhombohedral
1
208.98
271°C
1,564°C
52.1Jig
728 Jig
0.0123 Jig
13.45 x 1(}-6;oC
9.8g/em>
10.07 g/em>
3.2%
8.368 W I(m · K)
106.81l1'l · em
0.034 ± 0.002 barnsl atoms
muth glance (B~S3)' bismite or bismuth
ocher(B~03),and bismutite [(BiO)zC03·
~Ol. These minerals seldom occur in
sufficient quantities to be mined eco-
nomically. Instead, bismuth glance oc-
curs in minor quantities with copper
and lead sulfides, and the others occur
with tin and tungsten oxides. Thus, bis-
muth is a classic example of a metal re-
covered primarily from process residues.
In recent times, bismuth ore has been
mined only in Bolivia, where bismuth
production was restarted in 1989. In the
rest of the Western world, bismuth is
produced as a by-product from the
treatment of copper and lead ores. The
practice appears to be similar in the
former Soviet Union, where bismuth is
also recovered from lead-refining resi-
dues. In the United States, the lead and
lead-zinc ores of the West (e.g., Montana)
are the primary domestic sources for
bismuth. Imports of bismuth bullion,
originating particularly from Peru and
Mexico, supplement domestically re-
fined bismuth.
An increasingly important source of
bismuth is in the mining of tungsten ores
in the People's Republic of China and
the Republic of Korea. Bismuth ore,
consisting of bismuthinite and its
weathering products, bismutite and na-
tive bismuth, is a by-product of the
tungsten mines in several deposits. Re-
covery methods include rough hand-
picking and standard ore-dressing pro-
cedures. The bismuth ores recovered in
some operations contain 60% bismuth,3
and more than one-half of China's out-
put is produced in the form of bismuth
concentrates.
Table III shows the major sources of
bismuth raw material and the specific
ores mined. The mineralogy of the as-
sociated bismuth is also identified.
EXTRACTION
While the primary processes in the
recovery of bismuth differ depending
on the minerals and the major metal
mined, the refining processes are in-
variably identical. Only a small portion,
perhaps 0.5%, of current world produc-
tion is available from mines worked spe-
cifically for bismuth ore. Table IV is a
survey of the processes available for
extracting the bismuth as bullion. When
bismuth concentrate, typically oxide or
JOM • June 1992
 carbonate as in Bolivia or China, is avail-
able, it is leached with hydrochloric acid.
Bismuth is precipitated as bismuth oxy-
chloride after repeated dissolution and
precipitation removes several soluble
impurities. The dried oxychloride is
smelted with carbon using soda ash flux
to produce crude bismuth bullion.
In the past, high-grade bismuth glance
was smelted directly to crude bullion
with iron in the so-called precipitation
process, and charcoal provided a re-
ducing atmosphere. Soda ash was also
the conventional fluxing agent in this
route. In recent times, the primary ex-
tractive processes for most of the mar-
ket-available bismuth are the electro-
refining process for lead (the Betts pro-
cess) and the pyrorefining process for
lead (the Kroll-Betterton process). The
choice of one process over the other de-
pends on the strategy for lead refining
rather than bismuth production.
Cominco (Canada), Centromin (formerly
Cerro de Pasco) in La Oroya, Peru, and
most Japanese lead refineries4 use the
Betts process. In contrast, Asarco-Omaha
(Nebraska), Metallurgie Hoboken Over-
pelt (Belgium), Broken Hill Associated
Smelters (Australia), Brunswick-
Belledune (Canada), and Mitsubishi-
Cominco (Japan) practice the Kroll-
Betterton process. Copper smelting and
refining residues containing bismuth are
transferred to a lead circuit by several of
these companies. The typical route is
shown in Figure 1.
The Betts Electrolytic Process
The Betts process is named after Dr.
Anson Betts, who developed it in 1901,5
It starts with lead bullion, which contains
copper, antimony, arsenic, selenium,
tellurium, silver, gold, and bismuth. The
lead bullion, which is substantially de-
tinned and which exceeds 90% pure lead,
is cast into anodes and electrolytically
refined in an electrolyte of lead fluo-
silicate (PbSiF6) and fluosilicic acid
(H2SiF6). While lead is corroded from the
anodes and deposited on refined lead
cathode starting sheets, the bullion im-
purities, including bismuth, are retained
in the form of a black slime. The slime,
scraped from the anodes, is washed free
of soluble matter, and partially dried
before processing for bismuth and other
impurity metals. The dried slime is the
major process residue in lead electro-
refining.
Anode slimes from the lead refinery
may contain as much as 20.6 wt. % Bi, but
several operations report 5-10 wt.%.
Table V compares impurity loading as
reported for raw slimes at the La Oroya
operations of Centromin6 as well as
values typical of several operations. The
values listed as typical are modeled after
the compositions at Cominco's Trail,
Canada, smelter.
The recovery of bismuth is one of sev- cess because it selectively removes bis-
eral process objectives in the treatment muth from lead bullion that has been
of this process residue. The primary op- purified of other impurities. The process
eration is fusion of the dried residues to is named for Dr. Wilhelm Kroll, who
produce a slag which contains lead, an- proposed the use of alkaline-earth met-
timony, and arsenic. The more noble als for this treatment, and Jesse Betterton,
metals (gold, if present, and silver and then director of research at the Ameri-
bismuth) are concentrated in the phase can Smelting and Refining Company,
known as ''black metal." Black metal is who combined reagents in a systematic
air blown in converters to further purify examination of the process. 7
it of arsenic, antimony, and lead at about The procedure has remained prac-
850°C. Transfer of the metal to a cupel tically unchanged except for efforts to
furnace produces dore (a silver-gold al- conduct it continuously. Metallic cal-
loy) and a bismuth-rich cupel slag. cium and magnesium are added to lead
The cupel slag (Bip3-PbO) is reduced bullion from which mostimpurities have
in a reverberatory furnace to produce been removed. The net reaction is:
bismuth bullion.
Ca + 2Mg + 2Bi = CaMg2Bi2 (s)
The Kroll-Betterton Process
Calcium dimagnesium dibismuthide, the
The Kroll-Betterton process is fun- resulting intermetallic compound, is a
damentally different from the Betts pro- higher-melting, lower-density dross that
Table II. Mechanical Properties of Blsmuth 13
Property Value
Modulus of Elasticity 31.7GPa
Shear Modulus 12.4GPa
Poisson's Ratio 0.33
Hardness, Brinell 4-8
Surface Tension at 300°C 376dyne/cm
Surface Tension at 400°C 370dyne/cm
Table III. Sources of Bismuth
Mineral Major Source Concentrates
United States Lead, Copper,
BizS3
Former Soviet Union and Lead-Silver
Mexico
Peru
Canada
Australia
Bi20Jl Bi People's Republic of China Tungsten
Korea
Bi20Jl (BiO)2C03 Bolivia Bismuth, Tin
Lead Concentrate
Malte
Fumes
Converter 1-------------1
Anode Slimes
High-
Cupel
Litharge Slag Bismuth
Slimes Processing Metal
Slag
Dore Bismuth Refining
Figure 1. The transfer of bismuth in process residues from copper to lead smelting and subsequent
recovery.

1992 June. JaM 47

floats to the top of the bullion as the
temperature is lowered to the freezing
point of lead. The dross is removed by
skimming the crust offthe refining kettle.
The enriched bismuth dross typically
contains entrained metallic lead. Part of
this lead is removed by reheating the
dross and allowing the lead to liquate to
a pool under the dross. The liquated lead
is returned to the debismuthizing pro-
cess, while the dross is treated with lead
chloride or chlorine in kettles to remove
the calcium and magnesium. The prod-
uct from this step, "high-bismuth metal,"
is an alloy of lead and bismuth (nomi-
nally 7 wt. % BO.
BISMUTH
REFINING PROCESS
Practically all extractive processes for
bismuth result in a bullion which con-
tains lead and bismuth. Unlike Kroll-
Betterton bullion, Betts bullion and bul-
lion produced from bismuth concentrate
tend to also contain copper and various
amounts of arsenic, antimony, selenium,
and tellurium. Drossing with sulfur is
required to remove or control the copper
load. Otherwise, lead and the other
impurities are removed by bubbling
chlorine into the bullion.
Most bismuth refineries interrupt the
chlorine treatment at about 70% Bi to
desilver. This is cohducted by the Parkes
(zinc) process as in lead refining. Chlo-
rine refining is then continued until a
predetermined bismuth (99.95%) level
is achieved. Fine refining with caustic
often provides bismuth of greater than
99.99% purity. At Asarco-Omaha, the
only U.S. primary producer, bismuth is
also refined to 99.999%, which is high-
purity bismuth.
BISMUTH
CONSUMPTION AND
APPLICATIONS
Bismuth consumption is distributed
rather broadly among eight different
applications, each accounting for about
10-15% of the bulk consumption. These
applications are pharmaceuticals, cos-
metics, catalysts, industrial pigments,
Table IV. Extraction of Bismuth
Process Feed Material
- -
Leach-Reduce Bismuth concentrate
Bi-Sn concentrate
Roast-Reduce Sulfide + Oxide
Roast-Reduce Sulfide concentrate
Precipitation
Exchange Reaction Debismuthization dross
Reduction Cupel slag
Table V. Composition (wt.%) of Lead Electrorefinlng Slime Produced
at Centromin and by Other, Typical Operations
Slime Producer Bi Pb
Centromin 20.6 15.6
Typical 7.5 20
48
steel additives, aluminum additives,
electronics, and fusible alloys. The re-
fined metal output has steadily declined
in recent years to 3.5 million kilograms
(7.7millionpounds),about20% less than
the recent high value in 1985. World
production and demand have been
roughly in balance since then, but the
free market price appears to have been
eroded in the same period. Bismuth
prices in the five years preceding the
1990 Mineral Commodity Summaries B are
shown in Table VI.
The United States' consumption ofbis-
muth was about 1.36 million kilograms
in both 1988 and 1989, and this level of
consumption does not appear to have
changed. The distribution of consump-
tion in the United States is shown in
Table VIP The table shows that the
manufacture of chemicals accounts for
approximately one-half the consump-
tion of bismuth, and metallurgical addi-
tives-in steel and aluminum-account
for some 30%.
Compound Applications
Compound applications are uses in
which bismuth is first converted into a
chemical compound. These are the pro-
duction of pharmaceuticals, cosmetics,
catalysts, and pigments. It is important
to note that refined bismuth is the starting
material for these applications. Taken
together, compound applications ac-
count for the largest demand of primary
bismuth.
It would appear that the future of
therapeutic and cosmetic formulas re-
quiring bismuth remains a significant
determinant of bismuth demand. In this
regard, a report was recently released
announcing a new ulcer-treating drug
with antidine bismuth citrate as its active
ingredient.9
There is also development activitylO in
bismuth-based, nontoxic, inorganic yel-
low pigments as potential substitutes
for the effective but environmentally
undesirable pigments based on cadmium
and hexavalent chromium compounds.
Molybdenum-tungsten yellow, the sub-
ject of the report in Reference 9, is a solid
Reagent Refining
HClleach Chlorine
Fe,C
C Chlorine
C Chlorine
Fe
PbC~ Chlorine
C Chlorine
Cu Sb Te Ag
1.6 33 0.74 9.5
3.5 35 14
Table VI. Average Dealer Price of
Bismuth In the United StateS-
Year $/kg
1990 7.70
1989 12.67
1988 12.72
1987 8.03
1986 7.15
Table VII. Consumption, by
Percent, of Bismuth Materials
In the United States
End Use Consumption (%)
Compounds 49
Metallurgical Additions 29
Fusible Alloys 21
Other Alloys 0.8
Miscellaneous
1.0
solution of the vanadate, molybdate, and
tungstate of bismuth. With a bismuth
content of 54.7%, it is reported to be
suitable for the coloration of plastic and
paraffin products, and paints.
Bismuth trioxide, a yellow crystalline
solid available in powder form, is pre-
pared by blowing oxygen over molten
bismuth or by the decomposition of
bismuth nitrate. It is used in ceramic
dielectrics and varistors. Bismuth oxy-
chloride (BiOCl) is used in the manufac-
turing of cosmetic eye shadow, face
powders, and other cosmetics to pro-
vide iridescence. Bismuth phospho-
molybdate is used for its catalytic effect
in the manufacture of plastic fibers.
Alloying Additives
As early as 1941, workers at the Bat-
telle Memorial Institutell reported that
small additions of bismuth (0.1-0.5%) to
cast, corrosion-resistant, chromium and
chromium-nickel stainless steels pro-
duced significant improvements in ma-
chinability without deleterious effects
on other mechanical properties or cor-
rosion resistance. Significant application
of bismuth in free-machining steels be-
gan in earnest 20 years later, and it is
now a major area of consumption.12
Bismuth is also added to several alu-
minum alloys at levels of 0.2-0.7% to
also improve machinability. The con-
sumption of bismuth in aluminum al-
loys is actually comparable to the level
in free-machining steels. Bismuth is used
as an inoculant (200 ppm level) in mol-
ten cast irons to inhibit graphitization on
solidification.
Fusible Alloys
Bismuth is an important component
of many binary and multicomponent
alloys which have low eutectic or li-
quidus temperatures. Several of the
common compositions are referred to as
fusible alloys.
Fusible alloys are used in the manu-
facture of components in shut-offs for
water heating systems, safety plugs in
JOM • June 1992
compressed gas cylinders, releases for
fire protection doors, and automatic
sprinkler systems. In these applications,
the component is sufficiently strong at
ambient temperatures; however, at a
predetermined higher temperature, it
yields by fusion. Many compositions
have been tabulated by Howe13 and in
Reference 14. A typical example is
Wood's metal (SOBi-2SPb-12.SSn-
12.5Cd), which melts at 60.S°C.
The anomalous expansion on solid-
ification of bismuth also occurs in some
fusible alloys. In some others, the solidi-
fication shrinkage is unusually low, per-
mitting their use for gripping tools and
punches.
ACKNOWLEDGEMENTS
Permission granted by Asarco to present
the information in this review is gratefully
acknowledged. The author also thanks the
staff and workers at the Asarco Lead Refin-
ery in Omaha, Nebraska, for ongoing helpful
discussions.
References
1. R.B. Gordon and J.R. Rutledge, "Bismuth Bronze from
Machu Picchu, Peru," Science, 223 (1984), pp. 585-586.
2. H. Remy, Treatise On Inorganic Chemistry (New York:
Elsevier, 1956) p. 675.
3. KC Li and CY. Wang. Tungsten (New York: Reinhold,
1955), pp. 41-42, 46-47, 116.
4. K Moriya, "Lead Smelting and Refining-Its Current
1ST
PACIFIC RIM
INTERNATIONAL
CONFERENCE
ON ADVANCED
MATERIALS
AND
PROCESSING
lMiS (PRICM 1)
Minerals • Metals • Materials
Status and Future," Lead-Zinc '90, ed. T.S. Mackey and R.D. Thermfact Ltd. Tel: (613) 544-6159
Prengaman (Warrendale, PA: TMS, 1990), pp. 23-38. 447 Berwick Ave. (514) 340-4nO
5. A.D. Betts, Lead Refining By Electrolysis (New York: John
Town of Mount Royal, Fax: (613) 544-7900
Wiley & Sons, 19(8).
6. I.L. Barker, "Slimes Treatment and Silver Refining Opera· Quebec, Canada H3R 1Z8 (514) 340-584Q
tions by the Cerro De Pasco Corporation at La Oroya, Peru,"
Silver- Economics, Metallurgy and Use, ed. A. Butts and CD.
Coxe (New York: Van Nostrand, 1%7), ch. 6.
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with Alkaline Earth Metals, Including Magnesium, and with
Antimony," Trans. AlME, 21 (1936), pp. 205-225. of computational services involving the applica-
8. Anon., Mineral Commodity Summaries 1991 (Washington, tion of chemical thermodynamics to metallurgy,
D.C: U.s. Bureau of Mines, 1991), pp. 2fr.27. ceramics, malerials science and related areas of
9. S.M. Jasinski, "Bismuth" (U.S. Bureau of Mines Yearbook,
1988) ; see also Mineral Industry Surveys, Bismuth in the Third chemical engineering. The system is accessible
Quarter, 1990. by modem (TelenetiDatapac) or TCP/IP through-
10. Z. Wenpu et aI., "A Bismuth-Containing Pigment: Mo-
out the world. The system is user-friendly; assis-
lybdenum-Tungsten Yellow," Bull. of the Bismuth Institute, 56
(1989), pp. 7-9. tance is always available: workshops are sched-
11. H. Pray, R.S. Peoples, and F. W. Fink, "Addition of Bismuth uled each year.
for Producing Free-machining Stainless Steels," Proc. ASTM,
41 (1941), pp. 646-675. A complete range of consuitational services are
12. "About Bismuth in INcut 200: A new series of Free- provided by Dr. A.D. Pelton, Dr. C.w. Bale, Dr.
machining Steels," Bull. of the Bismuth Inslitute46 (1985), pp.
I~ .
W.T. Thompson, and our experienced staff.
13. Tabulated data are compiled from: H.H. Howe, "Bis- You (or we) can produce compulations of
muth," Rare Metals Handbook, ed. CA. Hampel (London: equalibrium and thermal effects, etc. for
Reinhold, 1%1), and S.P. Parker, ed.,McCraw-Hill Concise
Encyclopedia of Science and Technology (1984), p. 233. ,SLAGIMETAUGAS REACTIONS
14. Metals Handbook, 9th ed., vol. 3 (Materials Park,OH: ASM,
1980), pp. 79~1.
, PLASMA PROCESSING
,CHEMICAL VAPOUR DEPOSITION
ABOUT THE AUTHOR _ _ _ __ ,COAL GASIFICATION
'METAL-MATRIX COMPOSITE
Funsho K. Ojebuoboh earned his Ph .D. in INTERFACIAL REACTIONS
metallurgy atthe Colorado School of Mines in • FUEL CELL REACTIONS
1985. He is currently a research engineer at • CORROSION
Asarco in Salt Lake City, Utah. Dr. Ojebuoboh • MULTICOMPONENT PHASE
is also a member of TMS. DIAGRAMS
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