Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
Klaus Reinhardt, Th. Goldschmidt AG, Essen, Federal Republic of Germany
Herwig Winkler, Treibacher Chemische Werke AG, Treibach, Austria
1. Introduction . . . . . . . . . . . . . . .
2. Cerium Mischmetal . . . . . . . . . .
2.1. Preparation of the Raw Materials .
2.1.1. Wet Chemical Attack . . . . . . . . . .
2.1.2. High-Temperature Chlorination . . . .
2.2. Fused-Salt Electrolysis . . . . . . . .
2.2.1. Iron and Graphite Cells . . . . . . . . .
2.2.2. Ceramic Cells . . . . . . . . . . . . . . .
2.2.3. Oxide Process . . . . . . . . . . . . . . .
2.3. Properties . . . . . . . . . . . . . . . . .
2.4. Use of Cerium and Cerium Misch-
metal . . . . . . . . . . . . . . . . . . . .
3. Cerium Alloys . . . . . . . . . . . . . .
The authors thank I. S. Hirschhorn of Lan-
thanide Research Corporation, West Orange,
New Jersey, United States, previously with Ron-
son Metals Corporation, for reading the English
manuscript and for his helpful suggestions.
1. Introduction
Cerium is the most abundant rare-earth element
and exceeds in abundance such well-known el-
ements as tin, cobalt, and lead. The following
article treats pure cerium and rare-earth mix-
tures in which cerium content either exceeds the
naturally occurring composition or determines
the overall properties or economics. Other rare-
earth elements are treated under a separate key-
word (→ Rare Earth Elements).
The term rare-earth elements includes the
elements scandium, yttrium, and the lan-
thanides lanthanum, cerium, praseodymium,
neodymium, promethium, samarium, europium,
gadolinium, terbium, dysprosium, holmium, er-
bium, thulium, ytterbium, and lutetium, all of
which belong to group 3 of the periodic ta-
ble (definition of lanthanides → Rare Earth El-
ements). In this article the symbol R is used for
any rare-earth element. The term cerium group,

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a06 139
1
1 3.1. Cerium – Iron Alloy – Flint Alloy . . 9
2 3.2. Cerium – Cobalt Alloys – Permanent
2 Magnets . . . . . . . . . . . . . . . . . . 10
2 3.3. Cerium – Nickel Alloys – Hydrogen
3 Storage . . . . . . . . . . . . . . . . . . . 11
4 4. Cerium Compounds . . . . . . . . . . 12
4 4.1. Production . . . . . . . . . . . . . . . . 12
5
4.2. Uses . . . . . . . . . . . . . . . . . . . . . 12
6
5. Analysis . . . . . . . . . . . . . . . . . . 14
6
6. Economic Aspects . . . . . . . . . . . . 14
7 7. Toxicology and OccupationalHealth 14
8 8. References . . . . . . . . . . . . . . . . . 15
or light rare-earth elements, includes lanthanum
through europium inclusively.
The presence of the rare-earth elements lan-
thanum to lutetium at the position of lan-
thanum (atomic number 57) in the periodic ta-
ble is due to the fact that, starting with cerium
(Xe 4 f 1 5 d 1 6 s2 ), 14 electrons are able to enter
the inner 4 f orbital. Lanthanum, which has an
empty 4 f level (4 f 0 ), represents the stable elec-
tronic configuration. This configuration is also
attained by tetrapositive cerium, which explains
why cerium has not only the normal rare-earth
+ 3 oxidation state, but also a + 4 state. This ex-
ceptional oxidation state simplifies separation of
cerium from the other rare-earth elements.
Cerium was discovered in 1814 by
Berzelius and named after the asteroid Ceres,
which had been discovered in 1800/1801.
2. Cerium Mischmetal
Cerium mischmetalor more simply mischmetal
(MM) [8049-20-5] is a mixture of rare-earth
metals of the ceriumgroup with cerium as the
major constituent. Mischmetal is the lowest
priced rare-earth metal because no expensive
2 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
chemical separation is needed to produce it. It is
produced predominantly by fused-salt electroly-
sis of rare-earth chlorides. Pure rare-earth metals
of the cerium group are produced by fused-salt
electrolysis of a mixture of chlorides and flu-
orides. The electrolytic reduction of rare-earth
oxides of the cerium group dissolved in a flu-
oride electrolyte has been put into production.
Metallothermic reduction of rare-earth chlorides
of fluorides is also employed (→ Rare Earth El-
ements).
Mischmetal was first produced industrially in
1908 by Auer von Welsbach, who succeeded
in finding an outlet for surplus rare earth in the
production of lighter flints. At that time, mon-
azite was used exclusively as the source of tho-
rium needed for the manufacture of incandescent
mantles.
2.1. Preparation of the Raw Materials
Rare-earth minerals in which cerium predom-
inates over lanthanum, praseodymium, and
neodymium (the other elements in the cerium
group) are monazite [1306-41-8], (R,Th)PO4 ,
from beachplacers of India, Southeast Asia,
Australia, South Africa, and Brazil, associ-
atedwith cassiterite, rutile, ilmenite, and zir-
con and bastnaesite [1299-84-9], [12172-82-6],
RFCO3 , from the carbonatitic deposit of the
Mountain Pass mine in California andfrom the
iron ore deposit of Bayan Obo in Inner Mongolia
(People’s Republic of China).
Monazite and bastnaesite are generally con-
centrated by physical methods such as gravity
concentration, flotation, and magnetic separa-
tion [1, B 1, pp. 60 – 67]. The rare-earth concen-
trates are converted into rare-earth chloride hy-
drates by wet chemical methods or into anhy-
drous rare-earth chlorides by high-temperature
chlorination.
2.1.1. Wet Chemical Attack
After being ground (50 µm – 1 mm), the concen-
trates are attacked by acids or caustic soda [1,
B 1, pp. 67 – 104].
Monazite. At temperatures between 140 and
170 ◦ C, concentrated sodium hydroxide solution
(50 – 70 wt %) reacts with the phosphates:
RPO4 (s) + 3 NaOH
R (OH)3 (s) + Na3 PO4
Th3 (PO4 )4 (s) + 12 NaOH
3 Th (OH)4 (s) + 4 Na3 PO4
The attack is carried out in an autoclave [13].
More concentrated sodium hydroxide solutions
(> 70 wt %) react at lower temperature [14].
The rare-earth hydroxides are dissolved in hy-
drochloric acid. The thorium does not dissolve
if the pH is kept close to 4. Trisodium phosphate
[7601-54-9] is a saleablebyproduct after recrys-
tallization.
Bastnaesite. The carbonates are attacked by
hydrochloric acid. The residue of rare-earth
fluorides is converted by alkaline treatment
into rare-earth hydroxides, which can be used
to neutralize the acid solution resulting from
the hydrochloric acid attack [15]. Concentrated
sodium hydroxide solution attacks bastnaesite to
form rare-earth hydroxides, which are dissolved
in hydrochloric acid [16].
3 RFCO3 (s)+6 HCl −→ 2 RCl3 +RF3 (s) + 3 CO2 + 3 H2 O
RF3 (s)+3 NaOH
R (OH)3 (s) + 3 NaF
RFCO3 (s)+3 NaOH
R (OH)3 (s) + NaF + Na2 CO3
R (OH)3 (s)+3 HCl −→ RCl3 +3 H2 O
The rare-earth chloride solution obtained by
these various processes is evaporated to form the
hexahydrates (mp 120 – 130 ◦ C), which solidify
on cooling. The rare-earth chloride hexahydrates
must be dehydrated for fused-salt electrolysis.
Dehydration is carried out under conditions that
avoid excessive formation of rare-earth oxide
chlorides by hydrolysis:
RCl3 · 6 H2 O
ROCl + 2 HCl + 5 H2 O
The dehydration is carried out either in vacuo or
by adding salts like CaCl2 , NaCl, or NH4 Cl that
reduce hydrolysis.
Oxide chlorides increase the viscosity of the
electrolyte and cause reoxidation of the rare-
earth metals that are formed. However, rare-
earth oxide chloride content near 5 wt % is not
detrimental, perhaps even desirable, for one spe-
cial type of electrolytic cell, the ceramic cell.
Dehydration can then be carried out in metal
ovens or on heated rotating steel plates, at tem-
peratures between 170 and 600 ◦ C, depending
on the process. In modern plants, spray drying
 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds 3

and fluidized-bed drying are employed for the
dehydration process. Special materials like tita-
nium and Hastelloy can be used to avoid corro-
sion by the hydrochloric acid generated in the
off-gas during drying.
2.1.2. High-Temperature Chlorination
The chlorination of rare-earth ores [17] in a shaft
furnace at 900 – 1100 ◦ C produces anhydrous
rare-earth chlorides that can be used directly for
fused-salt electrolysis. The reaction proceeds as
follows:
3 RFCO3 + 6 C + 3 Cl2 −→ 2 RCl3 + RF3 + 9 CO
RPO4 + 3 C + 3 Cl2 −→ RCl3 + POCl3 + 3 CO
Bastnaesite yields a mixture of rare-earth chlo-
rides and fluorides; monazite yields the chlo-
rides. In the case of monazite, the radioactiv-
ity, caused mainly by radium, a disintegration
product of thorium, remains with the rare-earth
chlorides. In addition, ThCl4 must be recovered
from the off-gas to avoid environmental pollu-
tion. Therefore, thorium-free monazite should
be used if available. The recovery of POCl3
[10025-87-3] is an economic necessity.
Typical analyses of rare-earth chlorides from
various sources are listed in Table 1.
2.2. Fused-Salt Electrolysis
For proprietary reasons, there are no modern de-
tailed publications on the process technology for
production of mischmetal by fused-salt electrol-
ysis. The know-how of the producers covers op-
timization of electrolytic cell construction for
continuous operations, special refractories re-
sistant to the aggressive salt and metal melt, and
maximization of current efficiency by the choice
of the composition of the electrolyte, with a view
to the viscosity, temperature, oxygen content,
and solubility of deposited metal in the melt.
The kind of electrolytic-cell refractory char-
acterizes the two main processes for the pro-
duction of mischmetal: (1) iron/graphite and (2)
ceramic [18], [19].
Independent of the type of cell, the amperage,
voltage, electrode distance, and current density
are chosen to reach the reduction potentials of
the rare-earth metals and to avoid an excessive
electrolyte temperature, which may cause vapor-
ization of the electrolyte, attack of the refractory
lining by the electrolyte and metal, and forma-
tion of metal fogs.
Cerium deposits at a lower voltage than
praseodymium, neodymium, and especially lan-
thanum. Samarium and europium are reduced
at the cathode only to the + 2 oxidation state.
Stirring by the chlorine liberated at the anode
or diffusion allows both elements to migrate to
the anode, where they are reoxidized [20]. Metal
fogs reduce current efficiency similarly.

Table 1. Typical analyses of rare-earth chlorides from various sources

RCl3 · 6 H2 O from wet chemical treatment, wt % ∗ RCl3 from high-temperature

Element, as oxide
chlorination, wt % ∗

Brazil China France India Malaysia United Germany, Fed. Rep.

States

R2 O3 45.8 45.8 47 46 46.1 46 65 – 67

RF3 6 – 10
CeO2 /TRO ∗∗ 47.2 50.0 49 46 50.3 50 48 – 50
Na2 O 1 0.66 < 0.2
MgO 1 0.2 < 0.3
CaO 0.63 0.5 1 0.59 0.4 <2
BaO < 0.1 <3
Fe2 O3 0.03 0.005 0.02 < 0.1
PbO 100 ppm 22 ppm 230 ppm 10 ppm 15 ppm < 50 ppm
P2 O5 trace trace 0.02 0.01 < 0.2
SO3 0.1 0.06 0.14 0.05 < 0.1
SiO2 0.05 < 0.1

∗ Unless otherwise stated.

∗∗ The cerium(IV) oxide content divided by the total rare-earth oxide content (see 5).
4 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
Added rare-earth fluorides and alkali and
alkaline-earth chlorides and fluorides having
decomposition voltages higher than those of the
rare-earth chlorides lower viscosity, increase the
conductivity, and improve the metal yield.
2.2.1. Iron and Graphite Cells
The iron or graphite crucible or pot serves di-
rectly as the cathode. Iron crucibles made of
spheroidal cast iron are directly connected as the
cathode, whereas graphite crucibles, which are
protected by an iron housing against air oxida-
tion, are connected via this iron housing.
Graphite-lined iron pots are connected di-
rectly. Crucibles up to an electrolyte volume of
50 L are round; larger crucibles are rectangular.
The schematic design of a rectangular graphite-
lined iron cell is shown in Figure 1. The anodes
consist of graphite or special carbon and can be
moved vertically to adjust the amperage and cur-
rent density.
Figure 1. Schematic design of a rectangular graphite-lined
iron cell (Th. Goldschmidt AG)
a) Graphite anodes; b) Insulated housing; c) Graphite lin-
ing (cathode); d) Iron crucible; e) Hood; f) Seal; g) Feeding
chute and chlorine suction; h) Bottom tap; i) Electrolyte
melt; j) Mischmetal deposit
The electrolysis is started via short-circuit
heating by melting rare-earth chlorides and
mischmetal down until a sufficient amount of
melt is obtained for electrolysis. Already molten
chloride, for example, from the chlorination pro-
cess, also may be used. Fresh rare-earth chlo-
rides are fed as solids.
As a result of the higher heat losses by the iron
and graphite cathode, the so-called cooled cath-
ode, the mischmetal is electrodeposited in the
form of dendritic sponge or droplets, together
with solidified electrolyte, at the bottom of the
cell. The deposition of solid mischmetal dimin-
ishes the damage to the refractory lining.
Toward the end of the electrolysis, the metal
is melted by increasing voltage and amperage
or by external heating via gas or resistance heat-
ing. Before tapping, the temperature of the metal
must be 850 – 950 ◦ C. The temperature of the
electrolyte at the surface may be 100 ◦ C higher.
Addition of iron scrap lowers the melting point,
making the melt easier to handle. The total con-
tent of the cell is cast into molds by tipping
or bottom pouring; reoxidation of the molten
metal is prevented by the residual electrolyte.
The mischmetal settles to the bottom of the mold
and is covered by the electrolyte, which can be
removed after solidification with an air chisel.
The separation of the residual electrolyte from
the liquid metal can be accomplished via a mold
that acts as part of a siphon: the metal collects
at the bottom, while the electrolyte overflows.
Mischmetal may be recast more cleanly.
Immediately after tapping, the electrolysis is
restarted by feeding fresh rare-earth chlorides,
which melt instantly in the hot cell.
The residual electrolyte, in which europium
and samarium are enriched, especially when
rare-earth fluorides are involved, may be recy-
cled for further enrichment and later used for
winning those two elements [21].
The cells are covered with a hood. The chlo-
rine formed at the anode is removed from the
exhaust gases by alkaline scrubbing: the result-
ing hypochlorite is either reduced to chloride or
sold. Recovery of the chlorine itself is normally
uneconomical because of dilution by air.
In modern plants, direct current is supplied
by thyristor-controlled silicon rectifiers; in older
plants, it is supplied by transformer-controlled
selenium rectifiers. The rectifiers are connected
in parallel, series, or individually to the cells.
Cell voltage ranges between 6 and 15 V, depend-
ing on the radiative loss of heat. The amperage
may be as high as 50 kA. The current density
depends on the cell design: in large rectangular
cells it is ≤ 2 A/cm2 , in smaller ones it is much
higher. The current efficiency can reach 75 %.
 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
From 2 to 2.5 kg of rare-earth chlorides are
consumed to produce 1 kg of mischmetal. The
metal yield is between 85 and 95 %, depending
on the extent the residues are recycled.
For a 50-kA cell, the daily production is
nearly 1 t. The d.c. power consumption per kilo-
gram of mischmetal produced is 10 – 15 kW h.
2.2.2. Ceramic Cells
Figure 2 shows the construction of a ceramic cell
[19]. Electrolysis takes place in a ceramic cru-
cible. The crucibles of small, simple cells have a
diameter of ca. 30 cm and a height of ca. 50 cm.
Further development resulted in the bigger ce-
ramic cells now in operation.
Figure 2. Ceramic cell [19]
a) Graphite anode; b) Insulation; c) Ceramic crucible;
d) Iron housing; e) Current supply for cathode; f) Cath-
ode; g) Mischmetal; h) Electrolyte melt; i) Rare-earth oxide
chloride diaphragm
A block of graphite or iron at the bottom of the
crucible serves as the cathode. If iron cathodes
are used, contamination of mischmetal with iron
cannot be avoided. Mischmetal at the electrol-
ysis temperature of ca. 900 ◦ C attacks most of
the construction materials in the electrolytic cell.
The working life of the ceramic cells is limited
to a maximum of 1 year.
The current density and voltage are controlled
by raising or lowering an anode of amorphous
carbon. Service life of the anode is between 30
and 50 d.
The electrolytic process in ceramic cells is
started by short-circuit heating. The cells are
filled with anhydrous rare-earth chlorides and
short-circuited with an iron or carbon rod. If
molten electrolyte from other cells is available,
mischmetal lumps are placed in the melting
5
pots and covered with melt. Electrolysis can
be started immediately. The ceramic cells op-
erate continuously. Anhydrous rare-earth chlo-
rides are added as required.
Between metal at the bottom of the cell and
the electrolyte is built up a diaphragm of rare-
earth oxide chlorides, which operates as an elec-
trical resistance, generating the heat that keeps
the deposited metal in liquid form.
One or two times a day, molten mischmetal
is tapped, sucked, or ladled from the bottom of
the crucible.
During the process the anode is consumed
by oxidation. For this reason, the electrode must
be adjusted from time to time. Oxidation results
from contact with atmospheric oxygen or the
chlorine produced or from reaction with oxide
chlorides in the electrolyte. Therefore, a high ox-
ide chloride content in the rare-earth chlorides
causes considerable anode consumption.
The amount of molten electrolyte increases
during operation. Enrichment of europium and
samarium takes place. To maintain a constant
level of electrolyte, a part, the so-called slag,
is ladled out at regular intervals. This slag can
be treated chemically to recover Eu2 O3 and
Sm2 O3 . A typical composition of slag is pre-
sented in Table 2.
Table 2. Analyses of mischmetal slag, Treibacher Chemische
Werke AG, Austria
Element, as oxide Relative content, wt %∗
La2 O3 26.6
CeO2 31.9
Pr6 O11 4.1
Nd2 O3 19.8
Sm2 O3 14.3
Eu2 O3 0.4
Total 97.1
Total rare-earth oxide content (TRO) is 41.9 wt %
∗ The element oxide content divided by total rare-earth oxide
content (see chap. 5).
2.2.3. Oxide Process
On the basis of a process developed by the U.S.
Bureau of Mines [22], [23] and further improved
by Santoku Metal Industries, Japan, Santoku
now produces mischmetal from rare-earth ox-
ides. The process is similar to aluminum elec-
trolysis (Hall – Héroult process). It avoids emis-
sion of chlorine and the consequent expensive
purification of off-gas.
6 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds

Rare-earth oxides are dissolved in an elec-

trolyte consisting of alkali fluorides (to improve
conductivity), alkaline-earth fluorides (to reduce
melting point), and rare-earth fluorides (to im-
prove the solubility of rare-earth oxides) and
are reduced electrolytically to the rare-earth
metals. The electrolysis cell (Fig. 3) consists
of a graphite crucible with graphite anode and
molybdenum cathode, working under an inert-
gas atmosphere to prevent oxidation of the con-
struction materials. The electrolyte is initially
melted by resistance heating. Electrolyte and
electrodeposited rare-earth metals are kept liq-
uid by the joule heat. A cell produces ca. 500 kg
of metal per day. If bastnaesite is a raw material,
it must be specially purified prior to electrolysis.

Figure 3. Electrolysis cell for the production of mischmetal

2.3. Properties
Table 3 shows typical analyses of mischmetal
from various producers.
The physical and chemical properties of
mischmetal are determined by the properties of
its four main constituents – cerium, lanthanum,
neodymium, and praseodymium [1], [24]. There
can be no exact values for mischmetal because
the composition depends on the type of raw ma-
terial and treatment. However, the values cor-
respond most closely to those of the main con-
stituent, cerium. Table 4 lists several properties
for the four main rare-earth metals.
Table 3. Typical analyses of mischmetal from various producers, weight percent unless otherwise stated
from oxides [23]
a) Graphite anodes; b) Molybdenum cathode; c) Graphite
crucible; d) Liquid electrolyte; e) Molybdenum crucible;
f) Tapping pipe; g) Molten mischmetal
Mischmetal is ductile. The freshly cut sur-
face has a metallic gray appearance. In air, the
surface oxidizes to form yellow to greenish-
gray rare-earth hydroxide carbonates or oxide
hydrates. Some types of oil may protect the sur-
face against corrosion, but only for a limited pe-
riod of time. Alloying with 1 – 2 wt % of mag-
nesium increases corrosion resistance. Massive

Metal Producer

Treibacher Ronson Santoku Corona Fluminense Former Minmetals

(Austria) (United States) (Japan) (Brazil) (Brazil) (USSR) (China)

Total rare-earth metals 99.5 > 95 97.8 97.4 96.0 97 98.6

Relative content∗

La 23 18 – 28 22.9 17.5 17.9 25.1 19.6

Ce 49.8 50 – 55 51.9 54.2 55.3 53.2 54.9
Pr 5.6 4–6 5.4 5.6 7.3 5.2 6.1
Nd 18.6 12 – 18 16.2 16.0 17.4 14.0 17.1
Sm 0.2 < 0.1 0.4
Others 2.8 <2 3.6 6.7 4.8 2.8 1.9

Al 0.05 0.14 0.05 0.1

Pb 50 ppm 343 ppm 90 ppm 227 ppm 4600 ppm
Fe 0.05 <5 1 2.0 2.3 1.7 0.28
Si 0.20 0.1 0.54 0.1 0.05
Mg 0.03 < 0.5 0.20 0.20 0.2 0.033 0.35
Ca < 0.1 0.02 0.1 0.013

∗ The content of rare-earth metal divided by total rare-earth metals.

 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds 7
Table 4. Properties of lanthanum, cerium, praseodymium, and neodymium [1], [2], [4]

Property Unit La Ce Pr Nd

Atomic number z 57 58 59 60
Atomic mass Ar 138.9055 140.115 140.90765 144.24
Crystal structure at 293 K dhcp ∗ fcc dhcp ∗ dhcp∗
a0 nm 0.3774 0.51612 0.36725 0.36579
c0 nm 1.2159 1.18354 1.17992
Density  g/cm−3 6.146 6.770 6.773 7.008
◦
Melting point mp C 918 798 931 1021
Heat of fusion ∆H kJ/mol−1 6.2 5.5 6.9 7.1
◦
Boiling point bp C 3464 3433 3520 3074
Temperature at a vapor pressure of
◦
133 Pa C 2208 2174 1968 1741
0.133 Pa 1581 1581 1360 1197
Specific heat at 298 K J mol−1 K−1 26.2 27.0 27.0 27.5
Coefficient of linear thermal expansion at 298 K 10−6 K−1 4.9 8.5 6.79 9.98
Thermal conductivity at 300 K J s−1 cm−1 K−1 0.135 0.114 0.125 0.165
Electrical resistivity at 273 K µΩ cm 61 77 71 64

∗ Double hexagonal closest packed in the direction of the c axis.

metal burns above 150 ◦ C in pure oxygen; how-
ever, chips, turnings, and powder burn at this
temperature even in air. Mischmetal dissolves in
dilute mineral acids with evolution of hydrogen.
The ingots may be easily machined. How-
ever, the pyrophoric character of mischmetal
may cause autoignition of the turnings. Misch-
metal may be easily extruded at temperatures
just below its melting point. Rollability is ad-
versely effected by oxygen content. Nearly all
of the alloying elements cause brittleness.
2.4. Use of Cerium and Cerium
Mischmetal
The most important uses of mischmetal or
cerium are metallurgical. The metallurgical im-
portance of rare-earth metals is based on reac-
tions to form solids with oxygen, hydrogen, ni-
trogen, sulfur, arsenic, bismuth, and antimony,
reducing the effects of these elements on the
properties of the metals [25]. To avoid the for-
mation of harmful rare-earth oxide inclusions
by secondary reactions of the mischmetal with
refractories, slag, and atmospheric oxygen, the
mischmetal is plunged into the molten metal
or added under an inert-gas atmosphere. Met-
allurgical mischmetal can also be clad with alu-
minum or steel. Mischmetal is added as lumps,
rods, doughnuts, or wire [26].
Iron and Steel [27]. Rare-earth sulfides and
oxide sulfides are formed in liquid steel and
precipitate as globular particles uniformly dis-
persed, which, unlike manganese sulfides, are
not deformable during rolling and do not form
stringers. This is called sulfide shape control
and is used in microalloyed or HSLA (high-
strength low-alloy) steels to reduce anisotropy
in toughness, notch toughness, and bend forma-
bility. This is especially important for pipeline
steels used at subzero temperature in the Arctic.
Mischmetal may entrap hydrogen and dimin-
ish hydrogen-induced cracking.
Hot shortness in stainless steels can be re-
duced by removal of tramp elements (As, Bi,
Sb) together with deoxidation and sulfide shape
control. Heat and oxidation resistance can be
increased by mischmetal, which forms protec-
tive surface layers of rare-earth oxides together
with oxides of the steel components, for exam-
ple, Cr2 O3 , that are resistant to scaling.
Mischmetal or cerium-containing master al-
loys are added to cast iron to improve ductil-
ity, toughness, and the microstructure. Cerium
allows graphite to form nodules, causing nucle-
ation in spheroidal and vermicular cast iron, and
neutralizes the harmful effect of the tramp ele-
ments [28].
The addition rate depends on the applica-
tion and preparation of the steel or iron melt.
For sulfide shape control and nodularization of
graphite, up to 1 kg of mischmetal is added per
tonne. Other effects require even larger addi-
tions, up to 8 kg per tonne.
8 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds

Nonferrous Metals [29]. Addition of
mischmetal to copper alloys improves tensile
strength and deep-drawing properties. The heat
resistance and ductility of aluminum conductor
cables are improved without any significant de-
crease in electrical conductivity. Titanium alloys
show a higher grade of grain refinement, better
mechanical properties, and improved corrosion
resistance as a result of mischmetal additions.
The need for improved galvanizing compo-
sitions (increased corrosion resistance, fluidity,
wettability, and freedom from intergranular cor-
rosion) without affecting formability, weldabil-
ity, and paintability led to the development of
Galfan, which is the classical zinc – aluminum
eutectic alloy (95 wt % Zn, 5 wt % Al) with
0.05 wt % mischmetal [30].
In nickel- and cobalt-based superalloys for
turbine engines, cerium (yttrium is even better)
increases oxidation and sulfidation resistance at
high temperature. Similar effects are achieved in
chromium-based alloys, and by removing gases
cerium prevents embrittlement of niobium- and
tantalum-based alloys.
In the molten state the main constituents of
mischmetal are completely miscible with nearly
all non-rare-earth metals. Their large atomic
radii and their low electronegativities are the
reasons why there are only a few cases of their
solid solubility in other metals. One such case,
however, is the limited solid solubility of misch-
metal in magnesium [32]. As solids they do not
dissolve other metals; instead, they form inter-
metallic phases. With elements of the groups 4,
5, and 6 they do not form intermetallic phases
[32], [33].
The intermetallic phases, with a degree of
heteropolar bonding, may be brittle. Therefore,
rare-earth metals and alloys are unsuitable as
construction materials. Cerium phase diagrams
are generally used in place of mischmetal phase
diagrams [32], [34], [35].
Depending on the purity desired, alloying is
done in crucibles made of tantalum, molybde-
num, boron nitride, graphite, or clay graphite.
An inert-gas atmosphere, vacuum, or inert slag
cover are necessary.

Other Uses. Cerium and mischmetal are 3.1. Cerium – Iron Alloy – Flint Alloy
used as getters to absorb traces of gases in evac-
uated devices. The cerium – iron phase diagram is shown in
Mischmetal is said to increase the efficiency Figure 4.
of fuel consumption and to decrease CO and
NOx contents in the exhaust of internal combus-
tion engines if steam is passed through misch-
metal spirals before injection into the carburetor
[31].
In some of these uses, mischmetal (= MM)
can be replaced by CeSi [12014-84-5], MMSi,
or MMFeSi alloys produced directly frombast-
naesite by reduction in an arc furnace.
The pyrophoric character of mischmetal al-
loyed with iron and magnesium is used for flints
(see Section 3.1) and pyrotechnics.

3. Cerium Alloys
The atomic radii of lanthanum, cerium,
praseodymium, and neodymium differ only
slightly so that miscibility is complete in the
liquid state and close to the solidus curve. The
liquidus curves correspond to those of ideal mix-
tures. Figure 4. Ce – Fe phase diagram [35]
 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds 9

Pyrophoric Properties. None of the numer-
ous developments of cerium-free pyrophoric al-
loys of the last decades has been able to replace
the cerium – iron alloy invented and patented by
Auer von Welsbach in 1903. Lighter flint al-
loy consists basically of mischmetal and iron.
Some other metals are added in small amounts to
modify the pyrophoric properties and to improve
processing. Typical analyses of lighter flint al-
loys are shown in Table 5.
The frictional pyrophoric properties of
cerium – iron are based on a combination of mi-
crostructure and mechanical and chemical prop-
erties of the alloy. The typical crystal structure of
commercial alloy consists of tough, brittle pri-
mary crystals of Ce2 Fe17 enclosed by a peritec-
tic layer of CeFe2 embedded in a soft matrix of
CeFe2 and Ce (Fig. 4).
Mechanical friction generates primary cracks
in the intermetallic compound, initially leading
small particles with adherent matrix to break
away. Residual frictional and deformation heat
in the small particles heats them adiabatically
to ignition temperature. On ignition, these parti-
cles burn totally. Heat is emitted predominantly
by radiation, particle temperature reaching ca.
2000 ◦ C. The size of these particles, which de-
pends on the hardness of the lighter flint, in-
fluences the ignition behavior. Smaller particles
ignite rapidly, resulting in quick adiabatic heat-
ing, whereas larger particles emit a higher local
output of reaction heat.
Magnesium and cerium form an intermetallic
compound that ensures a high heat of combus-
tion. The temperature of the spark is also in-
creased by alloying with aluminum, which in
addition produces a spiky spark. Zinc and cop-
per improve fluidity during extrusion.
Manufacture of Lighter Flints. Lighter
flint alloy is produced by melting mischmetal,
iron, and the other metals in clay graphite or
other suitable crucibles heated in induction fur-
naces at 1000 – 1200 ◦ C under a protective salt
layer (CaCl2 , BaCl2 ). After removal of the salt
layer, the alloy is cast into preheated molds.
For better shape control of the CeFe2 crys-
tallites, the melt is cooled slowly. The as-cast
products are billets of 3 – 6 cm diameter. Aver-
age yield of alloy, based on raw material input,
is 95 – 98 %. Losses arise from air oxidation and
reaction with the crucible material.
After preheating at 400 – 500 ◦ C, the flint bil-
lets are extruded to rods on horizontal or verti-
cal extrusion presses at pressures between 20
and 50 MPa. Alloying with aluminum, magne-
sium, zirconium, titanium, and copper lowers the
amount of pressure required. Extrusion pressure
is also affected by impurities in the mischmetal,
the rare-earth distribution, and the iron content
of the alloy. During extrusion, the eutectic ma-
trix liquifies. After extrusion, the rods are cooled
rapidly in air or cooling oil. The diameter of the
rods usually ranges between 2 and 6 mm.

Table 5. Analyses of lighter flints of different producers, weight percent

Metal Producer

Treibacher Santoku Electro Centre Ronson

(Austria) (Japan) (France) (United States)

Total rare-earth metals 76.2 78.3 76.7 77.0

Relative content∗
Ce 51 52.3 53.3 51.5
La 22.7 24.7 19.2 23.1
Nd 16.6 14.3 16.5 16.5
Pr 5.4 5.0 6.4 5.8
Sm 0.3 0.4 0.4 0.3

Fe 20.6 19.3 20.4 20.0

Mg 2.2 1.8 2.1 1.5
Al 0.09 0.28 0.04 0.05
Cu 0.02 0.03
Si 0.22 0.29 0.22 0.2
Zn 0.54 0.03 0.34 0.5
C 0.02 0.08 0.06 0.01

∗ The content of rare-earth metal divided by total rare-earth metals.

10 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds

These rods are cut on horizontal or vertical

dies to the length of the lighter flint, usually
between 4 and 12 mm. A subsequent heat treat-
ment between 350 and 450 ◦ C improves the py-
rophoric properties considerably [36] by conver-
sion of Ce – Fe mixed crystals, formed through
rapid solidification during extrusion, into CeFe2
and Ce.
The lighter flints are sized on sorting ma-
chines, generally with sorting sieves. These
mechanically presorted flints are checked care-
fully by mechanical and optical sorting ma-
chines. Some producers make a final inspection
by eye: flints are moved over a conveyor belt and
imperfect flints are picked out by hand. Flints are
checked for length, diameter, and straightness,
as well as to see if the area of cut is circular as
desired and if cavities or burrs are absent from
the cut surface.
Durability of lighter flints is limited to 4 – 5
years normally. Humid air and a warm cli-
mate, such as prevails in the tropics, cause quick Figure 5. Ce – Co phase diagram [35]
decomposition of the flint, visible as a dusting
at the beginning of the decomposition process. The classic RCo5 [12017-68-4] permanent
For protection of the flint surface against corro- magnet alloys are based on samarium, which
sion, flints are normally coated and colored with gives the best hard magnetic properties. Re-
lacquer. placement of samarium, an expensive rare-earth
Generally, there is a distinction between the metal, by cerium or even by inexpensive misch-
normal lighter flints (most commonly 2.4 mm metal reduces the hard magnetic properties, es-
in diameter and 4 mm in length) and the lighter pecially because of the lower crystal anisotropy
flints for disposable lighters. Flints for dispos- field [37]. However, adding small amounts of
able lighters are manufactured in a length from samarium to the mischmetal and/or changing the
7 to 12 mm and a diameter from 2.3 to 2.5 mm, composition of the mischmetal [38] or partial
depending on the amount of gas filling in the replacement of cobalt [39], [40] makes magnets
lighter. Such flints should ignite at least 1000 with sufficient coercivity and energy product for
times before 50 % of the flint is used up. less sophisticated uses and increases the range
Accuracy of size is important for flints for of uses because of the lower costs.
disposable lighters because filling is carried out These alloys are manufactured by melting the
by machines and each faulty flint stops produc- metals or by calciothermic reduction of oxide
tion. Maximum tolerances of ± 0.1 mm in length and metal-powder mixtures [41].
and in diameter are acceptable. One kilogram of These magnets are used for electronic
lighter flints contains from 3000 to 10 000 flints. watches, microwave amplifier tubes, loudspeak-
ers, headphones and microphones, magnetic
coupling, bearings, sensors, clamp systems,
3.2. Cerium – Cobalt Alloys – Permanent switches, d.c. motors, servomotors, and step mo-
Magnets (→ Magnetic Materials) tors, mainly to achieve miniaturization.
Some magnetic properties are listed in
The cerium – cobalt phase diagram is shown in Table 6.
Figure 5.
 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds 11

Table 6. Intrinsic magnetic properties of RCo5 compounds at MMNi5 H6.3 , the nickel must be partially re-
room temperature [40]
placed [44] by aluminum [45], calcium [46],
Property SmCo5 CeCo5 MMCo5 ∗ cobalt [47], chromium [48], copper [49], iron
Saturation magnetization Bs , [50], or manganese [51]. Pressure – composition
T 1.07 0.77 0.89 isotherms are shown in Figure 7. Alloys of the
Anisotropy constant K, type CeMg11 M (M = Ni, Cu, Zn) also absorb hy-
106 J/m3 9.6 5.6 6.6 drogen [52].
Anisotropy field HA ,
MA/m 20 15.1 14.7
Curie temperature TC ,
◦
C 724 347 520
Theoretical energy product B2s /4,
kJ/m3 228 118 158

∗ The values for MMCO5 are only approximate, for composition

varies.

3.3. Cerium – Nickel Alloys – Hydrogen

Storage
The cerium – nickel phase diagram is shown in
Figure 6.

Figure 7. Pressure – composition isotherms for des-

orption in the LaNi5 – H, MMNi5 – H, and modified
MMNi5−x Mx – H systems at 293 K [44] MM represents
mischmetal, and M represents a metal (here Al, Co, Cr, or
Mn).

These systems may be used for hydrogen

transportation and storage; vehicular and sta-
tionary fuel supply, an ideal fuel from the eco-
logical point of view; air conditioning; refriger-
ation; heat pumps; storing and regaining waste
heat; and hydrogen-storage electrodes in alka-
line batteries. These systems may also be used
for purification [53] and isolation [54] of hydro-
gen and H2 /D2 separation.

Figure 6. Ce – Ni phase diagram [35]
LaNi5 [12196-72-4] has a high storage ca-
pacityfor hydrogen gas [42], up to the for-
mula LaNi5 H6.7 . To decrease costs, lanthanum
can be replaced by mischmetal [43]. How-
ever, to lower the higher hydrogen equilibrium
pressure and form hydrides up to the formula
4. Cerium Compounds
Cerium is the most abundant rare-earth element.
Nearly 50 % of the available rare-earth raw ma-
terial consists of cerium oxide. Cerium is also
the only rare-earth element that can be easily
separated from a mixture of rare-earth elements
by simple chemical methods, for cerium has a
tetravalent state.
12 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
4.1. Production
Cerium is separated from other rare-earth ele-
ments by oxidation of solutions resulting from
attack of bastnaesite or monazite. The oxidiz-
ing agent can be H2 O2 , hypochlorite, or atmo-
spheric oxygen, or anodic oxidation can be used.
Cerium precipitates as cerium(IV) oxide hydrate
[63394-44-5], [67285-52-3].
For example, cerium(III) rare-earth oxide hy-
drate is dried and oxidized by air to cerium(IV)
rare-earth oxide hydrate. The oxidized hydrate
is dissolved in nitric acid, and the solutions are
neutralized slowly. Cerium(IV) oxide hydrate is
collected by filtration. Initially, of the total rare-
earth oxides 45 – 50 wt % is CeO2 . This is in-
creased to 95 wt % in the product.
In a process of Molycorp [55], ground bast-
naesite ore concentrates are roasted, and cerium
is oxidized with atmospheric oxygen. Roasted
material is treated with hydrochloric acid to dis-
solve lanthanum, neodymium, praseodymium,
etc. The pH is adjusted to 4, and a cerium-rich
residue (≈ 90 wt % CeO2 ) is collected by filtra-
tion. This residue has high fluoride content and
poor solubility. To get soluble cerium salts out
of this material a subsequent digestion with sul-
furic acid or caustic soda is necessary.
Cerium salts are produced by liquid – liquid
extraction from rare-earth –cerium-containing
solutions (→ Rare Earth Elements). Cerium can
be extracted out of cerium nitrate – nitric acid so-
lutions in a few steps in the form of a cerium(IV)
nitrate complex in tributyl phosphate and there-
fore separated from the accompanying trivalent
rare-earth elements, which form less stable ni-
trate complexes. Purities of 99.99 % and better
can be achieved easily.
4.2. Uses
The principal uses for cerium compounds are as
polishing agents and as a component in glass.
Cerium Oxide Polishing Compounds.
Cerium-(IV) oxide [1306-38-3], CeO2 , has now
replaced other polishing oxides like iron oxide
(red rouge), silica(white rouge), and zirconium
dioxide almost completely. The special merits
of cerium oxide are its 100 % faster polishing
speed and its cleanliness.
Cerium oxide is used for polishing glass mir-
rors, plate glass, television tubes, ophthalmic
lenses, and precision optics. However, the ad-
vent of the Pilkington float process (→ Glass) in
the early 1970s significantly reduced the use of
cerium oxide in the manufacture of plate glass.
Cerium oxide polishing powder is produced
by calcining oxidic cerium mineral concentrates
in rotary kilns or other furnaces at temperatures
of ca. 1000 ◦ C. Calcined concentrates are milled
and cleaned by sieving or sifting afterwards. The
impurities (CaO, SrO, non-rare-earth elements)
must not exceed a certain level in the raw ma-
terial; otherwise, cerium oxide will agglomerate
during calcining and lose polishing capacity.
Polishing powders production can also start
from cerium salt solutions. Cerium carbonates
or hydroxides are precipitated and then calcined
in rotary kilns or muffle furnaces to oxide at tem-
peratures of ca. 1000 ◦ C. The calcined oxides are
milled and screened or sifted to get the desired
grain size distribution and to remove scratching
impurities.
Polishing powders made from mineral con-
centrates polish more slowly and less cleanly
than precipitated products. The former are
cheaper but are not used for high-performance
polishing processes (precision optics).
Additives improve suspension properties of
polishing powders in aqueous solutions and in-
crease polishing rate, for instance, preventing
foaming (antifoaming) and settling of cerium
oxide (anticaking) in tanks and pipes.
Pure cerium oxide is yellowish white. Small
amounts of Pr6 O11 in combination with other
rare-earth oxides give a brown oxide. The color
does not appear to affect the polishing properties
for fixed CeO2 content. Standard concentrations
are 50, 70, 90, and 100 %. The polishing rate
increases with CeO2 content. The average grain
size of polishing powders is normally 0.5 – 5 µm.
A narrow grain size distribution is advantageous.
There are many theories about the mecha-
nism of the polishing process [56]. According
to these theories, both a chemical and a physical
component, among others, are effective during
polishing [57]. The glass surface is hydrolyzed
by reaction with water (chemical theory) and
the silica gel layer formed is removed mechan-
ically by the polishing compound. Another the-
ory states that glass is removed mechanically
 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
(wear theory) and to some extent by chemical
reaction [58].
Cerium Oxide as a Glass Constituent.
Cerium oxide can be used to decolorize
soda – lime glasses for bottles, jars, etc. [59]. The
Ce4+ oxidizes Fe2+ impurities, which are al-
ways present in the raw materials and therefore
in glasses, to Fe3+ . A change from the blue-
green color of Fe2+ to the 10 times weaker yel-
low Fe3+ takes place. Arsenic, zinc selenite, or
manganese are used for the same purpose. The
combination of these materials with cerium re-
duces costs. Presently, cerium oxide has been
replaced by less expensive decolorizers.
Cerium protects glass against solarization
and browning, a discoloration caused by irradi-
ation. It is therefore a constituent of glass for the
faceplates of television screens, which are un-
der constant bombardment by an electron beam
[60]. Radiation-shielding windows for nuclear
and radiochemical uses consist of lead glass
stabilized by CeO2 . Since maximum transmis-
sion is necessary for these thick windows, only
99.99 % cerium oxide (15 ppm Fe max.) can be
used.
For phototropic glasses, as in phototropic eye
glasses, windshields, and window glasses that
darken in the sunlight and lighten in the shade,
cerium is a sensitizer.
Other Uses. Cerium rare-earth fluorides im-
prove the brightness of carbon arcs. Cerium flu-
oride oxide mixtures are mixed with carbon for
electrodes. These electrodes are used on movie
sets and as military searchlights to increase
brightness as much as tenfold [61]. Cerium ox-
ide (99.9 %) is used as white pigment in enamels
for tiles.
Basic oil-soluble cerium salts of organic
acids, such as cerium alkylsulfonates, alkyl sul-
fates, and alkyl phosphates, as well as cerium
octoates, serve as driers in paints and varnishes.
Cerium compounds that are soluble in organic
liquids find use as combustion additives in fuels
[62]. Particle emission in exhaust gases is re-
duced by 60 %. Diesel oil savings in the range
2 – 3 % are achieved. Cerium compounds added
to silicones increase the thermal stability.
Cerium oxide is used in self-cleaning ovens
as a catalyst [63].
13
In zeolitic cracking catalysts, cerium is a ther-
mal and hydrothermal stabilizer to extend the
life and increase the activity of the catalysts [64].
The following uses of cerium in noncracking cat-
alysts are listed by Peters and Kim [65]:
ammonia synthesis
hydrogenation
dehydrogenation
polymerization
isomerization
oxidation
automobile emissions control
5. Analysis
Mischmetal and cerium oxide can be analyzed
for total rare-earth content (TRO) and for indi-
vidual rare-earth elements [6], [66].
The determination of the total rare-earth con-
tent is carried out by dissolving the rare-earth-
containing material with acids or by alkaline fu-
sion. The rare-earth elements are precipitated as
hydroxides by adding NH3 , dissolved in HCl or
HNO3 , and reprecipitated as oxalates, which are
ignited to the oxides, R2 O3 , with the exception
of cerium, which forms CeO2 .
The individual rare-earth elements are deter-
mined by X-ray fluorescence (La), atomic ab-
sorption spectrometry (Y), and spectrophotom-
etry (Nd, Pr, Sm). Analysis by means of optical
plasma emission spectroscopy is a new, efficient
method. Cerium can be determined by titration
because it can be oxidized to the tetrapositive
state.
6. Economic Aspects
Total rare-earth production in the Western world
is 20 000 – 25 000 t of rare-earth oxides per year
in 1986, of which 45 – 50 % is cerium. Raw ma-
terial prices have stabilized for bastnaesite at $ 1
per pound TRO FAS Los Angeles, for monazite
at A$ 450 per tonne FOB Australia, and rare-
earth chlorides (RCl3 · 6 H2 O) at ca. $ 0.70 per
pound delivered.
The growing production of rare-earth raw
material and products from the People’s Repub-
lic of China should only stabilize the market and
not sensationally affect prices.
14 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
Rhône-Poulenc (France, compounds) and
Molycorp-Union Oil (United States, bastnaesite
and compounds) are the leading producers; other
producers are Treibacher (Austria, metals, al-
loys, and compounds), Santoku (Japan, metals,
alloys, and compounds), Ronson and Reactive
Metals (United States, metals and alloys), Indian
Rare Earths (India, compounds), and Corona and
Fluminense (Brazil, metals and alloys). In Ger-
many, Goldschmidt specializes in magnet alloys.
Further magnet alloy producers are Hitachi and
Research Chemicals (United States) and Sumit-
omo and Shin-Etsu (Japan).
Important producers of lighter flints in the
Western world are Treibacher, Electro Centre
(France), Santoku, and Ronson. Total world
market for lighter flints is estimated at ca. 700 t/a.
The share of flints for disposable lighters is more
than 60 %.
Modern steel technology has decreased de-
mand for mischmetal substantially. The met-
allurgical uses of rare-earth metals consume
less than 15 % of the total rare-earth produc-
tion. The production capacity for mischmetal is
4 000 – 5 000 t/a, but less than 50 % is in oper-
ation (1986). Mischmetal is sold at $ 4 – 5 per
pound, depending on quantity, shape, and size.
Total world demand for cerium-based pol-
ishing powders, the biggest consumer of
cerium oxide at present, is estimated to be
3 0000 – 4 0000 t/a. The price for cerium polish-
ing compounds depends on the cerium content
and ranges between $ 2 per pound for 50 % CeO2
and $ 5 per pound for 99.9 % CeO2 .
The market for more sophisticated uses –
electronics, magnets, etc. – is expected to grow.
The production of rare earths is profitable
only if the market for all the rare-earth elements,
which are produced in the relative amounts oc-
curring in their minerals, is reasonably balanced.
7. Toxicology and
OccupationalHealth
The rare-earth elements and compounds are con-
sidered to be only slightly toxic. No toxic effects
during production or use have been reported in
the rare-earth industry.
Progressive lung retention was observed af-
ter inhalation of dust containing rare-earth ox-
ides and fluorides from carbon arc electrodes.
The damage to the lung that was assessed by
X-ray did not seem to be attributable to the rare
earths, but to thorium and its disintegration prod-
ucts. Continual progress in rare-earth processing
has reduced the radioactive impurities in rare-
earth products substantially, so they are practi-
cally free of radioactivity today. Intravenous in-
jections of rare-earth salts damage the liver; oral
administration has no pathological effect on an-
imals [1, B 2, pp. 282 – 283], [67].
8. References
General References
1. Gmelin, system no. 39, Seltene Erden, A 1
(1938); A 2 – A 5, A 7, A 8, B 1 – B 7, C 1 – C 9,
D 1 – D 6 (1973 to date).
2. K. A. Gscheidner, Jr., L. Eyring (eds.):
Handbook on the Physics and Chemistry of
Rare Earths, vol. 1 (1978), vols. 2 – 4 (1979);
vol. 5 (1982), vols. 6 and 7 (1984), vol. 8
(1986) North Holland Publ., Amsterdam.
3. L. Eyring (ed.): Progress in the Science and
Technology of the Rare Earths, vol. 1 (1964),
vol. 2 (1966), vol. 3 (1968), Pergamon Press,
Oxford.
4. J. A. Gibson, G. S. Harvey: Properties of the
Rare Earth Metals and Compounds, Technical
Report AFML-TR-65-430, 1966.
5. F. H. Spedding, A. H. Daane: The Rare Earths,
J. Wiley & Sons, New York 1961.
6. F. Trombe, J. Loriers, P. Gaume-Mahn, C.
Henry La Blanchetais:
“Scandium-Yttrium-Éléments des Terres
Rares-Actinium,” in P. Pascal (ed.): Nouveau
Traité de Chimie Minérale, vol. VII, Fascicule
1 + 2, Masson, Paris 1959.
7. J. Helgorsky, A. Lévêque, T. Petzel, K.
Reinhardt: “Seltene Erden,” in Ullmann, 4th
ed., 21, 235 – 271.
8. E. Greinacher, K. Reinhardt: “Seltene Erden,”
in Winnacker-Küchler, 4th ed., vol. 2,
pp. 678 – 707.
9. K. A. Gschneidner, Jr. (ed.): Industrial
Application of Rare Earth Elements, ACS Ser.
no. 164, Washington, D.C., 1981.
10. I. H. Jolly, R. P. Smith: “Availability of Rare
Earths to Industry,” in Proc. Rare Earth Res.
Conf., 12th, 1976.
11. C. R. Neary, D. E. Highley: “The Economic
Importance of the Rare Earth Elements,” Dev.
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 Cerium Mischmetal, Cerium Alloys, and Cerium Compounds
12. J. Griffiths, Ind. Min. (London) 199 (1984)
April, 19 – 37.
Specific References
13. Soc. Prod. Chim. Terres Rares, FR 995 112,
1949 (C. de Rhoden, M. Peltier).
14. A. E. Bearse, G. D. Calkins, J. W. Glegg, R. B.
Filbert, Chem. Eng. Prog. 50 (1954) 235 – 239.
15. P. R. Kruesi, G. Duker, J. Met. 17 (1965)
847 – 849.
16. D. J. Bauer, V. E. Shaw, Rep. Invest. U.S. Bur.
Mines no. 6381, Washington, D.C., 1964.
17. W. Brugger, E. Greinacher, J. Met. 19 (1967)
32 –35. Th. Goldschmidt AG, DE 956 993,
1954 (W. Brugger).
18. I. S. Hirschhorn, J. Met. 20 (1968) 19 – 22.
BIOS Final Rep. no. 22 (file no. XXXIII-31),
1947, p. 133.
19. BIOS Final Rep. no. 400 (item no. 21), 1945,
p. 36.
20. D. Tang, R. Song, S. Du. M. Zao, Y. Minshou,
W. Yu, Proc. Int. Symp. Molten Salt Chem.
Technol., 1st, 1983, 103 – 106.
21. Th. Goldschmidt AG, DE 2 254 245, 1974 (E.
Greinacher).
22. T. A. Henrie, J. Met. 16 (1964) 978 – 981.
23. E. S. Shedd, J. D. Marchant, M. M. Wong, Rep.
Invest. U.S. Bur. Mines no. 7398, Washington,
D.C., 1970.
24. B. J. Beaudry, K. A. Gschneidner, Jr. L. Eyring
(eds.): Handbook on the Physics and
Chemistry of Rare Earths, vol. 1 North
Holland Publ., Amsterdam 1978, pp. 173 – 232
D. C. Koskenmaki, K. A. Gschneidner, Jr. L.
Eyring (eds.): Handbook on the Physics and
Chemistry of Rare Earths, vol. 1 North
Holland Publ., Amsterdam 1978,
pp. 337 – 378.
25. K. A. Gschneidner, Jr., N. Kippenhan:
Thermochemistry of the Rare Earth Carbides,
Nitrides, and Sulfides, IS-RIC-5, Rare Earth
Information Center, Iowa State University,
Ames, Iowa, 1972. K. A. Gschneidner, Jr., N.
Kippenhan, O. D. McMasters:
Thermochemistry of the Rare Earths,
IS-RIC-6, Rare Earth Information Center,
Iowa State University, Ames, Iowa, 1973.
26. K. Reinhardt: “Addition Techniques of Rare
Earth Metals for the Treatment of Special
Steels with Rare Earths,” in Proc. Rare Earth
Res. Conf., 12th, 1976.
27. A. Raman, Z. Metallkd. 67 (1976) 780 – 789.
L. A. Luyckx: “The Rare Earth Metals in
Steel,” [9] pp. 43 – 78.
15
28. B. Zao, E. W. Langer, Scand. J. Metall . 13
(1984) no. 1, 15 – 22, 23 – 31. H. F. Linebarger,
T. K. McLuhan: “The Role of the Rare Earth
Elements in the Production of Nodular Iron,”
[9] pp. 19 – 42.
29. A. Raman, Z. Metallkd. 68 (1977) 163 – 172.
30. S. F. Radtke, D. C. Herrschaft, J.
Less-Common Met. 93 (1983) 253 – 259. F. E.
Goodwin, S. F. Radtke: Galfan Galvanizing
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