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Calcium Metal
Related terms:
 Magnesium
 Strontium
 Barium
 Samarium
 Uranium
 Reductants
 Metallothermic Reduction
 Rare Earth
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Rare Earth, Titanium Group Metals, and Reactive Metals
Production
Osamu Takeda, ... Toru H. Okabe, in Treatise
on Process Metallurgy: Industrial Processes,
2014
2.9.3.2.5.2 Metallothermic Reduction [143–145]
The production process of calcium metal by
the metallothermic reduction process (see
Equation 2.9.43) is shown in Figure 2.9.43.
The raw material CaCO3 is calcined to
produce CaO. Low magnesia content (MgO)
is preferred for the reduction feed materials
because magnesia is preferentially reduced in
this process, thus lowering the reaction
efficiency for calcium metal. A magnesium
content of less than 0.5% is desirable. The
calcined material and reductant are mixed
and pelletized at a mole ratio of CaO:Al = 3:2.
As with ferrosilicon reduction of magnesium,
the pellets are charged into the retort and
reduced at 1200 °C under 10− 3 mmHg.
Calcium metal vapor condenses on a low-
temperature zone in the retort.
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Figure 2.9.43. The production process of calcium by
using the metallothermic reduction.
(2.9.43)aCaOs+bAll=cCag+dCaO·eAl2O3s
Figure 2.9.44 shows the results of a
fundamental study on the yield of calcium
metal during reduction. A small-scale
experiment (70 g of raw material) with a 26-
mm diameter retort was used [127].
Compared to the silicothermic reduction of
magnesium, both the reaction rate and the
yield are very low. In an experiment with a
100-mm diameter retort, a deposit of 0.4 kg
(40% yield) was produced from the reduction
of 2 kg of raw material at 1200 °C for 6 h. The
analytical example of an industrial product is:
0.70% Mg, 0.14% Al, < 0.01% Mn, 0.04% N,
and < 0.03% Fe [141]. Ultrapure calcium
used for producing uranium is produced by
repeated distillation of calcium metal
(see Table 2.9.32) [146].

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Figure 2.9.44. The yield of calcium by using the
metallothermic reduction [145].
Table 2.9.32. Composition of Ultrahigh-Purity Calcium for Producing Uranium Metal
Before and After Refining [146]

Element Concentration, C (ppm)

Before Refining After Refining

Li 0.2 &lt; 0.1

Be &lt; 1 &lt; 1

B &lt; 1 &lt; 1

C 50 38
Element Concentration, C (ppm)

Before Refining After Refining

Na &lt; 1 0.4

Mg 300–3000 3

Al &lt; 3 &lt; 2

Si &lt; 1 &lt; 2

V &lt; 10 &lt; 10

Cr &lt; 3 &lt; 3

Mn 45 50

Fe 5 &lt; 3

Co &lt; 3 &lt; 5

Ni &lt; 3 &lt; 3

Cu &lt; 3 &lt; 1

Zn &lt; 100 &lt; 100

Ag &lt; 0.1 &lt; 1

Sn &lt; 1 &lt; 3

Pb &lt; 1 &lt; 2

N 175 &lt; 10

O – 0.02 ± 0.03%

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Subsea Corrosion and Scale
Yong Bai, Qiang Bai, in Subsea Engineering
Handbook (Second Edition), 2019
17.4.1 Oil Field Scales
Oil field scales are generally inorganic salts
such as carbonates and sulfates of the metals
calcium, strontium, and barium. Oil field
scales may also be the complex salts of iron
such as sulfides, hydrous oxides, and
carbonates. Oil field scales may form in one
of following two ways:
•
Due to the change of temperature or
pressure for brine during production, the
solubility of some of the inorganic
constituents will decrease and result in
the salts precipitating.
•
When two incompatible waters (such as
formation water rich in calcium, strontium,
and barium and seawater rich in sulfate)
are mixed. Scales formed under these
conditions are generally sulfate scales.
Table 17.7 lists the most common water-
formed scales in oil
field waters. Table 17.8 lists the common
causes for the formation of these deposits.
Table 17.7. Common Oil Well Scale Deposits—Solubility Factors [13]
 Deposit Chemical Mineral Name Partial Pressure Most Import
Formula CO
pH Total Te
Pressure

Calcium carbonate CaCO3 Calcite X X X

Calcium sulfate CaSO4·2H2OCaSO4 Gypsumanhydrive X X

Barium sulfate SrSO4 Barite X X

Iron carbonate FeCO3 Celestite X X X

Iron sulfide FeS Trolite X

Iron oxide Fe2O3Fe3O4 HematiteMagnetite X

X

Sodium chloride NaCl Halite X

Magnesium Mg(OH)2 Brucite X X

hydroxide

Silicates Variable X X
Table 17.8. Common Oil Well Scale Deposits—Causes and Removal Chemicals [13]

Deposit Occurrence Chemical Mineral Name Most Frequent Causes of Scale

Formula Deposit

Calcium Common CaCO3 Calcite Mixing brines, changes in

carbonate temperature and pressure

Calcium Common CaSO4•2H2OCaSO GypsumAnhydrive Same as above

sulfate

Barium sulfate Common BaSO4 Barite Mixing of brines

Strontium Not SrSO4 Celestite Mixing brines, changes in

sulfate common temperature and pressure

Iron carbonate Common FeCO3 Siderite Same as above

Iron sulfide Common FeS Trolite Corrosion by sour crude or H2S

Gas

Iron oxide Common Fe2O3Fe3O4 HematiteMagnetit Reaction of oxygen with

 Deposit Occurrence Chemical Mineral Name Most Frequent Causes of Scale
Formula Deposit

e dissolved ferrous ion

Sodium Not NaCl Halite Evaporation of water and

chloride common addition of MeOH for hydrate
control

Magnesium Not Mg(OH)2 Brucite Excessive amounts of oxygen

hydroxide common enter the well or alkaline fluids
in well, high temperature

Silicates Variable Cooling of hot brine high in

dissolved silica
17.4.1.1 Calcium Carbonate

Calcium carbonate, the most common scale

in oil and gas field operations, occurs in every
geographical area. Calcium carbonate
precipitation occurs when calcium ion is
combined with either carbonate or
bicarbonate ions as follows,
(17.18)Ca2++CO32−→CaCO3
(17.19)Ca2++2(HCO−)→CaCO3+CO2+H2O
The preceding equations show that the
presence of CO2 will increase the solubility of
CaCO3 in brine. Increasing CO2 also makes
the water more acidic and decreases the pH.
The calcium carbonate scaling usually occurs
with a pressure drop, for example, at the
wellbore. This reduces the partial pressure of
CO2, thereby increasing the pH and
decreasing the CaCO3 solubility. The
solubility of calcium carbonate decreases with
increasing temperature.
17.4.1.2 Calcium Sulfate

The precipitation of calcium sulfate is given

by the reaction
(17.20)Ca2++SO42−→CaSO4
This scale may occur in different forms.
Gypsum (CaSO4•2H2O) is the most common
scale in oil field brines. It is associated with
lower temperatures. Anhydrite (CaSO4) may
occur at high temperatures. Theoretically,
anhydrite would be expected to precipitate
above 100°F in preference to gypsum
because of its lower solubility. However,
gypsum may be found at temperatures as
high as 212°F. With the passage of time,
gypsum will dehydrate to anhydrite.
A common mechanism for gypsum
precipitation in the oil field is a reduction in
pressure (e.g., at the production wellbore).
The solubility increases with higher pressure
because, when the scale is dissolved in
water, the total volume of the system
decreases.
17.4.1.3 Barium Sulfate

This scale is especially troublesome. It is

extremely insoluble and almost impossible to
remove chemically. Barium sulfate scaling is
likely when both barium and sulfate are
present, even in low concentrations.
(17.21)Ba2++SO42−→BaSO4
Barium sulfate scale is common in North Sea
and GoM reservoirs. These fields often have
barium in the original formation brine.
Seawater injection (high sulfate
concentration) for secondary oil
recovery causes the scale problem. As the
water flood matures and the seawater breaks
through, these incompatible waters mix and a
barium scale forms.
Generally, barium sulfate solubility increases
with temperature and salinity. Similar to
gypsum, BaSO4 solubility increases with an
increase in total pressure and is largely
unaffected by pH.
17.4.1.4 Strontium Sulfate
Strontium sulfate is similar to barium sulfate,
except fortunately its solubility is much
greater:
(17.22)Sr2++CO42−→SrSO4
Strontium sulfate solubility increases with
salinity (up to 175,000 mg/L), temperature,
and pressure. Again, pH has little effect. Pure
strontium sulfate scale is rare except for
some fields in the Middle East.
SrSO4 deposits in producing wells where the
strontium-rich formation water mixes with the
sulfate-rich injected seawater.
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Hydrogen–Metal Systems: Hydride Forming Alloys
(Properties and Characteristics, Database Information)
B.-H. Liu, in Encyclopedia of Materials:
Science and Technology, 2001
Hydrogen storage intermetallic
compounds are usually classified into several
groups according to their structure types such
as AB5, AB3, AB2, AB, and A2B. A represents
strong hydride-forming elements such
as rare-earth metals,
calcium, magnesium, zirconium, and titanium,
and B represents transition metals such as
nickel, cobalt, iron, manganese, and
chromium. In this discussion hydrogen
storage materials are classified into the
following categories: (i) AB5 alloys; (ii)
AB2 alloys; (iii) AB alloys; (iv) magnesium
and magnesium-based alloys;
(v) vanadium and vanadium-based b.c.c.
alloys; (vi) disordered alloys; (vii) alloy
composites; and (viii) complex hydrides.
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Properties and Processing of Crude Oil From Tight
Formations
James G. Speight PhD, DSc, in Deep Shale
Oil and Gas, 2017
4.4 Other Refining Issues
In general, tight crude oils have low nitrogen
and high paraffin content (Table 8.1) which
can offer advantages or disadvantages to
refiners. Heavy metals, such as nickel
and vanadium, are generally low, but alkaline
metals (calcium, sodium, and magnesium)
may be high. This is highly variable and, in
addition, other contaminants such
as barium and lead may be elevated.
Filterable solids can be higher
than conventional crude oils, with greater
volume and smaller particle size.
Refining tight oil extracted through fracturing
from fields such as Eagle Ford, Utica, and
Bakken has become prevalent in many areas
of the United States. Although these oils are
appealing as refinery feedstocks due to their
availability and low cost, processing can be
more difficult. The quality of the tight oils is
highly variable. These oils can be high in
solids with high melting point waxes. The light
paraffinic nature of tight oils can lead
to asphaltene destabilization when blended
with heavier crudes. These compositional
factors have resulted in cold preheat train
fouling, desalter upsets, and fouling of hot
preheat exchangers and furnaces. Problems
in transportation and storage, finished-
product quality, as well as refinery corrosion
have a high potential.
In addition to catalyst selection, an equally
critical component to minimizing risks and
challenges associated with processing
unconventional feeds is solid technical
service support (Bryden et al., 2014).
Understanding feed impacts earlier allows
opportunity to optimize the operating
parameters and catalyst management
strategies, enabling a more stable and
profitable operation.
Hydroprocessing of naphtha from tight oils is
necessary to increase octane number and
that of middle distillates to attain cold flow
properties of diesel fuel. Also,
hydroprocessing of atmospheric residue from
tight oils yields additional naphtha and middle
distillate feedstocks for other refinery
operations. Because of a great variability in
properties, the prehydroprocessing of tight oil
feedstocks feeds may be necessary.
Hydroisomerization is the principal reaction
during the hydroprocessing of atmospheric
distillates feedstocks, while hydrocracking
and ring opening are the principal reactions
when the atmospheric residuum from tight oil
is hydroprocessed (Furimsky, 2015). In fact,
one of the significant challenges for
hydrocrackers processing significant amount
of straight run material from tight oil crudes is
a lower overall gas oil make. This lower gas
oil yield provides less
overall hydrocracker feed and has the
potential to underutilize the unit capacity
compared to processing conventional heavier
crudes.
Refining the light tight crude oils is not an
easy process and consideration must be
given to desalter performance, corrosion, and
fouling control. Furthermore, while tight oils
have many physical properties in common,
the characteristics that differentiate them from
one another are, in many cases, the root
cause of a variety of processing challenges.
For example, the methods used to extract
tight oil supplies often result in the oil
containing more production chemicals and
increased solids with smaller particle size
than conventional crudes. When introduced to
the refining process, tight oils can stabilize
emulsions in the desalter, increase the
potential for system corrosion and fouling, as
well as negatively impact waste water
treatment.
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Functional materials for hydrogen storage
M. Felderhoff, in Functional Materials for
Sustainable Energy Applications, 2012
8.3.1 AB 5–compounds
A wide range of compounds with a
composition of AB5 are known for their
applications in hydrogen storage. Element A
is often a lanthanide metal (or the much
cheaper mischmetal, an alloy composed of
variable amounts of rare earth metals),
calcium or yttrium. In most cases the B
element is nickel, but can be partially or
completely substituted with ele– ments like Ti,
Sn or Al. The properties of the materials can
vary widely, depending on the substitutions
on both the A side or the B side. The most
significant material with regard to hydrogen
storage is LaNi5, which can absorb up to
1.4 wt% of hydrogen, producing a material
with the composition LaNi5H6. The enthalpy of
the formation is − 31 kJ mol−1 H2, resulting in a
plateau pressure of 0.16 MPa at 25°C. The
AB5 hydrides have been widely used in
commercial applications in the form of nickel-
metal hydride Ni/MH-batteries. The
AB5 hydrides represent the negative
electrode of the battery.
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Porous Powders and Metallic Foams
Oleg D. Neikov, in Handbook of Non-Ferrous
Metal Powders (Second Edition), 2019
Foaming of Melts With Blowing Agents (Alporas)
In this process with the trade
name Alporas, the foaming agent is
introduced directly into the melt. Shinko Wire
Company, Amagasaki, Japan, has been
producing n this way since 1986 with a
production volume up to 1000 kg/day [1].
In the first step, about 1.5 wt% calcium
metal is added to an aluminum melt at 953 K
(Fig. 11.8). The melt is stirred for several
minutes, during which its viscosity
continuously increases by a factor of up to
five because of the formation of calcium
oxide (CaO), calcium-aluminum oxide
(CaAl2O4), or perhaps even
Al4Ca intermetallics, which thicken the liquid
metal.

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Fig. 11.8. Flowsheet of the foaming of melt with blowing
agent process (Alporas).
After the viscosity has reached the desired
value, titanium hydride (TiH2) is added
(typically 1.6 wt%), used as a blowing agent
by the generation of hydrogen gas in the hot
viscous liquid. The melt soon starts to expand
slowly and gradually fills the foaming vessel.
The foaming takes place at constant
pressure. After cooling the vessel below
the alloy melting point, the liquid foam turns
into solid aluminum foam and can be taken
out of the mold for further processing. The
entire foaming process can last 15 min for a
typical batch
(2050 mm × 650 mm × 450 mm). The foams
produced in this way seem to excel in
homogeneity (Fig. 11.9). Typical densities
after cutting off the sides of the cast foam
blocks are between 0.18 and 0.24 g/cm3, with
the average pore size ranging from 2 to
10 mm.

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Fig. 11.9. The metallic foam structure.
(Courtesy of Southeast University, China.)
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Cement Products: Characterization by NMR and MRI
P.J. McDonald, ... M. Mulheron,
in Encyclopedia of Materials: Science and
Technology, 2005
Concrete—a mix of cement and aggregate—
has been used successfully as a building
material for thousands of years. However,
the hydration process by which the cement
reacts with water to form a strong,
microstructurally complex solid remains
poorly understood. Portland cement is a
mixture of calcium silicates and metal oxides.
In the presence of water it hydrates to form
an inorganic bonding agent,
calcium silicate hydrate (CSH) gel (Neville
1991). Nuclear magnetic resonance (NMR)
provides nondestructive ways of following this
hydration process and characterizing the
chemical and physical properties of the
resultant cement and concrete products.
Some of this information is unique to NMR
analysis; or is at least very difficult to obtain
by other means. Chemically resolved NMR
spectroscopy has been used extensively to
study cement chemistry, hydration kinetics,
and CSH gel morphology by monitoring the
chemical environment mainly of the hydrogen
and silicon, but also of the carbon and
aluminum, as well as the transport
of chlorides and other ions. There are already
excellent reviews on the use of NMR
spectroscopy for studying cement chemistry
(Richardson 1999, MacLaren and White
2003). This review concentrates on other 1H-
proton NMR techniques—principally
relaxometry, pulsed-field
gradient diffusometry, cryoporometry, and
magnetic resonance imaging (MRI)—that
have been used to probe the pore-structure of
cement and the dynamics of the water within
it, both during and after hydration. The rate of
hydration and the formation of the pore
structure can be followed by measurement of
nuclear spin relaxation times. Diffusometry
and cryoporometry offer additional,
complementary information. MRI adds spatial
resolution enabling
macroscopic heterogeneity of hydration,
water transport, adsorption of surface
treatments, and the formation of structural
defects all to be visualized and quantified.
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Function Cultivation in Transparent Oxides Utilizing
Natural and Artificial Nanostructures
Hideo Hosono, Masahiro Hirano,
in Nanomaterials, 2006
1.3.5 Formation of stable electride
 1)
C12A7 electride
An electride is a crystalline ionic salt in
which electrons serve as anions. Typical
examples are compounds of cryptands or
crown-ethers as cations and the electrons
as anions [69]. Although electrides are
promising for novel applications including
a field electron emitter due to their exotic
characteristics such as small work
functions, they are not stable at room
temperature and/or in a moist
atmosphere. Thus, syntheses of a stable
electride have been sought for practical
applications. The first thermally and
chemically stable electride was realized in
C12A7 [70], we eliminated the free
O2− ions from the cages by heating
a single crystal of C12A7 in
evacuated silica glass tubes together
with calcium metal, leading to the
formation of high-density (2 × 1021 cm−3)
electrons confined to the cages. The
resultant C12A7 is described as
[Ca24Al28O64]4+(4e−), i.e., C12A7 electride.
The electrons localize in the cages,
forming F+-like centers, thereby behaving
as substitution anions for the free O2− ions.
They can migrate by hopping to
neighboring cages, giving
electrical conductivity as high as ~ 100
S·cm−1. Further, they are coupled
antiferromagneticly, forming
a diamagnetic pair or a singlet bipolaron.
2)
Synthesis of C12A7 electride
We have developed three kinds of
processes for preparing the C12A7
electride: thermal anneal of single-crystal
C12A7 with calcium metal vapor [70],
direct solidification of C12A7 in a carbon
crucible [71], and hot ion implantation
of inert gas ions [72].
Figure 1.30 shows changes in optical
absorption spectra and the temperature
dependence of electric conductivity of a
C12A7 single crystal with annealing time
in calcium metal vapor at 700°C. The
absorption bands peaked at 2.8 and 0.4
eV and the conductivity at room
temperature is enhanced with annealing
time. It indicates that the electron
concentration increases with the
annealing and reaches ~ 2 ×
1021 cm−3 when the crystal is subjected to
the chemical treatment for 240 h,
corresponding to the almost complete
replacement of the free oxygen with
electrons. The C12A7 electride is formed
by the annealing of C12A7 single
crystals in calcium vapor at 700°C. The
electrical conductivity changes from
semiconductor to degenerated conduction
types with an increase in the electron
concentration. Even metallic conduction is
observed in the C12A7 electride with an
extremely high electron concentration.
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Fig. 1.30. (a) Coloration of single crystals processed
by Ca-vapor annealing and their optical absorption
spectra, and (b) electrical conductivity as a function
of temperature.
When a mixture of C3A and CA is melted
at ~ 1600°C in a carbon crucible with a
cap and is cooled down to room
temperature in an air, the solidified bulk
changes to C12A7 and exhibits a green
color and electrical conductivity (Fig.
1.31(a),(b)) [71]. Its optical absorption and
ERP spectra indicate that electrons are
incorporated in the solidified C12A7.
Thus, direct solidification in a carbon
crucible provides a simple mass-
production process for the fabrication of
the C12A7 electride, although complete
displacement of free oxygen with
electrons is very difficult. In this process, it
is most probable that C22− ions act as a
template for the formation of the C12A7
crystallographic phase, and they are
spontaneously released from the solidified
C12A7, leaving electrons in the cages
during the cooling process. When the
reduced C12A7 glass, which is obtained
by a rapid quenching of a melt with the
stoichiometric composition of C12A7 in a
carbon crucible, is crystallized in vacuum,
the resultant polycrystalline C12A7 bulk
becomes electrically conductive (Fig.
1.31(c),(d)). This supports our assumption
that C22− ions play a significant role in
the incorporation of the electrons in
C12A7.
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Fig. 1.31. Fabrication of C12A7 electride via melting
in carbon crucible with carbon cap in air. (a)
Fabrication procedure of electride by solidification of
the reduced C12A7 melt. (b) Powder X-ray
diffraction patterns of (1) C3A+CA and (2)
Crystalline single phase C12A7. (c) Fabrication
procedure for C12A7 electride by crystallization of
transparent reduced glass under vacuum. (d)
Powder X-ray diffraction patterns of (3) Transparent
glass and (4) Crystalline single phase C12A7.
The hot-ion implantation technique for the
formation of the electride is described
later.
 3)
Electron emission from C12A7 electride
We investigated electric-field electron
emission from the C12A7 electride in
vacuum [73]. Measured electron emission
properties were explained by involving
Fowler-Nordheim tunneling at a large
electric field >200 kV·cm−1 and by
thermionic emission at lower electric
fields. The work function estimated from
the emission characteristics was ~ 0.6 eV,
which is comparable to values reported
for conventional organic electrides.
However,
ultraviolet photoelectron spectroscopy
gave a much larger value ~ 3.7 eV for the
work function. The discrepancy may be
attributed to the so-called band bending
effect due to naturally formed n+/n− layers
on the surface (the surface is oxidized).
Using the field emission of electrons from
the electride at room temperature, a
triode-structured field emission display
(FED) device was constructed employing
the electride as a cathode and a ZnO:Zn
phosphor plate as an anode. Light
emission was clearly observed under
typical ambient light, demonstrating that
the C12A7 electride is promising for FED
devices (Fig. 1.32).

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Fig. 1.32. Current-voltage characteristic for electron
emission from single crystal C12A7 electride.
The inset is a photograph of the operation of a field-
emission-light-emitting device using a ZnO:Zn
phosphor.
Recently, we have also examined the
thermal field emission (TFE) from a flat
surface of the C12A7 electride single
crystal at temperatures up to 900°C and
applied external voltages of 0 ~6 kV in
10−5 Pa vacuum using the setup
shown in Fig. 1.33 [74]. The TFE started
to occur at ~ 650°C and its current
increased steeply at ~900°C, reaching
~80 μA (~ 1.5 A·cm−2) (Fig. 1.34). The
emission with a current of ~ 50 μA from a
80-μm-diameter area is sustained stably
for more than 90 h at an extraction field of
105 V · cm−1. The work function estimated
using the Richardson-Dushman equation
was ~2.1 eV, which is smaller than that of
LaB6 (~ 2.7 eV). These experiments
strongly suggest that the C12A7 electride
has a high potential both for cold electron
emission and TFE applications. The
different characteristics in two modes for
the electron emission are likely the result
of the difference in the surface states of
the C12A7 electride.
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Fig. 1.33. (a) Experimental setup for TFE
measurement, and (b) expanded pictures of TFE
head using C12A7 single crystal.

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Fig. 1.34. (a) Electron emission current as a function
of temperature. (b) Extraction voltage dependence
of electron emission current for several
temperatures.
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Extraction of Rare Earths for Advanced Applications
G. Balachandran, in Treatise on Process
Metallurgy: Industrial Processes, 2014
4.2 Rare Earth Metal Extraction Using Metallothermic Reduction [3,6,9–16]
Rare earth metal extraction is possible using
metallothermic reduction technique. Some of
the rare earths have standard free energy
formation of their oxide higher than that of
CaO. Similarly, the free energy of formation of
rare earth halide is lower than the respective
calcium halide. Hence, such halides or oxides
had the potential to be reduced by calcium
metal. The reaction is endothermic and hence
there is a necessity of supplying heat to the
reaction. The rare earth halide salts are
mixed with calcium granules and loaded into
a tantalum crucible. The loaded sample is
heated by induction heating in a vacuum
induction process. It is possible to use the
process with electric heating as well. The
schematic of the process with reaction is
shown in Figure 15. It should be observed
that Ta crucible is expensive and fabrication
is also expensive. When one uses fluoride of
the rare earth the product of the reaction is
CaF2 which has high melting point. Hence,
the reaction temperature should be as high to
make good separation of slag and metal.
Sometimes it is possible to use another halide
salt to lower the melting point of the CaF2 salt
so that the slag is fluid at lower temperatures.
In metallothermic reduction, suitable excess
of reductant such as Ca is added for the
reaction.

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Figure 15. Schematic of rare earth compound reduction
by calcium [12–14,16]. The heat source for the reaction
can be induction or resistance heating.
Using the same set-up it is possible to make
rare earth metal from oxides. The rare earth
oxide is reacted with Ca to form rare earth
metal and calcium oxide. Since CaO is a high
melting point oxide, lower temperature is
achieved by addition of a suitable halide salt
mixture which can lower the melting point of
the products of the reaction. The metal and
slag are completely molten to ensure clear
separation of slag and metal. This is possible
for La, Nd, and Dy metal extraction.
There is yet another process reported in
literature which was developed by General
Motor Corporation patented as Neochem
process [11] as per schematic in Figure 16. In
this process, neodymium oxide is reduced
with a molten salt mixture of CaCl2 and NaCl
with sodium as the reductant. Fe is also
added in the process to make Nd–Zn master
alloy. This process has advantage over the
others as cheaper sodium is used as a
reductant. Direct use of sodium reductant
does not reduce the rare earth oxide. The
mechanism of the reaction is shown in the
figure. The Na added forms Ca in situ, which
reduces the rare earth oxide. The Nd–Zn
master alloy is vacuum-distilled to make pure
Nd metal.
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Figure 16. The Neochem process used for extraction of
Nd as Nd–Zn master alloy with sodium reductant. The
Nd–Zn master alloy is vacuum-distilled to get pure Nd
metal [15].
It is sometimes advantageous to extract rare
earth master alloys instead of rare earth
metal. In that case, it is possible to add
master alloy metal powder or metal swarf
along with rare earth salt. This Ferro
neodymium (Fe–80% Nd)
or Lanthanum nickel (La–70% Ni) master
alloys can be extracted by adding Fe or Ni
respectively along with respective rare earth
in the reaction mixture. The typical lab scale
extraction schematic is shown in Figure 17.
The master alloy making technique lowers the
overall temperature of the process when a
low melting eutectic such as Fe–88% Nd is
attempted. In the case of samarium metal, it
is difficult to extract samarium with Calcium
metal as a reductant. It is mainly because
both Sm and Ca have high vapor pressure
and hence the product would be Sm–Ca alloy
instead of pure samarium. Hence, for
extraction of samarium pure metal a different
process technique is followed. Here,
samarium oxide is reduced with lanthanum or
misch metal instead of Ca. This is a favored
reaction because the free energy of formation
of lanthanum oxide is lower than that of
samarium oxide. Since lanthanum itself is
expensive, it is possible to produce samarium
metal using misch metal instead of pure
lanthanum. The metallothermic reduction is
carried out in vacuum and at high vacuum
level. The entire reaction takes place within
tantalum crucible. The samarium metal has
high vapor pressure and it is condensed on
top condenser zone of the tantalum crucible.
The samarium metal extraction schematic is
shown in Figure 18.

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Figure 17. The typical rare earth master alloy extraction
technique. The phases formed in the extracted Nd–Fe
master alloy are also shown [12–14].

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Figure 18. Extraction of Samarium metal by
lanthanothermic reduction [13]. Similar process is used
for extraction of pure Europium and Ytterbium.
It is also possible to make rare earth
alloy compounds directly by calciothermic
reduction using a solid state process known
as reduction diffusion process or co-reduction
processes. The schematic of the process is
shown in Figure 19. In both these processes,
the reactions are carried out as solid state
reactions at a temperature of the order of
1050–1100 ᵒC. In this process for the
manufacture of Sm–Co alloy, the samarium
oxide along with Co powder of suitable size is
reacted with Ca metal granules. Co powder is
very expensive and the process condition has
to be optimized for the required powder
particle size. The Sm2O3 is reduced by Ca to
form Sm metal and CaO. The CaO being a
refractory oxide holds the entire reaction
mass solid, The initial reaction product of Sm
is held long enough for Sm to diffuse into Co
to form SmCo5. This alloy powder remains
separated as solid powder by the reaction
products CaO. The reaction mass is crushed
and leached with mild acid such as oxalic
acid to recover SmCo5 alloy powder. The
process can be also carried out with
SmCl3 instead of Sm2O3. The process is
capable of making the multicomponent alloy
Sm2(Co, Fe, Zr, Cu)17 also. The ingredients
added should have preferably metallic
powder mixtures of the alloying constituents.

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Figure 19. Synthesis of Samarium–Cobalt alloys from
samarium oxide and Co powder by reduction diffusion
process [17].
The process of solid state reduction diffusion
is termed as co-reduction process, when the
part of alloying elemental charge is in oxide
form. That is, in Sm–Co alloy, instead of Co
metal cobalt oxide is added in the reaction.
The reaction between the metal oxide (such
as cobalt oxide) and Ca gives some
additional reaction heat for the reaction.
Using Fe instead of Co can give Sm2Fe17 type
powder which can be nitride and used as
another type of Sm–Fe–N magnet. The co-
reduction or the reduction diffusion process is
the predominant production process for
making Sm–Co alloy magnet. There are few
companies in the world, which operate the
process in tonnage levels.
The same reduction–diffusion technique can
be used for direct extraction of Nd–Fe–B
magnet using calciothermic reduction
technique [10]. The alloy composition is
targeted at Nd15Fe77B8. The reaction can be
carried out in a reactor shown in schematic
in Figure 20. The reactions involved are direct
reduction of Nd from its oxide followed by its
alloying in iron powder taken. The various
process reactions and details of a trial run in
a typical laboratory run was found to be
> 85%. This process is applied for both
chloride and oxide feed materials. The
temperature of the reaction is about 1000–
1100 ᵒC. The principles can be extended to
making LaNi5-based hydrogen storage
alloys as shown in Figure 21. The lanthanum
oxides can be substituted with mixed rare
earth oxides to form Mm–Ni alloys. The Ni
element is sometimes substituted with Co, Al,
and Mn. These have also been used to
successfully make the rare earth
alloys directly. It is possible to produce the
alloys in large-scale level reliably.

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Figure 20. Synthesis of Nd–Fe–B alloy from neodymium
oxide or chloride, iron powder and Ferro boron or B2O3 by
reduction diffusion process [13].
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Figure 21. Synthesis of La or Misch metal Mm–Ni–Co–
Mn–Al alloys made using reduction diffusion process
[3,18].
One of the main reductants used for the
extraction of rare earth metals is calcium
metal, which is also extracted by
calciothermic reduction technique or by
vacuum reduction of CaO by Al. The Ca used
for such reduction has to be of good quality
without oxidation and should be of granular
form.
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