Extractive Metallurgy of Rare Earths: C. K. Gupta and N. Krishnamurthy

Extractive metallurgy of rare earths
C. K. Gupta and N. Krishnamurthy
oped for mixed or simply separated rare earths. The

A comprehensive review is presented of the following two decades, 1940-60, were the most pro-
extractive metallurgy of rare earths. The topics ductive in terms of effective process development.
covered are: world rare earth resources and Most important were the development of modern
production; ore processing and separation of separation methods using ion exchange and solvent
individual rare earths; reduction, refining, and extraction. This resulted in the availability of sufficient
ultrapurification of rare earth elements; methods quantities of pure individual rare earth compounds
for rare earth materials analysis; and a selection of for the investigation of reduction processes to prepare
the numerous rare earth applications. World rare
pure metals and alloys and the evaluation of their
earth reserves are abundant and would last for well
beyond the next century. However, all of the 16 properties. Beginning in 1960, progress was made in
naturally occurring rare earth elements are not the production of purer rare earths, in the identifi-
equally distributed in the ore minerals. This, cation of new properties of rare earths, and in their
compounded with the problems specific to the use in a wider variety of commercial applications.
isolation and recovery of each of the rare earths, The usuable forms of rare earths encompass naturally
sets the stage for an unequal rare earth availability. occurring oxide mixtures and products synthesised
The close chemical similarity of rare earths looses from them, and high purity individual metals, alloys,
its importance when divergent physical properties and compounds. The current annual world demand
determine the processes for rare earth element
for rare earths is in the range 25 000-30 000 t (Ref. 4)
reduction and refining. The rare earth metals,
calculated as rare earth oxides. It has also been
alloys, and compounds have been as pure as could
be determined. Finally, the commercial demand for estimated that the world rare earth reserves are large
a rare earth has often been out of phase with its and sufficient to support the present level of consump-
chemical availability. The review addresses itself to tion for several centuries to come.
these points while providing a summary of the Rare earths have been of considerable technical
substantial body of information presently available and commercial interest and this is also borne out
on the extractive metallurgy of rare earths. by the substantial body of published literature5-29
IMR/239 and numerous international symposia and meetings
held during the past three decades.4 A considerable
© 1992 The Institute of Materials and ASM International. Dr
volume of the published literature refers to the extrac-
Gupta and Dr Krishnamurthy are with the Materials Group,
Bhabha Atomic Research Centre, Trombay, Bombay, India. tive metallurgy of rare earths which, in particular,
has traditionally been an active branch of rare earth
technology.
This review is confined to the extractive metallurgy
of rare earths. In the first three sections the status of
Introduction rare earth resources, ore treatment, and separation
The term 'Rare earths' denotes the group of 17 processes are reviewed. Subsequently, the reduction
chemically similar metallic elements which includes and refining processes, and preparation of industrially
scandium, yttrium, and the lanthanides.1 The lanthan- important rare earth alloys are discussed. The import-
ides are the series of elements with atomic numbers ant role of analysis in extractive metallurgy is then
57 to 71, all of which, except promethium, occur in presented, followed by a selection of the applications
nature. The rare earth elements, being chemically of rare earths - particularly the more recent ones.
similar to one another, invariably occur together in The review is concluded by highlighting the present
the source minerals and behave as a single chemical trends and indicating certain future projections for
entity. Thus, the discovery of the various rare earth the rare earths.
elements themselves occurred over the 100 year period
from 1788 to 1891.2,3 Then followed the problem of
separating them from one another for scientific study Resources
or industrial use. This has been one of the most All the rare earth elements except promethium (atomic
challeriging tasks of rare earth technology. While the number 61) occur in nature. In terms of inherent
efforts in separating the rare earths began with the abundance in the earth's crust,30 several rare earth
work of Mosander, who during 1839-41 separated elements are more abundant than many better known
fractions containing lanthanum and didymium from metals, Fig. 1. Among the rare earths the relative
the 'earth' ceria and fractions containing terbium and natural abundance varies widely, the most abundant
erbium from the 'earth' yttria. Much of the effort being cerium and the least thulium. However, more
directed to the separation of various rare earths than an element's estimated average crustal abund-
occurred from 1891 to 1940. During this period, from ance, the nature and extent of its concentration in
the available separated and mixed compound inter- mineral deposits influence its commercial avail-
32
mediates many rare earth metals and alloys were ability.31 Rare earths are dispersed elements ,33 and
prepared and commercial applications were devel- they are unfavourably and poorly concentrated. They
International Materials Reviews 1992 Vol. 37 NO.5 197

198 Gupta and Krishnamurthy Extractive metallurgy of rare earths
availability is very small in comparison. Hence, the presence

500 RE of a higher proportion of heavy rare earths in xenotime does
not have much impact on overall rare earth availability. Large
E 100 Zn Ce Cu
a. differences, therefore,
c.
Q)
50 YLaNd are inherent in the availability of different rare earths.
Pb
(,)
c
0
-0
c
10 Sm Monazite
~ 5 Monazite is a phosphate mainly of the cerium group
.c
0 (La-Nd) rare earths and thorium and is found in
Sn
E many geological environments. It occurs as an access-
~
~
!J)
u
0.1
0.5
1
~DD ory mineral in acidic igneous rocks, in metamorphic
rocks, in certain vein deposits, and due to its chemical
stability also develops into detrital mineral in placer
deposits and beach sands. Primary monazite deposits
have been commercially important in a few instances.
1 Abundance of rare earths and some common metals Notable among them are operations in South Africa
in earth's crust at Van Rhynsdorp and Naboomspruit, in the USA
in Colorado, and in China at Bayan Obo.37
Commercially, the most important sources of mon-
do not occur in minerals as individual rare earth azite are beach placers and associated dune sand
compounds. Any rare earth mineral usually contains deposits. They contain, in addition to monazite, other
all the rare earth elements with some of them enriched heavy minerals like ilmenite, rutile, and zircon. Some-
and some others in very low concentrations. Nearly times monazite co-occurs with placer tin or gold
35
200 minerals containing > 0·01 wt- % rare earths are deposits. Monazite containing heavy mineral sand
presently known. Of these only about a dozen, given deposits are found in large quantities in Australia,
in Table 1, occur in sufficient quantities to be consid- Brazil, India, China, Malaysia, South Africa, and the
34
ered as resources for commercial extraction. ,35 USA. The locations of these and many other deposits
Moreover, about 95% of the rare earths occur in are given in Fig. 3.38,39 The rare earth distribution in
only three minerals: bastnasite, monazite, and xeno- monazite is variable40,41 depending on the location,
time. These three, therefore, are the principal ore Table 2.In general, no two samples of a rare earth
minerals for rare earth extraction. mineral from different locations have exactly the same
The first seven lanthanides (La to Eu are usually distribution of mixed rare earths.
referred to as the cerium subgroup of the rare earth Xenotime
33
elements or 'light' rare earth elements and the
remaining eight elements, Gd to Lu, together with
Xenotime, like monazite, is a rare earth thorium
yttrium are said to belong to the yttrium subgroup
or 'heavy' rare earth elements. orthophosphate but contains up to 63% Y203 and
also a markedly higher proportion of heavy rare
The content of individual rare earths elements in
earths, Table 3. The mineral is a minor constituent of
monazite and bastnasite qualitatively reflect the rela-
granite or gneiss. 35 Having undergone a similar
tive abundance of rare earths in nature, Fig. 2. The
weathering, transportation, and concentration process
proportion of the heavier rare earths (Sm-Lu) content
as monazite, xenotime co-occurs with it in placer
in bastnasite is considerably less than in monazite
deposits but such deposits are relatively few. Commer-
which itself is less than that anticipated from the
cially significant quantities of xenotime occur in placer
crustal abundance data. In xenotime, yttrium and
cassiterite deposits in Malaysia, Indonesia, and
some of the lessabundant rare earths are present in
larger proportions. While the minerals bastnasite and
monazite are abundantly available in nature in
Table 2 Rare earth distribution in monazite from
almost equal quantities,36 xenotime occurrence and
different locations (percent of total rare earth
Table 1 Important rare earth minerals
oxide)
Rare Eastern Western
earth Brazil India Florida Australia Australia China
Mineral Composition
La 24·00 23-00 17-47 20-20 23-90 23-35
Bastanasite CeFC03 Ce 47-00 46·00 43-73 45-30 46-03 45-68
Monazite (Ce,La,Th,Y) P04 Pr 4-5 5-5 4-98 5·40 5·50 4-16
Xenotime YP04 Nd 18-5 20-00 17-37 18·30 17-38 15·74
Euxenite (Y,Ca,Ce,U,Th) (Nb,Ta,Tib06 Sm 3-0 4-0 4·87 4-6 2·53 3-05
Apatite Cas(P04hF Eu 0-055 0·16 0-10 0-05 0·10
Gadolinite Be2FeY 2Si2010 Gd 1 6,56 2-00 1-49 2·03
Loparite (Ce,Na,Ca) (Ti,Nbb06 Tb 0-1 0-26 0-20 0-04 0-10
Uraninite (U,Th,Ce,Y,Pb)02 Dy 0·35 1·50 0-90 1'15 0-69 1·01
Brannerite (U,Ca,Fe,Th'Y)3 TisO'6 Ho 0·35 (Eu-Y) 0·11 0-05 0-05 0-10
Doverite CaY(C03)2F Er 0-07 0-04 0-40 0·21 0·51
Pyrochlore (Na,Ca,REbNb206(F,OH) Tm 0·005 0-03 Trace 0-01 0-51
Allanite (Ca, RE,Thb(AI,Fe, Mgh' Si3012(OH) Yb 0·02 0-21 0·20 0,12 0·51
Perovskite CaTi03 Lu ND 0·03 Trace 0-04 0·10
Zircon (Zr,Th,Y,Ce)Si04 Y 1-4 3·18 2·10 2'41 3·05
International Materials Reviews 1992 Vol. 37 NO.5

Gupta and Krishnamurthy Extractive metallurgy of rare earths 199
monazite
crusta l distri bution
Tm
Sm
Ho Eu
Gd Ce
y
Tb
Dy
Er Ho
Yb Tm
Sm-Lu Lu y La
Tb Y
La Nd
Pr
La
Ce
bastnasite
2 Relative abundance of rare earths in major minerals
Table 3 Rare earth distribution in minerals (percent of total rare earth oxide)
Bastnasite Jiangsi clay
Xenotime, Uranium residues, Kola A
Rare earth California China Malaysia Canada apatite B
La 32·00 27·00 0·50 0·80 25·78 1'8-5'0 31-40
Ce 49·00 50·00 5·00 3·70 46·22 0·3-1·7 3-5·5
Pr 4·40 5·00 0·70 1·00 4·00 0·7-2·2 7·7-11
Nd 13·50 15·00 2'20 4·10 14'4 5·0 26-35
Sm 0'50 1·10 1·90 4·50 1·6 3·7 4-5'5
Eu 0·10 0·20 0·20 0·20 0·5 0·12 0·4-0·6
Gd 0·30 0·40 4·00 8'50 1·5 6·8 3·5-4·0
Tb 0·01 1·00 "20 0·1 1·0-1·5 0·25-0·
Dy 0·03 8·70 1·02 5
11·20 7-8 2-3·5
Ho 0·01 2·10 2·60 0·10 1·7 0·4-0'6
Er 0·01 1·00 5·40 5·50 0'15 5·0 0'8-1·5
Tm 0·02 (Tb-Lu) 0'90 0·90 0·02 1·0 0'1-0'3
Yb 0·01 6·20 4·00 0·08 3·0-4·0 0·6
Lu 0·01 0·40 0·40 0·4 9-11
Y 0·10 0·30 60·80 51·40 4·40 60

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Thailand and in the ilmenite, rutile, zircon con- silicate occurring commonly and widely distributed
taining hea vy mineral sands of Australia and in pegmatite bodies throughout the western USA and
4o
China. ,42 Recoverable quantities of xenotime also many other parts of the world. It is relatively low in
occur in the alluvial tin mine in the Mapuera region rare earth and titanium contents but might be pro-
of Amazanos State, 42 duced at a lower cost per tonne than monazite.
Brazil. Apatite and other phosphorites constitute a sub-
Bastnasite stantial resource for the rare earths.35,38,40,55-58
Unlike most of the rare earth minerals which are
Bastnasite is a fluorocarbonate of cerium and other found only in small quantities in a potential ore body,
rare earth metals and contains hardly any thorium. apatite occurs in large quantities like monazite and
The mineral occurs in a finely divided form or as bastnasite. Apatite is not a rare earth mineral but a
phenocryst in carbonatites. Quartz veins and epi- rare earth concentrating mineral. Rare earth ions
thermal fluorite bearing veins also contain this min- proxy calcium ions in the lattice because of the similar
eral. 37 Bastnasite was not so well known until the size of rare earth and calcium ions. The rare earth
discovery, in 1949, of a large carbonatite deposit in content of apatite is highly variable and ranges from
Mountain Pass, California.43 The ore contains about a trace to over 100/0. The amount and distribution of
600/0 carbonates (mainly calcite), 20°/0 barite, 10°/0 rare earths being dependent on the nature of the host
rare earth fluorocarbonates, and 10°10 other minerals rock. Rare earth rich apatites are found at the Kola
including silica. A smaller bastnasite deposits occurs Peninsula and at Vishnevye Mountain, CIS,38,40 at
(Fig. 3) in Burundi (Karonge). the Phalaborwa complex in South Africa,39 at several
The world's largest deposit of rare earths is found locations in the USA including in the iron ores of
at Bayan Obo in Inner Mongolia where bastnasite Mineville, NY, California placers, 59 and in Florida.55
and monazite co-occur as associated minerals in iron Phosphorite samples from the large Phosphoria For-
ore.44,45 The three ore bodies of Bayan Obo are mation of Idaho, Montana, Utah, and Wyoming
deposited as lenticular veins in dolomitic limestone. average 0'160/0 rare earths.35,37 In spite of their low
The Bayan Obo ore, called biotite, comprises more rare earth content apatites could become an import-
than 100 kinds of minerals considerably intergrown. ant source of rare earths because they are processed
The main minerals are of iron, rare earths, and in large quantities. The reserves of rare earths from
46
niobium as well as fluorite. Bastnasite and monazite phosphate sources have been estimated to be in excess
6o
account for about 700/0 and 300/0, respectively, in the S Mt. ,61
rare earth fraction of the ore47 and Bayan Obo Pyrochlore is another rare earth concentrating
deposits contain an estimated 36 Mt of rare earth 35
mineral and a promising source of rare earths. ,42
oxide of (REO) which is about SOO/o of the total world In this mineral, rare earths substitute in the alkali
rare earth 40 position. Large deposits of this mineral are known to
reserves. occur at St. Honore and Oka, Que.,62,63 Araxa,
Other rare earth resources Brazil,38 and at various places along the Rift valley
in East Africa. The rare earth content of Oka pyroch-
In addition to the three major minerals there are lore averages almost 10°10 and ranges from 2·5 to
several other rare earth resources which are important 11·so/0 REO.
but with no large scale processing at present. The Large quantities of rare earths are contained in
mineral euxenite occurring in the placer deposits of perovskite ore bodies.32 Perovskite is also a rare earth
Idaho is a complex tantaloniobate of titanium, rare concentrating mineral, the rare earths substitute cal-
earths, thorium, and uranium. These co-occurring cium. Rare earth containing varieties, enriched essen-
metal values and its heavy rare earth content make tially in light rare earths, are mainly associated with
euxenite processing attractive.48 Gadolinite is another alkalic igneous rock suites. Zircon is also known to
important source of yttrium and the heavy rare earths. accept a spectrum of rare earth elements in the
Recently, gadolinite deposits have been found in mineral and can be considered as a probable source
Canada in Quebec and Yellowknife, NWT.4o,49 The of yttrium and heavy lanthanides.32 It has been
uranium ores brannerite and uraninite contain rare recently established that granite like subalkaline rare
earths and such ores occur in the Precambrian quartz metal metasomatites located near faults may serve as
pebble conglomerate at Elliot Lake, Ont.,50,51 Fig. 3. an important source of yttrium and the other rare
64
Brannerite also occurs in association with gold in the earths. In the Jiangxi province of the People's
Witwatersrand deposit in South Africa42 and at Rad- Republic of China (PRC) a large reserve of a rare
ium Hill, Australia.38 Rare earth minerals often occur earth containing clay (Longnan Clay) has been
39
associated with iron ores. Apatite rich tailings of the reported. ,45 Over 1 Mt of rare earth oxide are
iron ore mine at Mineville, Ny52 are being considered con tained in this reserve. This ore is characterised by
as a potential source of rare earths.42 Magnetite a low cerium content (0'3-5'5°/0) and higher sam-
deposits at Dover, NJ contain xenotime, doverite, arium, europium, and terbium or higher yttrium
and bastnasite.53 Incidentally, the gadolinite deposit concentrations, Table 3.
in Quebec and China's Bayan Obo deposits are also As shown in Fig. 3, commercially significant rare
iron ore-rare earth mineral associations. A large earth mineral deposits are found throughout the
<;leposit of the mineral loparite occurs in the Kola world. In spite of the large number of indicated
Peninsula, CIS. The supply of loparite is associated locations, about SO% of world rare earth reserves are
with the huge titanium recovery operations in the concentrated in the PRe, 11% in North America,
Peninsula. 54 Allanite is a rare earth-calcium-iron and 50/0 in India. The distribution by country of rare

earth reserves is also indicated in Fig. 3. The major minerals

constituting these reserves are monazite, bastnasite, and
xenotime; in Canada the uranium ores; and in the CIS
apatites and loparite. 50
The rare earth element scandium does not occur o
in the rare earth minerals. The major source of W
scandium is uranium ores which contain about 0·1 0/0 0::: 40
+-
scandium. Some scandium is also recovered as a ..:x:
byproduct of wolframite. Scandium content in wolf- c MALAYSIA

o INDIA
ramite is of the order of 500-800 ppm and this is -.;:
considered an important potential resource in the g
"'C
30 BRAZIL
USA. The only mineral that contains a large percent- o

~
age of scandium is thortveitite. This mineral is very c-
rare and isnot counted as an important source of o ::3
20
c
scandium. Slags from blast furnaces used in the c
production of cast iron and tin smelting have also <!
been sources of scandium.65 Several rare earths are 10
found in the elements formed in the fission of uranium

USA
and plutonium. The fission products from nuclear
reactors are the only source 66 1970 1975 1980 1985
of promethium.
World rare earth production 4 World rare earth production

Commercial mining of rare earth reserves began a
100 years ago. Monazite was the major rare earth
source from the beginning of the industry until 1965.58 coproduct of bastnasite in Bayan Obo ore processing.
Thereafter bastnasite production equalled or exceeded China's contribution to world monazite production
monazite production. At present, bastnasite is the was not known before the 1980s but it has grown
67
world's major source of rare earths and constitutes considerably during the past few years. ,70 The pub-
67
62% of world output of rare earth minerals. Incident- lished data on world rare earth production during
71
ally, no bastnasite was produced before the 1950s. the past 20 years are plotted in Fig. 4. Except for
Production of other RE minerals has largely remained the USA and part of the PRC's contribution, the rare
sporadic and small in proportion.40,58 earth production in other countries is mostly derived
Monazite was first produced in Brazil in 1885 from from monazite. The major amount of monazite is
68
the beach sand deposits. Within two years pro- obtained as byproduct from the extraction of ilmenite,
duction started in the USA from placer deposits in rutile, or zircon in Australia, Brazil, India, or from
the Carolinas and continued till 1910. Production placer cassiterite mining in Malaysia. Since 1967
began from Indian beach sand deposits in 1911. India Australian beach sand deposit has become the major
and Brazil were the principal sources of world rare source of monazite supply and in 1988 Australia
earth supply until the late 1940s when Australia and continued to dominate, contributing nearly 37% of
Malaysia also started regular monazite production. the total world monazite production.67 Monazite does
Monazite has also been produced occasionally or in not occur in great enough concentration to be recov-
small quantities in other countries such as Egypt, Sri erable as a primary ore mineral. It is essentially a
Lanka, Korea, Madagascar, Indonesia, and in Saskat- byproduct and the monazite production figures are
chewan, Canada. Production restarted in the USA in susceptible to influence by the market for the other
1948 with the recovery of monazite as byproduct in co-occurring minerals. In Brazil, however, the heavy
mining Florida beach sands for titanium minerals mineral sand mining is conducted primarily for mon-
39
and zircon. Since early 1950 monazite has been azite value rather than for ilmenite, rutile, or zircon.
produced commercially in the states of California, In the past, thorium content in monazite enhanced
Colorado, Georgia, Florida, Idaho, and the Carolinas, the economics of monazite mining,37 but at present
though at present it is being produced only in Florida safety regulations concerning the radioactivity of thor-
and North Carolina.40 Monazite has also been re- ium are affecting monazite production and sale.69
covered from a hard rock deposit by Amax at their Bastnasite is a less problematic source of rare
Climax, CO mine. Monazite production data in the earths. It hardly contains any thorium. It is mined as
USA have not been disclosed but the tonnages do the primary product by the major producer, the USA
not appear to contribute substantially to world mon- from the large bastnasite deposit in Mountain Pass,
43
azite production. CA. Ore grades in the deposit average about 7 wt_%
An unique vein deposit was discovered in 1950 at REO. This high concentration has made it possible
Van Rhynsdorp in the Republic of South Africa. This to mine the ore in its own right. It is the only rare
remained the major source of monazite for a decade earth operation in the world that derives its total
68
during 1953-63. In the CIS a considerable quantity revenue from the rare earths.42
of monazite is probably produced but no production Production began from the Mountain Pass deposit
data are available.58 The Chinese monazite pro- in the 1950s and this has remained the only source
duction comes from the placer like deposits in the of bastnasite for over three decades. The only reported
provinces of K wangtung and 69 and as a production of bastnasite outside the USA was the
Kiangsi
50,000 Ce
La
10,000 Nd
5000 Pr
0
w
0:+-: 1000 Sm Y
.. 500
western world cumulative

...:x: Gd Dy
:c
Q)
production to 1985
~ (0.635 Mt REO)
0
Q)
>
0 100 Er world reserves
u
50 Eu Yb ( 45 Mt REO)
+-
~ Q) Tb Ho Lu
(/)
Q) world cumu lative demand
:;:: 10 Tm to the year 2000
c
0
:J
(0.810 Mt REO)
0 5
1 ~ ~ ~ ~
5 Quantities of individual rare earths

theoretically recoverable from world rare 6 Estimates of world long term rare earth availability
earth reserves
occasional very minor production in Burundi. Pro-
4o Rare earth recovery
earth from Kola apatite. ,42
duction began in China in the 1980s. In China from apatite is technically feasible during the manu-
bastnasite is produced as a byproduct of iron ore facture of phosphoric acid. A considerable amount of
mining in Bayan abo. Chinese mine production research has been conducted on the process. Haskin
capacity was about 6000 t REO in 1982 and rose and Paster32 have observed that more rare earths are
phenomenally to over 20000 t REO in 1985.72 Bast- being presently discarded during phosphate pro-
nasite accounts for the major fraction of Chinese duction than is needed to meet the current world
output. According to Robjohns67 in the present total demand for these elements. Apatite could become a
Chinese production capacity of 20100 t REO, bast- steady source of byproduct rare earths because of the
nasite accounts for 14 000 t, monazite 4500 t, an ion regular demand for phosphate fertilisers. In 1986 over
adsorption ore (Jiangxi clay) 1200 t, and xenotime 400 t. 1000 t of monazite were recovered from phosphate
Xenotime production is less than 1% of the total sources in the USA.60 Earlier, Adams and Staatz
51
tonnage when it is compared with monazite or bast- had estimated that about 4000 t of contained yttrium
73 were being mined from the Retort and Meade Peak
nasite. It is recovered essentially as a byproduct of
processing tin ore in Malaysia, Thailand, and China. members of the Phosphoria Formation, USA.
In Australia processing of heavy mineral sands also According to Haskin and Paster32 the processing
yields minor amounts of xenotime. Some xenotime of large deposits of perovskite for titanium could yield
has also been recovered in Brazil from the Ptinga byproduct light rare earths in large quantities.
alluvial tin mine.42 While the USA, Brazil, India, Australia, and China
The proportion of heavy rare earths in monazite have been themajor suppliers of rare earth minerals
is small but monazite remains the commercial source in the past, Hedrick36 predicted that future supplies
of heavy rare earths. This has been so because of the would come mainly from China, the USA, and India.
larger scale of monazite operations and its higher The reserves in Australia and Brazil are either rapidly
heavy rare earth content than bastnasite. being depleted or are not available for exploitation
Several other sources particularly those providing because of environmental restrictions. Even though
heavy rare earths have also been exploited for com- in terms of total REO content the world rare earth
mercial production. These include euxenite from reserves amount to an impressive figure of about
Idaho and gadolinite from Canada.40 A rare earth 45 Mt, theamount of individual rare earths theoret-
recovery plant has been in operation intermittently ically recoverable from this vast reserve varies greatly
between 1967 and 1978 and, after modernisation, as indicated in Fig. 5. Hedrick36 has calculated the
since 1986 at the Denison Mines, Elliot Lake, ant. theoretically recoverable RE content from world
for the recovery of yttrium and heavy rare earths reserves assuming that one half of the world's rare
from uranium leach solutions.49 In 1988 nearly 100 t earth reserves are in bastnasite and one half in
of contained Y203 was produced from this source.67 monazite and these ores could be mined and separated
A certain amount of rare earths has also been reco- without mining, milling, or refining losses.
vered from the Witwatersrand uranium deposit in The estimated long term rare earth availability is
South Africa.42 presented in Fig. 6.40 In relation to the western world
Rare earth production in the CIS has been from cumulative production to 1985(635 000 t REO) and
loparite and apatite in addition to monazite. 58 A the US Bureau of Mines estimate of cumulative
plant in Finland earlier recovered byproduct rare demand to the year 2000 (810 000 t), rare earth

204 Gupta and KrishnamurthyExtractive
metallurgy of rare earths beach sands (1-4
% HM)
rubble, shells,
quartz, mica
preconcentrate (.v90 % HM)
quartz, mica
non mag mag: ilmenite
non cond cond: ilmenite non cond cond
magnetic separa tion ilmenite ,rutilE: ,garnet,

sill imani te
non cond cond:
ilmenite, leu coxene

conc tai li ngs
magnetic separation
mag: non mag: mag: non mag: mag: non mag
monazite zircon monazite zircon monazite zircon

7 Physical beneficiation of beach sand minerals
reserves appear to be very substantial. Recent dis-coveries of out. 74 For example, a lean deposit containing 2-50/0
rare earths in geological environments hitherto unexploited %
HMs is first concentrated to 20-30 HMs on cone
also suggest that the undiscov-ered resources are probably concentrators. This product is then fed into spirals
1o which give a concentrate of more than 80% HMs.
very large. However, the inherent unequal availability of
The separation of individual minerals is then
rare earths, deter-mined primarily by their distribution in
achieved by exploiting the small gravimetric differ-
monazite and bastnasite would remain a continuing problem.
ences or the slight differences in magnetisability and
surface ionisation potential between the various co-
35 Among the beach
Resource processing occurring minerals. ,37,68,74-76
sand minerals, the specific gravity of monazite is the
Physical beneficiation
highest. Ilmenite, garnet, xenotime, and monazite in
Monazite and xenotime decreasing order of magnetisability, behave as mag-
In the placer deposits, monazite occurs as a minor netic materials. In electrostatic separation, ilmenite
constituent along with sillimanite, garnet, magnetite, and rutile behave as conducting materials and others
while the major minerals are ilmenite, rutile, zircon, non-conducting. Xenotime is more strongly magnetic
and quartz. Occasionally trace quantities of other than monazite and in magnetic separations concen-
minerals such as cassiterite, chromite, picotite, badde- trates with ilmenite. Being a poor electrical conductor,
leyite, cinnabar, and native metals such as gold and xenotime is electrostatically separated from ilmenite.
platinum are also present. The beach sand deposits Leucoxene, when present, can cause problems in the
exhibit a considerable variation in mineralogy and separation of monazite from ilmenite. A reduction
35
chemical composition depending on the location. ,40 roast at 600°C (Ref. 77) converts free hematite in
The flowsheets for their beneficiation are therefore leucoxene into magnetite and enables easy separation.
variable in detail. However, as the task is essentially The flowsheet for heavy mineral processing in
the separation of already crushed minerals with quite Thailand for the recovery of xenotime, with monazite,
similar physical properties, the flowsheets have several chromite, rutile, zircon, and garnet as byproducts is
37
features in commo,n. An outline of the major steps in given in Fig. 8. The preconcentrate is separated on
the processing37 is given in Fig. 7. shaking tables into three products with different
The highest concentration of heavy minerals (HMs) specific gravities before processing on an electrostatic
in beach sand are found in the Mana valakurichi separator, an induced roll separator, and a cross-belt
%
(70-80 HMs and 4-7% monazite) and Chavara separator. Finally, the mineral concentrate of monaz-
deposits (70-80% HMs and 0·7-1 % monazite) of ite, xenotime, and rutile is treated again on a shaking
India. Preconcentration by wet gravity methods is gen- table.
erally not required for these deposits. With the Orissa The dredging operations formerly operated in the
deposit of India (20% HMs and 0·4% monazite) and gold placers of Idaho and the tin placers of South
for most other deposits throughout the world, bulk East Asia are similar. 35, 78 Before the separation of
concentration of the heavy minerals is needed before the heavy mineral concentrate, the gold was removed
the actual separation of individual minerals is carried by amalgamation and cassiterite was recovered using

heavy mineral sand crude ore
rubble ,shell
quartz, mica
pre-concentrate
quartz, mica
garnet, quartz non-magne tic tailings

turmaline ( 11% REO)
ilmenite
hematite tailings for
magnetite
Nb extraction
garnet
rutile fLotation concentrate
C mixed bastnasite, monazite: 56 % REO)

ilmenite
magnetite
monazite monazitel xenotime turmaline bastnasite monazite

xenotime concentrate concentrate
(68% REO) (47% REO)
8 Flowsheet of heavy mineral sand processing in Thailand
10 Physical beneficiation of Bayan Obo
ore
a series of jigs. The separation of monazite, columbite, to be crushed before they are concentrated by
and euxenite from heavy mineral dredge concentrate, exploiting gravimetric, magnetic, or surface wettabil-
however, is achieved in a dry plant using a com- ity differences. At Mountain Pass, the ore contains
bination of high intensity magnetic separation, high 7-12% bastnasite and is obtained by open cast
tension separation, and dry and wet tabling.48 mining. Bastnasite is beneficiated by hot froth flo-
7
The dressing of South African monazite deposits, tation,4 ,80,81 Fig. 9,and barite, calcite, strontianite,
occurring in association with copper minerals,78 was quartz, apatite, galena, hematite, and monazite are
done by flotation to recover both monazite and separated from it and discarded as tailings. Bastnasite
copper concentrates. Beneficiation by flotation had concentrate containing 600/0 REO is delivered
also been developed for Indian monazite 72,77 and for to a downstream leaching process for further
the recovery of monazite from molybdenite flotation concentration.
tailings at the Climax, CO, mine 79 Numerous minerals occur intimately intergrown in
of Amax. the rare earth bearing Bayan Obo iron 35
ore. ,46 In
Bastnasite physical beneficiation, in addition to the rare earths,
The bastnasite mined from Mountain Pass and the rare earths magnetite, fluorite, hematite, and niobium oxide are
containing iron ores of Bayan Obo have recovered as valuable products. The rare earths are
obtained from the non-magnetic tailings of hematite
bastnasite ore processing and are concentrated by flotation, Fig. 10.
("-"7 °/0 REO) The flotation concentrate contains 56% REO and
J'----- both monazite and bastnasite. For separating bastnas-
ite and monazite slight difference between their
crushing, grinding,]
and cLassification specific gravities is made use of in the shaking table.
While the bastnasite concentrate thus obtained is of
high grade (68% REO), the monazite product has
only 47% REO. The low monazite content has been
attributed to its extremely intimate intergrowth with
taiLs associated strata. The total recovery of the rare earths
("'2 % REO) from the ore is about 720/0.
Chemical treatment
Monazite
The recovery of mixed rare earths and the removal of thorium
concentrate from monazite is accomplished by a variety of methods,76
( rv 6 0% REO ) after chemically attacking the mineral with sulphuric acid or
9 Physical beneficiation of Mountain Pass bastnasite sodium hydroxide. The sulphuric acid method has been used
most extensively
206 Gupta and KrishnamurthyExtractive
metallurgy of rare earths monazite
concentrate
digestion , 200-220°C
grey mud
residue: unreacted monazite

Si02, Th02' ZrSi04
solution: RE, Th, U sulphates, phosphates
sodium
oxalate
solution soLution: U
Th, U, heavy RE
Th,RE oxalate
neutralization NaOH
topH2.3
RE hydroxide
ppt:
RE hydroxide
raff inate :R E
ppt: to pH 2.8 extract: Th,Ce
U,RE(minor)
solvent extraction ppt: Th, Ce (IV)
0.1N sodium
T BP purification of
U or Th NH40H nitrite
by product RE U or Th R E hydroxide aq: org:
pure cerium nitrate thorium nitrate
11 Monazite processing by acid treatment
68 depending on the
in the USA. In this method,82,83 cially significant processes essentially involve precipi-
acid/ore ratio, temperature, and concentration, either tation of thorium pyrophosphate or basic salts from
thorium or the rare earths can be selectively solu- the leach liquor and the subsequent recovery of the
bilised or both thorium and rare earths totally solu- rare earths in solution as double sulphates, fluorides,
bilised. Rare earths and thorium are subsequently or hydroxides,89,90 or even the selective solubilisation
recovered from the solution, Fig. 11. The process of of thorium in the ore treatment stage itself, as ori-
rare earth recovery based on rare earth double ginally developed by Soc. des. prod. chim. des Terres
91 93
sulphate precipitation was largely developed by Rares. - The sulphuric acid process does not yield
Pilkington and Wylie and has found industrial appli- pure products and is no longer in commercial use.
84 86
cation. - Yttrium and heavy rare earth double The flowsheet for the present commercial process
sulphates are quite soluble and go with thorium. Even for monazite treatment using caustic soda is given in
in the stepwise neutralisation procedure investigated Fig. 12. The phosphate content of the ore is recovered
at Ames,87,88 yttrium and heavy rare earths are as a marketable byproduct, trisodium phosphate, at
precipitated along with thorium as a basic compound. the beginning of the flowsheet, and this has been
The rare earths however, are, recoverable from the a major attraction for the commercial use of this
thorium fraction during the solvent extraction for the process. The practical development of caustic soda
purification of thorium and uranium. Solvent extrac- treatment is credited to de Rohden and Peltier94 and
tion with tributyl phosphate (TBP) from an aqueous considerable work on the process was carried out at
95
8N nitric acid solution of thorium and mixed rare the Battelle Memorial Institute. ,96 In the usual
earths permits the recovery of thorium, uranium, industrial practice, fine ground monazite is attacked
cerium, and cerium free rare earths. Other commer- with a 60-70% sodium hydroxide solution at
International Materials Reviews 1992 Vol. 37 No.5
monazite concentrate
decomposition
70 % NaOH 140°C,4 h
mud
solution evaporation/ Na3P04
crystallization (by product)

residue:
RE, Th,U hydroxides
ppt: extract:
Th
Th,U,RE (minor) RE sulphate
solution
RE ChLoride processing for
pure U or Th solution
by product: Na2C03~ RE nitrate

RE
pure U or Th RE carbonate
1
(Gd
a heavy RE)
RE2(S04}j. N02S04·nH20
RE chloride RE hydroxide RE carbonate
12 Monazite processing by alkali treatment
140-150°C.97-99 In the Soviet practice, the grinding calcite with 10% HCI and calcining. The decompos-
and caustic digestion is performed in one step100 and ition of bastnasite (Fig. 13) has been extensively
104
this enables about 50% saving in caustic soda con- investigated at Ames ' and the US Bureau of
1
sumption. Krumholz98 achieved a clean operation by Mines. 0S,106 Baroch et al.104 described a process
digesting the ore with caustic soda at 170°C under a involving nitric acid digestion and solvent extraction
p~essure of several atmospheres. The mixed rare earth in which over 98% of the original rare earth content
thorium hydroxide cake is processed for rare earths was recovered starting from the crude bastnasite ore
and thorium recovery by a variety of methods. containing 7-10% REO. Starting with bastnasite
The direct dissolution of mixed rare earth hydrox- concentrate, Shaw et al.106,107 have described a pro-
ide in nitric acid and the separation of rare earths by cess in which the concentrate was dissolved in warm
extracting thorium and uranium with TBP is attract- concentrated sulphuric acid and the rare earths were
ive but complicated because of interference arising recovered as water soluble sulphates. The sulphuric
from partial oxidation of cerium.101 An effective pro- acid treatment process has found commercial
cess for removing thorium completely and in a high application 103 for purifying the rare earths from
state of purity is by solvent extraction with higher the common elements, such as Fe, Pb, Si, and Ba,
amines. The amines function best with a sulphate occurring in the ore.
108
102 In the Molycorp process the flotation concen-
solution. ,103 trate is heated in air at 620°C to eliminate CO2 and
8astnasite oxidise cerium to the tetravalent state. The calcine is
Chemical treatments start either with crude ore or treated with 30% HCI to dissolve the non-cerium
bastnasite concentrate. The 60% REO concentrate rare earths, yielding a marketable cerium concentrate
can be upgraded to 90 % REO by leaching away the containing 55-60% The ceria residue also
Ce02.
208 Gupta and KrishnamurthyExtractive metallurgy of rare earths
bastnasite (7-10 % REO)

carbon mixing, briquetting, drying
binder
Cl2
bastnasite concentrate ( 60% REO) chlorination 1000-1200°C
fused RE chloride off gas:
volatile chlorides -10

mesh
Sr, Ca
residue: residue:
50-60%
residue: REF3 Ce02 gangue
crude RECl3 TBP
NaOH solution: extract:
RE sulphates RE
residue: sOlution: extract: raffinate
RE(OH)3 NaF Eu other R E
residue: NaOH
t
for Eu
gangue RE hydroxides recovery
RE hydroxides
RE chloride
13 Chemical processing of bastnasite
contains mixed rare earth fluorides. The process of chlorides are recovered in a molten form. In addition to
extraction of rare earths from bastnasite by leaching with bastnasite, it is possible to process a variety of ores such
109 as allanite, xenotime, euxenite, and gadolin-ite by this
hydrochloric acid was patented. In these processes
the fluorides in the ore are not removed completely. The chlorination method. The silicates and phosphates
fluorides, however, are decomposed by treatment with require higher temperatures than the oxidic ores,
68 niobates, and tantalates of the rare earths. Recently,113a
caustic soda. The rare earth hydroxides are then process of enrichment of mixed monaz-ite-bastnasite
leached with HCI. The bastnasite concentrate can be concentrates, involving exposure to a high temperature
treated with caustic soda, to convert the fluoride plasma followed by hydrochloric acid leaching has also
component to hydroxide. 68,110 Following this with been investigated.
dissolution in hydrochloric acid, a rare earth chloride
solution is obtained from which the hexahydrate,
REC13.6H20 can be crystallised. Direct alkaline roasting Xenotime
of the ore to convert the fluoride in the ore into soluble The acid process for xenotime breakdown 114,115
alkali fluoride, then water leaching, followed by involves attack with concentrated (930/0) sulphuric acid,
separation of unconverted barite by flotation was the Fig. 14. Rare earth phosphates are converted to water
process investigated by Kasey.lll soluble sulphates by leaching xenotime concen-trates in
Rare earth ores can be directly chlorinated at high
112 concentrated H2S04 at 250-300°C for 1-2 h (Ref. 115).
temperatures on a production scale. The process Such leaching was uneconomical for con-centrates
essentially consists of conversion of the components in containing less than 100/0xenotime. These are treated by
the ore to chlorides by reaction with carbon and wetting the solids with sufficient acid and heating the
chlorine at 1000-1200°C followed by separation mass at 300°C followed by water leaching. About 80-
according to their volatility. The anhydrous rare earth 90% of rare earths are solubilised.
International Materials Reviews 1992 Vol. 37 . NO.5
xenotime euxenite
RE chloride solution:
Nb;ra,Ti
ppt:
hydrated oxides of
Nb,Ta,Ti
oxalic acid
RE sulphate RE nitrate RE chloride
14 Chemical processing of xenotime RE oxalate RE sulphate

16 Chemical processing of euxenite
The recovery of rare earths by processes such as
double sulphate precipitation is not possible because
The rare earths from gadolinite have been recovered
yttrium and the heavy rare earth sulphates are quite
by leaching the ground ore with nitric or hydrochloric
soluble. The sulphate solution is directly taken for
acid and precipitating the rare earths as oxalates
separ~tion: In an alternative. process, the fine ground
thus effecting the separation from associated Fe and
xenotIme IS treated by fusIng with molten caustic 118
Be. Concentrated sulphuric acid or a mixture of
soda at 400°C (Ref. 116), or by mixing with sodium
11 sodium hydroxide and sodium peroxide have also
carbonate and roasting at 900°C for several hours. ?
been used to attack the ore. The processes for chemical
After leaching out the phosphates, the hydroxide
treatment of gadolinite are outlined in FIg. 15.
resid~e is .dissolved in a minimum amount of hydro- Euxenite has been treated by reductive chlorin-
chlonc aCId and filtered from impurities such as silica '
a t lon, 119120 ~ 11 d b y d' 'II ' of the chlorides
cass~te,rite? etc. The rare earths are recovered b; , 10 owe IStI atIon
to separate rare earths, titanium, niobium, and tantal-

precIpItatIon as oxalates.
um fractions. Solvent extraction has also been used
The processing of uranium ores of Elliot Lake
to remove tantalum-niobium chloride and rare earth
(Ont.) mines generates a uranium barren solution that
metals from the chlorination residue. 58 The ore is
contains considerable amounts of yttrium and other
also amenable to treatment by fusion with ammonium
rare earths, Table 3. These acid solutions are treated
sulp~ate or caustic s?da or by digestion with hydro-
with lime and air in pachuka tanks to a pH of about fluonc or sulphunc L acid or mixtures of the
8·5. The resultant oxidised slurry is thickened. The t 58,120-122 F' 16 ,. IS d ecomposed on an
.wO', \ Ig. . opante
thickener underflow is recovered for further treatment
Industnal scale by chlorination 121 in the CIS. Rare
and the clear overflow is sent to the tailings. The
earth oxides, are recovered from· apatites in the CIS
underflow is acidified with H2S04 to a pH of about 58
and Poland by decomposition with concentrated
4·2 to redissolve yttrium and the rare earths. The rare
nitric acid.
earth solution is filtered off from the iron thorium
The product obtained after chemical processing of
aluminium, etc., in the solids. The rare earths are the~
rare earth minerals contains the rare earths in essen-
precipitated with ammonia gas, thick~ned, and dried.
The concentrate contains approximately 8-15% tially th~ same ratio in which they were originally
present In the ore. This is because of the similar
y203 and 12-30% total including yttrium.
RE203 chemical behaviour of the various rare earth elements
exhibited in the reactions involved in these treatments.
gadoLinite
Operations such as double sulphate precipitation used
conc.HN03 for separating thorium result in partial rare earth
separations in the two fractions one enriched in the
or cerium group rare earths and the other enriched in
conc.HCl NaOH the. yttr~um group rare earths. The separation of
cenum, IS als.o a~complis~ed during chemical pro-
cesses, Inv.olvlng Its OXIdatIon to Ce(IV). The subject
of separatIon of rare earths is reviewed in the section
RE chloride 'Separation processes' below. Perhaps no other
branch of rare earths extractive metallurgy has
oxalic attracted so much attention and research effort as
acid the separation of naturally occurring rare earth ~ix-
~ tures Into pure individual compound intermediates.
i precipitation
, I Separation processes
RE oxalate solution: Be, Fe RE hydroxide The various processes for separating individual rare earths
15 Chemical processing of gadolinite from naturally occurring rare earth mixtures
mixed RE hydroxide by selective precipitation. The precipitation of even

99·8 % pure eerie salts does not completely remove
cerium from solution and additional cerium removal
steps are necessary to prepare other rare earths free
rkr
of cerium.68 A process, considered particularly effec-
tive for cerium recovery from any acid leachate solu-
Ce (IV) + RE(III)hydoxides
tion containing rare earths, uses air oxidation and
solvent extraction, Fig. 17. A number of reagents have
HN03 been studied for the solvent extraction of Ce(IV)
nitrate and TBP is the preferred extractant for large
residue: solution: 125
scale operations. ,126
( 95 Ce02 ) Ce free RE
%
Unlike Ce(IV), both Pr(IV) and Tb(IV) are not
stable in aqueous solution. The higher oxides Pr02
and Tb407 form, precipitate, and settle,127,128 when
a solution of rare earth hydroxides in fused potassium
solution hydroxide is oxidised either by anodic oxygen or by
potassium chlorate. The oxides are recovered by
200;0 TBP decantation 129 or by dissolving away 128
the melt. ,13o
Selective reduction
Samarium, europium, and ytterbium can easily be
separated after reducing them to the divalent state.
Unlike cerium, these elements are much less abundant
and separation using reduction is carried out only
after they are enriched by other procedures. The first
pure cerium nitrate solution
application of selective reduction for the separation
17 Separation of cerium by selective oxidation
of a rare earth was by Yntema.131 Using a mercury
cathode he electrolytically reduced Eu(III) to Eu(II).
Lithium amalgam electrodes were used by
essentially utilise small differences in basicity resulting from
Onstatt132-134 for separation of Sm from Eu and Yb
123
the decrease in ionic radius from lanthanum to lutetium. by selective electrolytic reduction. Recently, the
The basicity differences influence the solubilities of salts, the continuous electrolytic reduction of Eu(III) to Eu(II)
hydrolysis _of ions, and the formation of complex species, in rare earth chloride solutions derived from monaz-
and these properties form the basis of separation procedures ite was demonstrated in a redox flow cell. 135
by fractional crystallisation, fractional precipitation, ion Marsh 136-138has separated samarium, europium, and
exchange, and solvent extraction. In addition to a trivalent ytterbium, from rare earth mixtures in a buffered
oxidation state, Ce, Pr, and Tb can occur in the tetravalent acetate solution by reductive extraction into dilute
state, and Sm, Eu, and Yb exhibit dival-ency. Selective sodium amalgam. The separation is clear and com-
oxidation or reduction of these elements is useful in effective plete and the method is amenable to countercurrent
separation because in the divalent and tetravalent states the operation. It has been used commercially117 for the
elements exhibit markedly different chemical behaviour recovery of Sm and Vb. The recovery of pure
compared with that in the trivalent state. europium from such amalgams can be achieved by
treatment with cold concentrated hydrochloric acid
which causes precipitation of the sparingly soluble
EuCI2.2H2Q.139 Both Sm and Yb are rapidly oxidised
Selective oxidation to very soluble trihalides whereas the oxidation of Eu
The most abundant rare earth, cerium, can be separ- proceeds very slowly in the absence of oxygen.
ated relatively easily and early in the separation On an industrial scale the method developed by
sequence. This simplifies subsequent separation of the McCoy140,141 has found acceptance. In a chloride
less abundant rare earths. Cerium is removed from solution, Eu(III) is reduced to Eu(II) by zinc and the
the rare earth mixture after oxidation of naturally divalent Eu is recovered as sulphate, Fig. 18. Zinc
occurring Ce(III) to Ce(IV), Fig. 17. This valence does not reduce Sm or Vb. When Eu is present only
change occurs when bastnasite is heated in air at in a low concentration, EuS04 is recovered by copre-
650°C (Refs. 87,88), or when the hydroxides are cipitation with BaS04. The mixed sulphate precipitate
dried in air at 120-130°C (Refs. 86, 93). In aqueous is washed with an oxidising acid solution to reoxidise
hydroxide suspensions oxidation is effected by and dissolve Eu(III) leaving BaS04 undissolved. The
125
chlorination 124 or electrolysis. ,126 Bauer and purity of the Eu recovered in this process can be
Lindstrom 127 have suggested an effective method of improved to 99·9% by precipitating EuCI2.2H20
cerium removal from a complex lanthanides solution from concentrated HCI. Recently, the separation of
by an oxidation-precipitation process using ozone as Eu has been achieved by photochemical means using
142
the oxidising agent. Once oxidised, Ce(IV) is separ- a laser. An intense light beam of uniform wave-
ated 76from the trivalent components in the rare earth length (190 nm) applied to an aqueous solution of
hydroxide-oxide mixtures either by selective dissolu- Eu(III) results in its reduction to Eu(II), and precipi-
tion of trivalent species with dilute acid93 or by tation as EuS04 when sulphate ions are present. The
complete dissolution in concentrated acid 86 followed quantum efficiency of Eu(II) precipitation could be
Eu - Sm -Gd concentrate RE chloride solution
( 0.5 - 0.7% Eu) ( Ce free)

Zn,CH3COOH, ppt:
MgS04,8aCl2 heavier RE
precipitate waste
(Ba,Eu) 504
precipitate
90 % La203
Zn.
CH3COOH, solution
MgS04
precipitate deionized mother liquor
EuS04 water ( recycle)
pure crystals
(La203 99.98 % )
19 Separation of lanthanum by fractional
crystal Iisation
%
99.9 EU203
18 Separation of europium by selective neodymium and the double magnesium nitrates

reduction 2RE(N03h.3Mg(N03h.24H20, for obtaining con-
centrates containing the middle rare earths samarium,
europium, and gadolinium. The double manganese
increased 143by photolysing the solution with a small nitrates 2RE(N03h.3Mn(N03h.24H20 have also
amount of acetone. been used in the separation of the eerie group. In
A method of separating samarium, europium, and the separation of the yttric group, the
ytterbium studied by Spedding et al.144.145 is based bromates RE(Br03h.9H20 and ethyl sulphates
on the fact that Sm, Eu, and Yb metals cannot be RE(C2H5S04h.9H20 have been found useful.
obtained by metallic reduction of their halides.146 Erbium, thulium, lutetium, and yttrium have been
During reduction of a mixture of anhydrous rare separated 155using a rare earth hexa-antipyrine iodide
earth halides with calcium, the halides of Sm, Eu, and salt. A sodium rare earth EDTA salt has also been
156
Yb are not reduced and remain in the slag from which useful for separating gadolinium, terbium, dys-
they are subsequently separated. prosium, and yttrium by fractional crystallisation.
Samarium, which only reduces to the divalent state, The separation by fractional crystallisation of these
also accummulates in the fused salt slag when the salts has been used commercially117 to separate and
mixed rare earth chloride is electrolytically reduced raise to 99% purity oxides of Gd, Tb, and Dy.
to mischmetal. This slag has been an inexpensive The lanthanum end of the series, where the differ-
source of samarium for some time.147 ences in cationic radius between adjacent rare earths
Before 1950, in addition to the separation pro- are greatest, is the most amenable for separation by
cedures based on selective oxidation or reduction, the fractional crystallisation. Lanthanum forms the least
methods based on fractional crystallisation and frac- soluble double nitrate. Starting from a cerium free
tional precipitation were widely used for rare' earth rare earth concentrate, a procedure for separating
·separations. The considerable effort spanning over lanthanum in high purity involves the following steps,
100 years that was applied to the problem of separa- Fig. 19. From the rare earth concentrate solution
tion using these techniques has been extensively 900/0 La203 can be precipitated out using an air-
reviewed.148-154 ammonia mixture.157 From this product high purity
lanthanum is then obtained by purification using
Fractional crystallisation countercurrent crystallisation of the double nitrates
different salts and double RE(N03h.2NH4N03.4 H20. is particularly slow
More than half a dozen The fractional crystallisation
salts have been used for the separation ofrare earth and tedious for the heavy rare earths and in the
elements by fractional crystallisation.152 This method Sm(III)-Gd(III) region, because the property differ-
has been considered to be the best of the classical ence between rare earths decreases as the atomic
separation procedures for producing the individual number increases. For example, a bromate salt of a
elements in high purity.68 The most successful com- thulium fraction recrystallised 15 000 times still con-
158 159
pounds have been the double ammonium nitrates, tained ytterbium and erbium. Feit had to crys-
RE(N03h.2NH4N03.4H20 for the removal of tallise the rare earth bromate every day for 4 years
lanthanum and separation of praseodymium and to obtain good holmium.
Fractional precipitation yttrium and gadolinium could be purified by adsorp-tion on

As with fractional crystallisation, a number of com- activated carbon. After over half a century gap, Russell and
170
pounds have been studied for the separation of rare Pearce showed that the simple procedure of adsorption of
earths by fractional precipitation. The hydroxides160 tripositive rare earth ions
and double sulphates,161 in particular, have been on an ion exchanger and their removal by elution
widely used. Double chromate precipitation has also with sodium chloride effected no greater separation
162
been used to separate rare earths from yttrium. than fractional crystallisation or precipitation. This
Among the rare earth elements, hydrolysis occurs was subsequently found true for most cation exchange
171
least extensively with La which remains mostly in media. While there is a decrease in the affinity of
solution. For large scale operation, ammonia is used the lanthanides for the resin from La(III) to Lu(III),
for carrying out hydroxide precipitation from the i.e. as the size of the hydrated ion is reduced, the
84 107
nitrate ,163 or chioride solutions. The preliminary affinities of the various rare earth elements for the
enrichment of yttrium group rare earths and the resin are not sufficiently different to result in satisfac-
extraction of yttrium from yttrium concentrates are tory separation,170,172 because the separation factors
also possible by this method. Lever and Payne117 for adjacent rare earths undergoing simple cation
have used fractional precipitation of basic nitrates to exchange are quite close to unity. This situation was
separate a high proportion of yttrium from a heavy changed by the use of complexing agents to enhance
rare earths concentrate. separation factors.173,174 The successful separation of
The double sulphates RE2(S04h.Na2S04.nH20 rare earths by ion exchange was subsequently demon-
are usually precipitated by addition of sodium sul- strated at Ames and at Oak Ridge by employing a
phate to the rare earth solution. The elements La, citric acid-ammonium citrate eluant at regulated pH
Ce, Pr, Nd, and Sm form sparingly soluble double and was reported in a series of papers published in
sulphates, whereas those of Ho, Er, Tm, Vb, Lu, and the Journal of the American Chemical Society.173-182
Yare soluble; Eu, Gd, and Dy form double sulphates The separation was achieved as a result of the different
of intermediate solubility. Generally, the use of this stabilities of the citrate complexes formed by the
method is confined to crude separation of the rare individual rare earths in the mixture.183-186 The
earth mixture into three groups.161 However, the citrate elution has been performed successfully under
185
elements La and Y can also be readily separated. a wide range of conditions and has proved effective
Yttrium 164 exhibits interesting behaviour in frac- for the separation of up to several hundred grams
tional precipitation and is amenable to purification each of the light rare earth elements. The differences
by a combination of hydroxide and double sulphate between the complex formation constants of adjacent
precipitations. The separation factor, however, is very heavy lanthanides are not as large as those between
small. In double sulphate precipitation yttrium the light rare earths and the citrate process has not
behaves like holmium and in basic precipitation, it been very successful in separating bulk quantities of
behaves like neodymium. By the first method the heavy rare earths. The extreme dilution of the eluant
elements La-Dy can be removed and in the second was also an economic disadvantage.
method the elements Eu-Lu are removed. Besides the citrate, a number of eluting agents and
Marsh 165,166used a method in which the mixture process conditions have been actively evaluated, and
to be separated was partially complexed with EDTA they have been reviewed by Powell.164,185,186 Vickery
and the uncomplexed part precipitated with sodium first investigated 187the use of amino polyacetic acids
sulphate. Earlier, Beck167 had proposed a similar such as NTA and EDTA as eluants but encountered
method using oxalic acid as precipitating agent and the problem of aqueous insolubility. This and many
nitrilo triacetic acid as the complexing agent. other limitations of the elution process was solved in
Double chromates of rare earths with ammonium the band displacement technique developed by Sped-
or potassium, precipitated from chloride solutions ding et al.188,189 in 1954, using the resin in a special
have been found suitable for the industrial production cation state. Compared with citrates, complexing
of high purity yttrium.97,168 For the separation of the agents such as ethylene diamine tetra-acetic acid
heavy rare earths a method based on fractional (EDTA) and 2-hydroxyethylene diamine triacetic acid
thermal decomposition of fused nitrates has also been (HEDTA) not only form 1: 1 chelates of greater
investigated. stability over wider pH ranges but also give greater
In the years preceeding 1947, the methods outlined differences in stability between adjacent rare earths
thus far were the techniques available for separating and allow higher concentrations to be used. Commer-
the rare earths. For most of the rare earth elements, cially, the most useful complexing agents are EDTA
these procedures were relatively inefficient and labori- and HEDTA. The acids diethylene triamine penta-
ous. The purity of the end products obtained was acetic acid (DTPA) and 1,2 diamino cyclohexane
also not comparable with that subsequently achieved tetra-acetic acid (DCTA) also provide high separation
185
in the modern methods of ion exchange and solvent factors. ,186 Powell has discussed the separation
extraction, which dominate the commercial separa- potential of each of these chelating agents and notes
tion of rare earths starting in the 1950s. EDTA and HEDTA as the most useful. EDTA can
Ion exchange effectively separate all of the rare earths and yttrium
from each other with the exception of Eu-Gd and
Yb- Lu pairs because of small difference in separation
The first attempt at ion exchange separation of rare factor and adverse kinetic effects, respectively. The
earths dates back to the late 19th century when Dy- Y separation is also very slow with EDTA
Hoffman and Kruss 169 demonstrated in 1893 that because of the small differences in the stability of the

two complexes. There is, however, a large difference could be countered to some extent by increase in
between the stabilities of HEDTA-Dy and HEDTA- temperature.
Y complexes and so this pair can be separated by The development of band displacement with
HEDTA. 117 HEDTA is particularly useful in the ammonium ethylene diamine tetra acetate as the
separation of the Tm- Yb- Lu fraction and good complexing agent established ion exchange as the
separations are possible with either La-Ce- Pr- Nd- main commercial process for rare earth separation
Y-Sm or Ho-Er-Tm-Yb-Lu mixtures. The separa- from the mid 1950s. The fact that it is feasible to
tion of Sm-Eu-Gd- Tb-Dy-Ho mixture with separate a mixture of 15 rare earths into components
HEDTA is poor because of small differences in chelate exceeding 99'99% purity in one pass through the
stabilities. An advantage of HEDTA elution is that system and that the process can be scaled up to
hydrogen ion retaining beds can be used as multitonne quantities, with possibilities for recovering
H3(HEDTA) is considerably more soluble in cold and recycling water and retaining ion and complex ant,
water than H4(EDTA). This permits easy recycling of have led to the continued commercial use of ion
reagent. The HEDTA complexes of heavy rare earths exchange even after the entry of solvent extraction in
such as Tm, Yb, and Lu show only limited solubility the field. A major limitation of the band displacement
and restrict the eluant concentration. technique or of displacement ion exchange chroma-
For the rapid separation of yttrium, Silvernail and tography is that the technique is inherently a batch
Wyoski 190 have reported a two stage elution pro- process. Recently, Taniguchi et al.196 have succeeded
cedure that makes use of the different positions of in adapting fixed column band displacement
yttrium in the elution sequence with different chelating chromatography to the continuous annular
agents. In the EDTA system, yttrium elutes between chromatograph (CAC).197 This technique, called
Tb and Dy where as in HEDTA it elutes between Nd continuous displacement chromatography (CDC),
and Sm. The heavy rare earths are first separated by combines the processing capabilities of fixed
elution with HEDTA leaving yttrium in the Nd column batch displacement chromatography with the
fraction. This fraction is then eluted with EDTA to continuous operation of the CAe and is applicable
separate yttrium from neodymium. to any displacement chromatography separation that
Temperature plays a crucial part in ion exchange can be performed using conventional batch
separations. Ketelle and Boyd 180 first reported the fixed column chromatography.
shifting in the position of yttrium with change in Solvent extraction
temperature during elutions with 50/0 citrate. This
was followed by investigations191-194 on elutions at The beginning of solvent extraction separation of rare
87-90°C with citrate, lactate, and also EDTA, particu- earths was made by the observations of Hopkins and
198
larly for the separation of Y, Sm, Eu, and Tm. Quill in 1933 and a little later by Fischer and
194 199
Lindstrom and Winget showed that the hydrogen associates in 1937. They found differences in the
ion could be used as the retaining ion in rare earth distribution of various rare earth trichlorides between
separations with EDTA if the system is operated at water and partially miscible alcohols and ketones.
90-95°C, when H4(EDTA) becomes more soluble. Appleton and Selwood 200 found a separation factor
185
Powell ,186 points out several other advantages of of 1·06 for the partition of lanthanum-neodymium
operating at 92°C. These include improved HETP thiocyanate between water and n-butyl alcohol and
(height equivalent of a theoretical plate) values and suggested that continuous countercurrent extraction
an increase in Gd- Eu and Eu-Sm separation factors. might be effective for separations. Higher separation
At all temperatures, with EDTA, Y elutes between factors of 1'29-1'55, depending on experimental con-
Tb and Dy but with increase in temperature to 92°C ditions, were obtained for the lanthanum-neodymium
Tb separation improves and there is a decrease in pair by Templeton and Peterson201,202 for the distri-
Dy- Y separation. The rise in temperature also makes bution of their nitrates between water and n-hexyl
EDTA elution more effective for rare earth separation alcohol. The important observation that Ce(IV) can
from non-rare earth impurities as, for example, in the be separated readily and completely from the trivalent
case of Th-Pb- Yb-Lu mixture which is difficult to cations in an aqueous nitric acid solution by extrac-
separate at room temperature. tion with tributyl phosphate (TBP) was first made
203
As pointed out above, HEDTA gives poor separa- by Warf and later investigated by Bauer
tion of the elements Sm- Ho at room temperature. A et al. 125,204A flowsheet for the purification of cerium
much better separation becomes possible at 92°C and recovery of cerium nitrate by TBP extraction is
because of improvement in the adjacent element given in Fig. 17. Peppard and collaborators at the
separation factor with rise in temperature.186 The Argonne National Laboratory205,206 have studied the
solubilities of species Tm (HEDTA), Yb (HEDTA), extractability of rare earths with TBP from concen-
and Lu (HEDTA) increase with increase in temper- trated hydrochloric and nitric acid solutions and
ature and eluant concentrations up to 0·072 M have showed that extractions with TBP are most effective
been successfully used at 92°C compared with the in nitrate systems and that the TBP-nitric acid system
maximum concentration of only 0·018 M at room could be used to separate the trivalent rare earths
temperature. In HEDTA elutions, there is a consider- from one another. In 1953 Weaver et al. at Oak
able shift in the position of yttrium with change in Ridge National Laboratory207 isolated the first kilo-
temperature; Morton and James have studied195 the %
gram of pure Gd203 (98 Gd203) using TBP-nitric
isolation of yttrium on a large scale as a result of this acid solvent extraction, from a mixed rare earths feed
shift. Powe1l186 has also pointed out that the poor containing 25%Gd203. Using a similar technique,
kinetics observed in ion exchange elutions with DTPA 208 obtained better than 98% pure
Weaver Sm203.
bastnasite concentrate rare earth chloride feed

( 60% REO) (from monazite)
conc.HCl residue: Ce
1M DEHPA
extract: raffinate:
2.5M HCl
acid scrub Y concentrate
I
Eu other RE solvent ( 60% Y2 O~
4M HCl solvent (recycle) Sm - Eu - Gd (recycle)
concentrate
soda ash iron precipitation
_-L __ Eu recovery
10% DEHPA ~traction J
-T-
5M HCl --- .....~ping•... I
Eu (III) solution
chloride • 2M HCl
zinc redu~tion
amalgam ----1 I 15M HCl
Eu (II) chloride solution
H2S04
·1 preci~itation 5M HCl
Eu S04
Gd concentrate Sm concentrate
EU203 (99.9% pure) ("'80% Gd203 ) ("'90% Sm203)
21 Flowsheet of rare earth separation by solvent

extraction at Indian Rare Earths - I
20 Flowsheet of recovery of eu ropi um from

bastnasite DEPHA may be used either in chloride or sulphate
systems both for obtaining rare earth concentrates
from complex mixtures and to isolate individual rare
The separation of rare earths from monazite using earths in high purity. Nair and Smutz218 obtained
209
TBp was investigated by Bochinski and associ- 99.8°/0 pure lanthanum using DEPHA in a 14 stage
210
ates ,211 and Foos and Wilhelm 118 extended this countercurrent extraction from a didymium chloride
0
work to study the separation of yttrium and heavy feed containing 450/0La203' 35°/oNd203, 10 /0Pr601b
212
rare earths. Callow has proposed a complete and 50~Sm203' By selective stripping of a preloaded
scheme for the separation of all the rare earths by solvent Bauer et al.219 recovered > 99°/0 pure sam-
solvent extraction. The separation of rare earths beyond arium oxide. The organic solvent (l M DEPHA in
186 kerosene) was loaded with a RE mixture 60°/0 in
terbium with TBP however, has been difficult.
Commercially, TBP probably finds use in the Sm203 and the aqueous scrubbing solution contained
0
Rhone- Poulenc rare earth separations213 presently 1'5°/oHCI and 20 /0NH4Cl. One of the most promin-
carried out only by solvent extraction in mixer- ent applications of DEPHA is the commercial pro-
220
settlers. Starting from mixed rare earth nitrate solu- duction of europium from bastnasite, demonstrated
tions obtained by processing monazite, successive in 1965 by the Molybdenum Corp. of America,
extraction processes yield high purity La, Ce, Pr, and Fig. 20. DEPHA is used for the preconcentration of
Nd. The residue containing the rest of the rare earths europium to about 150/0 from a rare earth chloride
is separated by a variety of extractants such as di, feed derived from bastnasite. Europium is recovered
2-ethyl hexyl phosphoric acid (DEPHA), tertiary in high purity from this by the reduction method.
carboxylic acids (versatic acid), and quaternary The chloride feed solution to the europium recovery
ammonium compounds. Thorium Ltd (UK) have also circuit contains 0·2 g europium per litre. The solvent
used a batch solvent extraction process using TBP is 10°/0 DEHPA in kerosene and the extraction is
for the separation of individual rare earths from nitric performed in 5 mixer-settler stages. More than 98 °/0
acid solution.214 of europium in the solution is extracted. The loaded
Peppard et al.215 first suggested the use of D EPHA organic is stripped with 4M HCI. The strip solution
for rare earth separations. DEPHA extracts better contains iron as an impurity and this is precipitated
from a chloride than from a nitrate medium. The out with soda ash at pH 3·5. Following iron removal,
distribution coefficient increases with increase in the Eu-bearing solution is subjected to a second
atomic number but the actual variation is compli- solvent extraction with DEHPA in 5 mixer-settler
216 217
cated. DEPHA gives good separation factors stages. Europium loaded in the organic is stripped
for all the rare earth elements. The average separation with 5M HCL. The aqueous solution is passed
factor for adjacent RE elements is 2·5 compared with through a column of zinc amalgam to reduce Eu(III)
about 1·5 in TBP systems. DEPHA gives highest to Eu(II). Sulphuric acid is added to the divalent
separation factors in the region Sm- Lu. europium solution to precipitate europium sulphate.

feed solution: solvent feed solution
( La, Pr ,Nd ,Sm nitrates)

undiluted TBP raffina te : Pr ,La
diluted ! raffinate
TBP
i
extract: extract: t
raffinate:
Sm,Nd Pr La solvent light RE
(recycle) fraction
aqueous: Sm, Nd
undiluted
TBP
extract: raffinate:
Sm Nd
22 Flowsheet of rare earth separation by solvent solvent heavy RE
extraction at Indian Rare Earths - II (recycle) fraction
Reduction and selective precIpItation purifies extraction

europium from the heavy rare earths. More than
99'95% pure EU203 is obtained by calcination. raffinate
From the europium barren solution, gadolinium is
extracted by DEHPA in a 10 stage mixer-settler. The
solvent yttrium
raffinate'is neutralised with soda to precipitate sam-
( recycle) product solut ion
arium and the heavy rare earths. Raffinate from the
europium (first solvent extraction) circuit contains La, 23 Separation and recovery of yttrium by solvent
Pr, and Nd, which are precipitated with ammonia extraction
and sodium hydro sulphide.
The mixed rare earth chloride solution derived
from monazite contains less than 1% of any of the By adding diethylenetriamine penta-acetic acid
229
heavy rare earths. At the Indian Rare Earths plant (DTPA) to a primary amine, Bauer et al. enhanced
221
at Alwaye, solvent extraction with DEHPA is used the separation factors from 1·5 to 5·4 for La-Ce, to
for a quick initial concentration of the heavy rare 8·0 for Ce- Pr, to 3·7 for Pr- Nd, and to 7·0 for Nd-
earths and for the production of concentrates of Sm. Quaternary ammonium compounds dissolved in
various individual rare earths such as Sm, Eu, Gd, an aromatic diluant have been used in commercial
and Y, with purities ranging from 60 to 95%, Figs. separation in Norway for producing 99'999% yttrium
21,22. from an extraction raw material containing about
Versatic acid - a mixture of tertiary carboxylic 60% Y203, derived from xenotime.230 The extraction
acids with 9-11 carbon atoms - is used as the flowsheet (Fig. 23) is based on the different extraction
extractant with Shellsol as the diluent - in some behaviour of rare earths in nitrate and thiocyanate
213
commercial separation processes. The separation systems. Yttrium extracts like a heavy rare earth in
factors for La-Ce and Ce-Pr are 3 and 1'8, the nitrate system and like a light rare earth in the
respectively - higher than those for TBP extraction. thiocyanate system. In the nitrate medium the light
For Pr-Nd and so on the separation factors are lanthanides extract more readily and are just separ-
similar to the TBP system. Versatic acid extractions ated followed by the extraction of heavy lanthanides
are performed with mixer-settler contactors using using quaternary ammonium nitrate and thiocyanate
chloride solutions as the aqueous phase. which leaves yttrium in the raffinate. To separate it
Many other types of solvents have been examined from non-rare earth impurities, yttrium is extracted
for use in rare earth separations.222-226 Of these, from the aqueous phase. Yttrium nitrate is then
tertiary amine extraction has received particular stripped with very pure water and precipitated as
attention. Gruzensky and Engel227 have reported on oxalate. In another process patented by Molycorp,231
the processing of euxenite concentrate for yttrium versatic acid is used to separate the heavy rare earths
using tri-n butylamine solvent in 3-methyl 2-butanone and the quaternary amine-nitrate process to separate
and an aqueous phase of 8M HN03. They obtained the light rare earths, leading to the recovery of
a product of 83% yttrium oxide starting from a feed yttrium.
containing 47% yttria. Other amine types such as tri- For the recovery of rare earths from sulphate
iso-octyl amine (TIOA), methyl di-octyl amine solutions resulting from uranium processing at Deni-
(MDOA), dodecyl amine (DDA), and alamine, have son Mines, Elliot Lake (Ont.), solvent extraction has
also been used for the separation of rare 228 been 214 The flowsheet is given in Fig. 24.
earths. used.
Elliot Lake uranium ore for the production of extremely pure materials,34
commercial production of materials at 99'9% or even
H2S04 ---.1 acid l:aChing I 99'99% purity with liquid-liquid
103
extraction been
claimed. ,196 Although the details of actual pro-
leach liquor cedures, sequence of various operations and identities
of certain organic solvents are usually not disclosed
in publications, the solvent extraction technology has,
in the two decades starting from the mid-1960s, been
uranium barren solution
expanded to commercial scale separation/purification
of at least 11 of the 15 rare earths that occur in
air
lime
bastnasite, monazite, and xenotime ores.232 Solvent
extraction would not be the method of choice in at
slurry least two instances: (a) when product purity exceeding
solids: tails 99'9% is required, and (b) when the lesser abundant
lanthanides, such as Tm, Yb, and Lu, are to be
clarified solution isolated in a commercial solvent extraction circuit.196
Solvent extraction has been the process used for
the recovery and isolation of scandium from its
H2SO4
resources which are essentially non-rare earth min-
DEHPA raffinate: tails erals. In the processing of uranium, during solvent
extraction, scandium is extracted and concentrated
extract together with uranium. In the subsequent purification
H2SO4
of the uranium, the scandium is separated. Three
HN03
_I stri~PingI _I stri?ing 1 processes for accomplishing this separation and recov-
ery of 99% pure scandium have been reviewed by
65
RE nitrate solution thorium Gschneidner. The processes likely to be used for
sulphate
large scale, high purity scandium recovery from wolf-
ramite use solvent extraction for separation.65 The
lime,
NH3
processes employed for opening thortveitite use
chlorination,233,234 or fluorination,235 to obtain a
scandium rich material which is subsequently dis-
solved and the scandium recovered in pure form by
using ion exchange and solvent extraction.
rare earth oxide concentrate There are several areas of applications of rare
24 Flowsheet of rare earth recovery from Elliot lake earths where the separated rare earths recovered as
uranium ore oxides are used directly. Many other applications
require rare earth metals and alloys.
Reduction processes
The uranium barren solution from the ion exchange
circuit is treated with lime and air in pachuka tanks.
The pH is controlled to precipitate iron, some amount
of thorium, and other impurities. These are removed The investigations on the preparation of pure rare
from the solution using thickeners, filters, and clarifi- earth elements began almost a century after the first
ers. The clarified solution is acidified with sulphuric rare earth was discovered.
acid and fed to the solvent extraction circuit. The Several processes have been developed for the
solvent used is 10-12 vol._% DEHPA in kerosene production of rare earth metals of different purities.236
with no modifier and the extraction takes place in a These methods include: (a) reduction of anhydrous
countercurrent centrifugal extractor. Under extraction rare earth chlorides or fluorides; (b) reduction of rare
conditions used at present all the rare earths and earth oxides, and (c) fused salt electrolysis of rare
yttrium are loaded in the organic phase. The loaded earth chlorides or oxide-fluoride mixtures. A qualitat-
solvent is stripped with nitric acid in a centrifugal ive picture as to which reactive element is usable as
contact or. Thorium and uranium present in the aque- reducing agent for rare earth metals preparation is
ous solution are loaded into the organic together with given by the free energies of formation of the oxides,
the rare earths. The rare earths are separated from fluorides, and chlorides, and their dependence
thorium and uranium during stripping. The yttrium- on temperature. The data for the rare earths and
rare earth containing nitric acid solution is treated some potential reducing agents237 are given in
for precipitation. Slaked lime is added tothe solution Fig. 25. In oxide systems, the order of stability
to consume all the free acid. Ammonia gas is then is CaO > RE203 > MgO > Al203 »Si02, whereas
added to the solution to precipitate yttrium and other among the fluorides it is CaF 2> REF 3> LiF >
rare earths. The dried precipitate contains 30-35% NaF> MgF 2 » AIF 3, and among the chlorides,
Y203 and 60-700/0 RE203 including yttrium. KCI > NaCI ~ LiCI ~ CaCl2 > RECl3 > MgCl2 » AICI3.
The solvent extraction process has the advantages The indicated order of stabilities, however, can be
that more concentrated solutions can be used and it changed in real systems by changing the activities of
is economical for handling large quantities of mater- one or more of the reactants or products. When no
ials. Although ion exchange is regarded as superior such change is effected, the above data indicate that

Another important interstitial impurity is carbon.

All the rare earths are known to form dicarbides
-200
REC2, most of them (La-Sm, Gd-Ho, Y) form
sesquicarbides, RE2C3, and some also form mono-
carbides (e.g. SeC, LaC) and subcarbides RE3 C (Y,
~ Sm, Gd- Lu). 239 The rare earth carbides are high
u melting and form extensive solid solutions, with
.....•... -400
C\J
l.1..
oxygen and nitrogen. The solid solubility of carbon
.....•...
C\J
in rare earth metals is also considerable.238 For
0 example, yttrium dissolves up to 1·3 wt_%C at 1520°C
0+-
0 and La takes up to 0·3 wt_%C at 775°C. The high
Q) -600
-0 stability of the lower carbides of rare earths and also
E
.....•... of the carbon- RE solutions makes the attack of rare
~J~ earth metals on graphite crucibles an important pro-
c
0
cess leading to contamination of rare earths with
"0 carbon.
t -800 Rare earth metals show strong affinity for nitrogen.
.g The mononitrides of the rare earths are comparable
0+-
0
>.
in stability with those formed by metals such as
~ titanium or zirconium.239 They have high melting
points and very low decomposition pressures. The
Q)
c
-1000
Q)
Q)
Q)
metals also form nitrogen solutions.238 For example,
Lt cerium dissolves up to 0·3 wt_% nitrogen at 750°C.
The equilibrium nitrogen pressures over these solu-
tions are expected to be still lower. Thus, rare earths
-1200 are very good getters of nitrogen from the reaction
environment and do not easily degas with respect to
nitrogen.
IIIIIIIIIIIIIIII III Silicon, like carbon, forms rare earth silicides and
400 800 /200 1600 2000 solutions. Rare earth silicides are all disilicides rep-
resented by the formula RESi2 but silicides of other
Temperature,Oc stoichiometries have also been reported.239 Silicon is
25 Free energies of formation of selected oxides, an impurity to be included in the reduction and
fluorides, and chlorides refining of rare metals. The use of ceramic crucibles
including graphite for rare earth metal preparation
therefore involves the problem of rare earth metal
calcium is the only choice for the reduction of rare contamination by crucible corrosion (and an atmo-
earth oxides and fluorides, whereas the chlorides can sphere other than high vacuum or an inert gas of
also effectively be reduced with lithium, sodium, or equivalent purity leads to atmospheric contamination
potassium. of rare earth metal). Among the refractory metals,
Rare earth metals are highly reactive, particularly niobium, molybdenum, tantalum, and tungsten are
at the high temperatures required for their prepar- resistant to attack by liquid rare earth metals and
ation. The halide reduction, which usually involves might serve as crucible materials.24o,241 The metals
the metallothermic reduction of pure anhydrous hal- in the listed order show decreasing solubility in the
ides with pure metallic reductants, is a standard liquid rare earth metals at high temperatures, tungsten
method of reactive metals preparation and is meant being the least soluble. However, tungsten embrittles
to be an oxygen free process. However, oxygen and and has poor mechanical properties compared with
other interstitial impurities such as carbon, silicon, tantalum and therefore tantalum has been the best
and nitrogen do find entry into the reduced metal by crucible material for the preparation of high purity,
various ways. This is traceable tothe extreme stability rare earth metals. It has been noted by Gschneidner
147
of the solutions and compounds formed by these and Daane that the use of ceramic oxide crucibles
elemen ts with the rare earths metals. puts an upper limit of 95-98 at.-% on the purity of
The stability of oxides formed by the rare earths the rare earth metal, while the use of tantalum has
suggest that the rare earths could act as reducing allowed the purity level to rise to 99 at.-% and higher.
agents for oxides of lesser stability and thus would In the development of reduction methods, following
attack most of the refractory crucibles including zir- the early demonstration of feasibility of a reduction,
conia, alumina, and magnesia, and also such refrac- the emphasis has been on preparation of increasingly
tory linings. Also, several rare earths form solid pure metals by improving conditions so as to minimise
solutions with oxygen238 and these have even greater the possibility of contamination.
stability and the process of a rare earth metal picking Metallothermic reduction
up and dissolving oxygen from oxides of comparable
(e.g. MgO) or greater (e.g. CaO) stability cannot be
ruled out. However, no experimental data are pre- In the earliest successful attempt on rare earth metal
sently available on the activity of oxygen in solid and preparation, metallothermic reduction was used and
liquid rare earth metals to give a quantitative picture. this technique, to date, remains the most widely

HCl
Ca
Ar Li
RE-Mg alloy
as reduced metal RE sponge RE metal crystals
RE metal sponge
RE metal ingot RE metal ingot RE metal ingot

La ,Ce, Pr Y,Sc Y RE meta l ingot
26 Processes for preparation of rare earth metals through the chlorides
to 300°C in the presence of under reduced

applied. The purity of the metallothermic reduction NH4CI
246
product depends among other things on the purity pressure. The dehydration of the hydrated mixed
of the starting materials; pure oxides, anhydrous rare earth chloride obtained by wet chemical treat-
chlorides and fluorides, and that of the reductants. ment of monazite or bastnasite has been carried out
While the purities of the rare earth oxides are essen- on a large scale for supplying the electrolytic cells for
tially determined by the separation step, the purities the preparation of mischmetal. The process consists
of chlorides and fluorides are determined by the of melting the chloride in cast iron, steel, or ceramic
methods of their preparation starting from the oxides. vessels from which air is exc1uded247 until a porous
Preparation of rare earth ch lorides solid product is obtained. The product, however,
contains some oxychloride.
Anhydrous rare earth chlorides required for sub- The trichlorides of rare earths have the disad-
sequent metal winning either by metallothermic vantage of being very hygroscopic but this could
reduction or by fused salt electrolysis can be prepared be overcome as suggested by Moriarty242 if the
by many methods, Fig. 26. One of the important chloride is handled in hot lumps while shielded from
processes, representative of direct anhydrous chloride the atmosphere.
preparation is reductive chlorination of the rare earth Chloride reduction processes
oxide in presence of carbon or a carbonaceous mater-
112
ial. This method gives high yield of pure chloride. The major investigations in the metallothermic
Direct chlorination of a monazite or bastnasite ore reduction of rare earth chlorides are summarised in
248
has also been used by Th. Goldschmidt to prepare Table 4 and Fig. 26. Mosander is credited with the
anhydrous mixed rare earth chlorides. Solid state first recorded preparation of a rare earth metal. He
reaction of rare earth oxide with excess ammonium reduced cerium trichloride with potassium in a stream
chloride at about 200°C, followed by removal of the of hydrogen to obtain a cerium metal powder. The
excess ammonium chloride by heating in vacuum at product, however, was impure. Following Mosander,
300°C and above has been used to prepare trichloride there has been about a dozen attempts to reduce the
in excellent yield.242 Another widely used method is rare earth chloride257 but invariably the product
based on the dissolution of rare earth oxide in hydro- obtained is a metal powder dispersed in an alkali
chloric acid, crystallisation of the chloride hexahy- chloride slag. Klemm and Bommer249 also obtained
drate, and conversion to anhydrous salt. Dehydration a similar product but the metals were of better
of hexahydrates has been carried out243-245 by slowly purity because they carried out the reduction after
heating them up to 400°C under dry HCI flow and sealing the rare earth trichloride with potassium in
reduced pressure, or by heating the hydrated chloride a quartz ampoule and thus avoided atmospheric

contamination. A powder product dispersed in slag molten at reaction temperatures, permitting clean slag
results from insufficient heat of reaction to melt the metal separation.
reaction products. Product melting and better slag- An effective method in rare earth metal preparation
metal separation can beachieved by (a) the use of a at reaction temperatures less than the metal's melting
booster reaction to supplement the enthalpy of the point is to obtain the metal in a sponge form as in
main reaction, and (b) forming low melting reaction the Kroll process for titanium.
243
products such as the alloy and a multicomponent low Block and Campbe1l prepared large quantities
melting slag. Trombe and Mahn25o,251 obtained of high purity yttrium metal by reducing the chloride
cerium, neodymium, and gadolinium by reduction of with Na or Li. The chloride and Li were loaded in a
their trichlorides with magnesium. A magnesium-rare molybdenum crucible and heated at 850-900°C for
earth 'llloy was obtained. The magnesium was 4-5 h under an inert atmosphere. The excess Li and
removed by vacuum distillation. Trombe and Mahn LiCI were removed by vacuum distillation at
claimed rare earth metal purities of 99.5-99.8°/0. Iya 900-950°C and metal was obtained in 95-99°/0 yield.
used a similar process258 to prepare scandium. In sodium reduction, sodium was distilled into the
252
Keller et al. following the earlier work of Mold- YCl3 crucible and the reduction was carried out at
259 260
enhauer and Karl used calcium to reduce CeCI3• 800-850°C for 5-7 h. NaCI slag was poured off. The
They prepared large amounts of massive cerium metal remaining trace NaCI and excess Na were removed
by reducing CeCl3 with Ca in dolomite lined steel by distillation at 850°C. Recovery of metal was
bombs. Here, additional heat to achieve good slag- between 61 and 85°/0.
metal separation was provided by using a Ca-I Nolting et a1.254 and Moriarty242 have used lithium
booster reaction. The metal was vacuum melted to vapour reduction of rare earth trichlorides to prepare
remove Ca or CaCl2 slag and was obtained in over yttrium and other high melting rare earth metals.
98°/0 purity with about 95°/0 yield. This technique YCl3 kept in a tantalum crucible is reduced with
was used by Spedding et al.244 to prepare La, Pr, lithium vapour and the process is carried out inside
and Nd metals. The attempt to prepare higher melting a sealed stainless steel chamber. After the reduction
gadolinium using higher reaction temperature was the LiCI slag is distilled away from the yttrium
complicated by frothing of the CaCl2 slag which crystals. The crystals are consolidated by arc melting.
prevented clean slag-metal separation. The bomb was The commercial lithium reduction process is similar
also attacked by the molten metal leading to impurity to Nolting's but commercial grade Li and titanium
pick up. Spedding and Daane253 subsequently carried crucibles were used. The rare earth chlorides are
out the reduction in a tantalum crucible which was purified in situ by distillation. Croat256 has described
heated to temperatures above the melting point of Li reduction of DyCI3, HoCI3, and ErCI3. The anhy-
the metal reduced. The reduction was carried out drous chlorides were reduced at 900°C in a tantalum
under vacuum or inert atmosphere inan induction retort using Li or Li-5 wt-O/oCa as reductant. Calcium
furnace. La, Ce, Pr, Nd, and Gd metals were prepared helps in reducing oxygen content by purifying lithium
with 99°/0 yield. The use of a booster reaction was during distillation. Non-volatile CaO is formed at the
not necessary and tantalum was more resistant to expense of relatively volatile Li20 and the deoxidised
molten rare earth metal attack. Li vapour goes for reduction. Metals of up to 99·97
The chloride reduction as described for the five wt-O/o (99·7 at.-% purity) could be prepared by this
metals could not be applied to the higher. melting process by double distilling the chloride before
metals because of excessive chloride volatilisation and reduction. The overall yield of oxide to purified
reduced yields. The need for high temperatures for recovered metal was of the o.rder of 70°/0. The purity
reaction has been overcome by resorting to the pre- of the as reduced metal from the chloride process is
paration of metal as lowmelting alloys. Calcium was more than that from the other halide reduction
used as the reducing agent. Yttrium metal was pre- process - the fluoride process.
pareq255 by calcium reduction of yel3 in the presence Fluoride reduction processes
of magnesium. Scandium was also prepared261 by
reducing ScCl3 with Ca and/or Mg. Yttrium and Historically, the investigations on the metallothermic
scandium form alloys with magnesium which become reduction of rare earth fluorides started much later
Table 4 Chloride reduction processes

Year Reactants Process Result Ref.
1827 CeCI3-K Heated in hydrogen flow Ce metal powder in slag matrix 248
1937 REClrK Heated in closed quartz ampule Pure RE metal powder dispersed in slag 249
1943 RECI3-Mg (Ce,Nd,Gd) Chloride added to molten Mg bath Low melting RE-Mg alloy; Mg distilled off 251
1945 CeCI3-Ca Bomb reduction; Ca-I booster Consolidated Ce separated from slag 252
1952 RECI3-Ca (La,Pr,Nd) Bomb reduction; Ca-I booster Consolidated RE metal separated from slag 244
1952 RECI3-Ce (La,Ce,Pr,Nd) Heated in Ta crucible under vacuum Consolidated RE metal separated from slag 253
1959 YCI3-Na or Li Heated in Mo/Ta crucible under inert gas Y sponge, slag distilled off 243
1960 YCI3-Li Li vapour reduction of YCI3 in Ta crucible Y crystals; slag distilled off 254
1967 inside a steel bomb
YCI3-Ca, Mg
Heated to 950°C Low melting RE-Mg alloy; Mg distilled off 255
1968 RECI3-Li Li vapour reduction of RECI3 in Ti RE crystals; slag distilled off 242
(La,Ce, Pr,Nd,Gd, Dy, Ho,Tb, Er,Lu,Y) crucibles inside steel bomb
1969 RECI3-Li or Li-Ca (Dy,Ho,Er) Li vapour reduction of RECI3 RE crystals; slag distilled away 256

HCl
NH4HF2 RECl3'x H2O
hydrofluorination aq.HF
7000 C REF3' Xl H2O
LiF
REF3 HF gas
Ca Ca REF3 -LiF fused
mixture
Ar Ca-Mg
He
Y-Mg alloy RE-Mg alloy
as reduced
RE metal
Y sponge RE metal sponge
high pure RE metal RE metal ingot Y metal ingot RE metal ingot

27 Processes for preparation of rare earth metals through the fluorides
than those using the chlorides. The use of rare earth fluorides HF -Ar atmosphere. In a later investigation from the
circumvents the problems associated with the use of same laboratory, Beaudry et ai.265 have noted that
hygroscopic and volatile chlorides. this melting step is not necessary to prepare fluorides
of sufficiently high purity for metal preparation, par-
Preparation of rare earth fluorides Starting from ticularly for the light rare earths. The oxygen contents
their oxides, the rare earth fluorides can be prepared of La, Ce, Pr, and Nd prepared from topped and
by any of the following three methods,262-264 Fig. 27. untopped fluorides were found to be nearly the same.
The hydrofluorination of the oxide with anhydrous However, the metallic impurities such as Cu, Ni, Fe,
HF has been successfully carried out with conversions Cr, and Si, which remain in the fluoride after the low
in excess of 99%. Large scale preparations use rotary, temperature hydrofluorination, are reduced in the
fluidised bed, and vibrating tray reactors. The hydro- topping process.266 In the commercial practices,
fluorination of oxides with ammonium bifluoride is topping is not done.236 262
carried out as batch process by heating the rare earth The fluorides prepared by the aqueous methods
oxide with 30% excess of high purity NH4F.HF in a have been found to have slightly higher oxygen
platinum boat inside an Incone1 chamber at 300°C contents than the fluorides prepared by the dry
under a stream of dry air. Fluorides ofall the rare methods. The industrial preparation242 of rare earth
earths have been prepared by this method with con- fluoride consists of (a) precipitation of REF 3 from
versions as high as 99'99%. On an industrial scale, aqueous solution, and (b) molten salt purification of
reaction of the oxide with the ammonium fluoride, is REF 3' However, the RE fluorides could not be satis-
carried out in steel retorts. For high purity metal factorily dehydrated for industrial scale operations,
preparation, the preparation of high purity fluoride with the result that the oxygen content of the metals
is don~ in two steps. A mixture of anhydrous HF and prepared increases.
600/oAr is passed over RE203 at 700°C for 16 h. The Reduction of rare earths fluorides The important
oxide is contained in a platinum boat and the Inconel
furnace tube is lined with platinum. The fluoride thus fluoride reduction methods forrare earth metal pre-
obtained contains about 300 ppm oxygen. By a pro- paration are summarised in Table 5. In one of the
cess known as 'topping' the oxygen content is reduced earliest attempts on fluoride reduction, Eyring and
271
to less than 20 ppm. The topping is done by melting Cunningham prepared metallic praseodymium by
the fluorides in a platinum crucible under a dynamic passing barium vapour over praseodymium fluoride

at 1100°C under reduced pressure. Gray developed a crucibles originally used were later replaced by tan-
technique,267 in which the rare earth fluoride was talum and the reductions were carried out under a
reduced with lithium in a molybdenum crucible positive pressure of argon. La, Ce, Pr, Nd, Gd, and
enclosed in a steel bomb. Iodine was added to lower Y have all been prepared with yields varying from 80
the slag melting point. Reductions were conducted to 98%. Calcium was used as the reducing agent in
up to 1200°C and cerium, lanthanum, and neodymium later experiments.
metals were prepared. The most successful method of The temperature necessary for fluoride reduction
fluorides reduction by calcium was soon developed was lowered in the large scale production of
at Ames by Daane and Spedding268 269
in their continu- yttrium through the formation of an intermediate
ing efforts to circumvent the difficulties associated low melting alloy with zinc or, more successfully, with
with the application of chloride reduction procedures magnesium. Yttrium trifluoride was reduced by cal-
for preparing high melting rare earth metals. cium in the presence of magnesium and calcium
The greater stability and lower vapour pressure of chloride in a zirconium or titanium crucible. The Y-
calcium fluoride permitted reduction temperatures as Mg intermediate alloy and the CaF 2-CaC12 eutectic
high as 1700°C - higher than the highest melting - both of which are molten at the reaction temper-
point of a rare earth metal. It was thus possible to ature of 950°C, form and there is good slag-metal
prepare, Er, Ho, Dy, Tb, and Tm in a consolidated separation. The alloy thus obtained is crushed, vac-
form. Tantalum was used as the crucible material, uum treated, and electron beam melted to yield the
thus greatly reducing contamination of the RE metal metal. This method does not appear to have been
from the crucible. tried with other heavy rare earth elements such as
256
In the Ames process, Fig. 27, the rare earth fluoride Dy, Ho, and Er. The fluoride process flow sheet
and calcium loaded in a tantalum crucible are extern- (Fig. 27) given by Moriarty242 for the industrial pro-
ally heated in an argon atmosphere to about 50 K duction of rare earths before 1960 uses Li- Mg alloy
above the melting point of the highest melting com- as the reducing agent instead of calcium. The metals
ponent in the reaction mixture. It takes only a few Y, Nd, Pr, Gd, and Dy have been prepared by forming
minutes for the reduction to go to completion, their magnesium alloys and distilling them to give
resulting in good slag-metal separation. The excess pure metals. Yttrium metal of comparable purity has
calcium and adhering slag are removed from the also been obtained by the reduction of a ternary salt
metal by vacuum melting and high purity metal is mixture of YF 3- MgF 2- LiF with lithium at 1000°C
obtained with 97-990/0 yield. Any rare earth metal, yielding a Li-Mg alloy and LiF slag.255
independent of its melting point, except Sm, Eu, and While the advantages of the fluoride reduction
Yb - which form stable divalent halides, can be route include high metal yield and the high purity of
reduced to metal by this process. It is, however, very metal obtained after vacuum refining to remove the
important to provide a contamination free environ- excess calcium (about 2%), the disadvantages are the
ment during reactants and products handling as well high cost of the fluorine chemicals that end up as low
as during reduction in order to obtain a pure metal. 269 value CaF 2 and the high cost of the reducing agent
In the industrial practice for calcium reduction of calcium. The process is technically not problematic
rare earth fluorides,272 the fluoride is mixed with but is an expensive method of making rare earth
granular calcium and placed in tablet form or as metals. This is also due to the very expensive reactor
rammed material, into a steel reactor that is lined and batch nature of the process.
inside with tantalum which is coated with a layer of A large fraction of the overall cost of metallothermic
calcium fluoride. After closing and evacuating the reduction processes is the cost of the raw materials.
reactor, the metallothermic reaction is initiated by a It can be generally stated that the price of fluorides
spark discharge and proceeds within minutes to form » of chlorides > of oxides. If the cost of the
a rare earth metal ingot in the bottom part of the reductant is compared, for the same amount of
reactor topped by solidified CaF 2 slag. reduction capability or reduction equivalents, lithium
Besides calcium, a number of metals and alloys and calcium metals turn out to be the most expensive
such as Li, Mg, AI, Na, Zn, Mg-Zn, and Li-Ca were reducing agents followed by sodium, and magnesium
evaluated by Haefling et al.270 for reducing YF 3' They comes last. 272 The purity of the calciothermic metals
found Li or Li-Ca alloy to be most suitable as is high and its application is justified only when they
reductants. The production of Ce, La, and Nd metals are the only reductants that can be used or if high
had originally been carried out at Johnson and Mat- purity metal is required.
they117 by following Gray's technique of reducing the The metals Sm, Eu, and Yb cannot be prepared
rare earth fluoride with lithium. The molybdenum by metallothermic reduction of their chlorides or
Table 5 Fluoride reduction processes

Year Reactants Process Results Ref.
1952 REF3-Li-1 (Ce,La,Nd) Heated to 1200°C in Mo crucible enclosed Consolidated Ce, separated from slag 267
1953 REF3-Ca (Gd, all RE except in steel bomb Consolidated RE metal well separated from 268
Heated in Ta crucible under argon
Sm,Eu,Yb) Bomb reduction slag
1956 YF3-ZnF2-Ca Low melting Y-Zn alloy; Zn distilled off; 269
Heated in Zr or Ti crucible under argon Low melting Y -Mg alloy; Mg distilled off
YF3-CaCI2-Ca-Mg
1961 Heated in Ti crucible Low melting Y-Mg alloy; Mg distilled off 270
YF3-Li-Ca-Mg; YF3-Li-Mg

fluorides because such reductions only proceed up to rare earths. Besides, many of the rare earths are
the formation of the respective stable dihalides. Fortu- volatile at high temperatures and the simultaneous
nately, however, these metals can be prepared by vaporisation of reduced metal and CO would lead to
direct reduction of their oxides. reverse reaction occurring and also carbon contamin-
Reduction of rare earth oxides ation. These factors have made carbo thermic
reduction very difficult for rare earth metal
production.
Oxide reductions of reactive metals are based not An interesting possibility of carbothermic reduction
only on the reducibility of the oxide by a suitable has emerged from the work of Anderson and
274
reductant but also on the possibility of removing Parlee. The method proposed by them involves
oxygen from the as reduced, residual oxygen contain- the use of a suitable liquid metallic solvent to lower
ing metal. Besides forming highly stable oxides, the the chemical activity of the reduced dissolved metal
rare earth metals also form highly stable solid solu- to a level where no carbides can form. In addition,
tions with oxygen. This oxygen, however, is removable the method avoids high temperature refractory attack
by techniques such as pyrovacuum deoxidation and and vaporisation loss. The method has yet to be tried
distillation, and by processes involving chemical get- for rare earths.
tering, electro refining, or ultrapurification methods The important oxide reduction investigations are
such as electro transport. However, the isolated pos- summarised in Table 6. The early attempts to produce
sibilities of oxide reduction and deoxidation have not rare earth metals by reduction of their oxides were
resulted in a typical oxide reduction-refining flow- made between 1890 and 1912 by Winckler,286,287
289
sheet for rare earth metal production. Matignon,288 and Hirsch. Using magnesium or
Even though the thermodynamic stability of calcia calcium as the reducing agent, they invariably ended
qualifies calcium as a reducing agent for rare earth up with a product mixture consisting of magnesium
oxides, the high melting point of calcia (2600°C) is a oxide or calcium oxide and the metal, which could
275
definite disadvantage. During the calcium reduction, not be separated. Several decades later Mahn
consolidated rare earth metal is not produced because pursued the Mg reduction route. He dipped fused
the enthalpy of reaction is not sufficient to melt both oxide blocks of Nd, Gd, or Y group elements into
the metal and calcia slag and permit their separation molten magnesium heated to 1050°C. The oxide block
by gravity. The reduction yields at best rare earth was rapidly attacked by the magnesium metal but
metal dispersed in the slag matrix. Aqueous pro- the products obtained were dilute solutions « 5%)
cessing to recover this metal powder usually results of rare earth in magnesium. In 1953, Daane et al.276
in further oxygen contamination. accomplished a major breakthrough in oxide
The only other element that can reduce rare earth reduction and devised an effective reduction-distil-
oxides is carbon. In fact, at about 1750°C and a CO lation method for the preparation of the volatile rare
pressure below 100 Pa, carbon is the most efficient earth metals: Sm, Eu, Tm, and Yb.263,290 In this
reducing agent. However, even the reduction of rare process, La chips and the rare earth oxide are inti-
earth oxides by carbon in vacuum is beset with mately mixed and the mixture is heated under high
problems. Together with reduction, the formation of vacuum in a tantalum crucible fitted with a long
carbides take place. The rare earth carbides are high tantalum condenser. The crucible is maintained at a
melting and form extensive stable solid solutions with high temperature (1400-1600°C) so that the metal
oxygen and nitrogen. It has been possible, however, produced by lanthanum reduction of the oxide sub-
to avoid the formation of carbides by employing limes to be collected as crystalline condensates on the
appropriate conditions of temperature, CO/C02 walls of the condenser. Metal is obtained in up to
273
ratio, and high vacuum. These conditions are 98 % yield and contains La, 0, and H residual impur-
arrived at with the aid of Pourbaix-Ellingham dia- ities which can be removed by subliming the metal
grams. These diagrams or thermodynamic data for once more. The lanthanum reduction process has
constructing such diagrams are not available for the been feasible because (a) lanthanum oxide has the
Table 6 Oxide reduction processes

Year Reactants Process Results Ref.
1950 REz03-Mg (Nd,Gd, or Y) Rare earth oxide blocks dipped in molten Mg heated Mg-5%RE alloy 275
REz03-La (Sm,Yb) to 1050°C

1953 Reduction-distillation in Ta crucible and condenser Pure RE metal concentrate 276
1957 SmZ03-C Red uctio n-d isti lIation Impure Sm condensate 277
1959 REz03-Zr (Eu,Sm) La Reduction-distillation in Mo crucible and condenser Pure RE metal 146
1959 SmZ03-Ca Reduction-distillation Sm containing residual Ca in low yield 133
1959 REz03-C Carbothermic reduction RE carbide formation 278
1961 REz03-Ce Reduction distillation Pure RE metal condensate 279
1968 REz03-La (Sm,Tm,Yb) Reduction-distillation in Mo crucible and Ta Pure RE metal condensate 242
°
REz03-La (Dy,Ho) condenser
1968 Red uction-d isti lIation Residual La, in condensate 280
1969 DYz03- Th Redu ction-d isti lIation Dy condensate; purified by redistillation 281
1987 Gdz03-CaClz-Mg Heated to reaction temperature and slag leached off Gd metal powder 282
1987 Ndz03-Ca Reduction carried out in CaClz-NaCI bath and metal Nd-Zn or Nd-Fe alloy 283
extracted by Nd-Zn or Nd-Fe alloy pool 284,285
1988 Ndz03-Na Reduction carried out as with Ca Nd-Zn or Nd-Fe alloy

reaction mixture containing 1·4 kg of oxide to get

about 1 kg of metal in the condensate. Thecondensate
is consolidated by inert atmosphere melting and
casting in an induction furnace. Samarium, thulium,
$ -zn RE
RE-Zn alloy
and ytterbium are prepared
ditions.
236
,279 Europium
handling in an inert atmosphere.
under similar con-
is more reactive and requires
charging in a melt The metals Dy and Ho, which are less volatile than
the group of four metals discussed above, have also
Ta crucible- ~f' NaCl,
been prepared by direct reduction.280 Heating the
condenser TcaCl2
assembly fluid melt compacted oxide and lanthanum turnings mixture at
about 1500°C, resulted in the distillation of Dy or
reduction Na Ho metal. Metals were obtained in "" 85-99% yield
in the condensate and the lower vapour pressure
extraction difference betwen La on the one hand, and Dy and
750°C
Ho on the other, manifests in a higher La content
condensate RE-Zn alloy
(up to 1 wt-%) in the condensate. The oxygen contents
as sublimed RE powder RE metal were also higher (about 0·1 wt-%). Using zirconium
as reductant, much purer metals « 1 wt ppm Zr and
< 150 ppm oxygen) were obtained but the yields were
less (20-33 0/0). Dysprosium oxide was reduced with
metal thorium filings at 1390-1750°C (Ref. 281) and the
Sm,Eu,Tm,Yb (RE =Gd ) (RE=Nd) condensate was redistilled at 1600°C to yield a metal
28 Processes for preparation of rare earth metals by containing only 10 ppm thorium and 70-120 ppm
oxide red uction oxygen. Achard295 and also Kobisk and Grisham
296
have also applied the direct reduction technique

to prepare some of the less volatile rare earth
highest heat of formation among all the rare earth oxides, (b) metals.
282
lanthanum is relatively non-volatile, and Okajima has described a process for preparing
(c) the metals Sm, Eu, Tm, and Yb have high vapour rare earth metal powder by oxide reduction. Fine
pressures. gadolinium oxide powder was mixed with CaCl2
Besides lanthanum, reductants such as cerium, powder and Mg granules and the mixture was heated
mischmetal,279 zirconium,146 and even thorium to 1100°C for 1 h. Gadolinium metal powder, at over
236 90% yield, was obtained from the product by leaching
have been used for preparing the rare earth metals it with water followed by decantation, alcohol
by reduction-distillation. Commercial mischmetal
washing, and vacuum drying.
can be used as reductant after vacuum melting it to
Recently, neodymium metal has been successfully
remove impurities such as Mg, AI, and the residual
produced at General Motors by a molten salt process
halides normally present. Because of the high temper-
involving the reduction of Nd203 with calcium or
atures involved, Tm prepared by reaction between 283
is carried out by reacting
sodium. ,284 The reduction
Tm203 and mischmetal contains a few ppm of Nd or
Nd203 with calcium in a molten salt bath (CaCI2-
volatile heavy lanthanides present in the mischmetal,
NaCI), at 750°C and simultaneously extracting the
La or Ce is used if high purity Tm is desired.
132 reduced metal into a molten Nd-Zn or Nd-Fe alloy.
Onstatt ,133,291-294 used calcium in place of lan-
The Nd-Zn alloy product was treated in vacuum to
thanum for the reduction of Sm203 and the Sm metal
remove zinc and produce Nd metal. The process has
was distilled. Distillation had to be repeated 3-4
been made commercially more attractive by the use
times to reduce the Ca content in the reduced metal
of sodium instead of calcium as the reducing 285
to less than 0·1 0/0. The metal yield was only about agent.
40%. The calcium reduction method turns out to be
more laborious and less effective than the lanthanum Electrolytic processes for rare earth metal
method. reduction
The carbo thermic reduction of rare earth oxide was
278 277 While the chemical reduction processes are limited
largely found to yield the carbide. Achard tried
generally by the availability of reducing agents that
using carbon in the reduction-distillation process for
form stabler chlorides, fluorides, and oxides than the
Sm preparation. The distilled product contained con-
rare earth metals, the electrolytic reduction of com-
siderable oxygen. However, a second distillation in a
pound intermediates for the preparation of metals is
tantalum apparatus at 13-1'3 mPa resulted in pure
not limited by considerations of chemical stability. It
malleable samarium. The purities of Eu and Yb
can be calculated from the standard free energy of
obtained in a similar process were better.
formation of compounds that an applied voltage
Commercially, the oxide reduction distillation pro-
as small as 4 V should be more than adequate to
cess, called the 'direct reduction technique', has been
dissociate even the stablest chemical compound.297
employed since 1959 to produce 99'90/0 pure (nuclear
242 When other considerations for carrying out electro-
grade) rare earth metals. The flow chart of the
lytic reduction are satisfied, this process offers an
process is given in Fig. 28. The reduction reactor
effective method for reducing the stable rare earth
consists of a molybdenum crucible and a compounds to metals.
tantalum
condenser. It takes about 2-3 h of slow heating of a
The electrolytic methods presently account for the largest 301 307
years later, Hirsch and Thompson produced cerium
quantity of rare earth metals commercially produced
in good yield by electrolysing the industrial grade anhydrous
throughout the world. Among the widely used rare earth fused chloride in an iron crucible which served as the
metals, La, Ce, Pr, and Nd have cathode, with a graphite anode.
melting points which permit their recovery in the In addition to cerium chloride the electrolyte con-
liquid state by electrolysis of relatively inexpensive sisted of KCI, NaCI, and BaCl2 added in small
fused chlorides at temperatures less than 1100°C. quantities to increase the resistance of the bath and
Winning of the rare earth elements in the liquid state check its decomposition. The metals obtained in these
facilitates slag (electrolyte) - metal separation, mini- studies were not very pure mainly because of contami-
mises contamination of the reduced metal, enables nation from the cell material, electrodes, electrolyte,
continuous operation, and high volume levels of and insufficiently separated rare earth start materials.
production. Such electrolytic processes are inherently The first attempt at reducing electrode contamination
simpler compared with the complex metallothermic was by Kremers and Stevens,302 who electro lysed
reduction procedures. Added to these factors, the low lanthanum chloride in a bath containing NaCI and
cost of dc as the reducing medium compared with KF using a W or Fe cathode. The metal prepared
the reducing metal makes the electrolytic method when using a W cathode did not contain tungsten
cheaper than any metallothermic process. The techni- and the metal prepared in iron cells was always
cal feasibility of preparing limited quantities of high contaminated with iron. Molybdenum was also recog-
melting rare earth metals such as Sm, Gd, Dy, and nised as a suitable electrode material following Guert-
Y in a consolidated form has also been demonstrated ler's308 report that molybdenum is insoluble in the
by employing the fluorides aselectrolytes in place of rare earths at 'red heat'. The preparation of La, Ce,
chlorides. These studies have been carried out in and mischmetal was pursued by Kremers et al.,309,310
specially designed high temperature cells. In such Weibke,311 Gray,267 Eastman et al.,312 and Kojama
cases, the metallothermic processes still remain more and Sato.313
attractive in comparison. Instead of as pure metals, In a direct attempt at preparing high purity rare
if the rare earth metals are recovered as binary alloys earths, Trombe et al.314-318 replaced C and Fe with
having melting points in the range of 600-1000°C, Mo cathodes. Using pure chemicals and closely con-
the electrolytic process has been found applicable to trolled conditions they prepared small quantities of
all the rare earth metals with the added advantages reasonably pure metals. Trombe's303,316 bath con-
of liquid product recovery and low temperature oper- sisted of CeCI3- KCI-CeF 3, contained in an externally
ation. Morrice and Wong298 have reviewed the heated graphite pot which served as the anode. The
research up to 1979 in electrolysis of rare earth metals cathode was a Mo rod and the electrolysis was carried
from fluoride and chloride electrolysis. out at 850°C producing 99·9% pure metal. Gray267
Electrolysis of chlorides essentially repeated Trombe's experiment and
obtained cerium metal which was at best 99'7% pure.
Among the electrolytic processes most investigations The contamination from cell materials remained
ha ve been directed towards electrolysing rare earth unavoidable.
trichlorides in a molten alkali chloride bath, Table 7. Commercially, the production of rare earths by
The possibility of electrolytic reduction of a molten fused salt electrolysis of chlorides247,298,304,319,32o is
salt for preparation of rare earth metals was first carried out in cells constructed of a ceramic refractory,
demonstrated by Hillebrand and Norton299 in 1875. iron, or graphite, using an iron cathode and graphite
They succeeded in preparing a few grams of Ce, La, anode. Besides RECI3, the electrolyte contains NaCI,
and Di (Nd + Pr) in a coherent form by electrolysing KCI, BaCI2, or CaCl2 and the bath is molten even
fused rare earth chlorides using iron electrodes. This at 650°C. The liquid rare earth metal is collected
work was followed up by Muthmann et al.3oo,30s,306 beneath a cover of salt initially in solid form. The
between 1902 and 1907 and they prepared many metals in the rare earth metal is tapped periodically through a
cerium group (Ce, La, Pr, Nd, Sm) by electrolysing fused rare spout in the cell bottom or the cell is emptied by
earth chlorides in a water cooled copper vessel with carbon tilting. Lanthanum, cerium, and didymium metals of
electrodes. A few better than 99% purity can be prepared by this fused
Table 7 Electrolysis of rare earth chlorides

Year Electrolyte Electrodes* Cell Productt Ref.
1875 RECI3 Fe Porcelain Coherent deposits of Ce,la,Di 299
1902 RECI3-NaCI-KCI Carbon Water cooled copper Several kg of Ce,la nodules 300
1912 CeCI3-NaCI Graphite (A) Iron Massive Ce 301
Cell (C)
1923 laCI3-KF-NaCI Carbon (A) Iron la metal (0'77% Fe) 302
W(C)
1931 CeCI3-CaF2 Carbon (A) Fluorspar Ce ingot (99'8% pure) 303
Mo (C)
1940 RECI3-NaCI-KCI Graphite (A) Refractory lining la,Ce,Di,mischmetal (99·5-99·9% pure)
Fe (C)
1986 NdCI3-LiCI-LiF Graphite (A) Alumina Nd (98% pure) 304
W(C)
* A anode; C cathode.
tDi - Nd+ Pro

salt electrolysis if carefully purified starting materials a tungsten or molybdenum liner. 322 Operation of the
are used and air is excluded by enclosing the cell. cell under an inert gas cover reduces atmospheric
The current efficiencies of the chloride cells are usually contamination. The required temperature profile in
between 45 and 50%. the cell is maintained by supplementing the heating
The maximum operating temperature of the chlor- by electrolysis current with additional heating by ac
ide cell is 1100°C and neodymium which melts at current between a pair of graphite anodes.
322
102loC is the highest melting rare earth metal that The low melting Ce and La 327 of 99.90/0 purity,
can be produced by chloride electrolysis. The metal exceeding the levels attained by Gray, have been
yield in the preparation of neodymium by chloride prepared in kilogram quantities by continuous elec-
electrolysis is however very low.304 Besides volatility trowinning of the oxide dissolved in the REF 3-LiF-
of bath constituents which becomes unacceptable at BaF 2 bath. Both metals were collected on a Mo/W
higher temperatures, the strong solubility of metals hearth and tapped from cell bottom into ladles in an
322
in their chlorides and the attack of the cell wall inert atmosphere casting chamber. The current
materials by rare earth metal limit the operating efficiency achieved for Ce and La were 75-95% with
temperature. Considerably higher temperature oper- the metal yield exceeding 970/0 in all cases. Such
ation, however, is possible in cells employing fluoride continuous electrowinning would probably also be
electrolyte baths. feasible for Nd metal. 283
Oxide-fluoride electrolysis The preparation of Nd, Pr, and didymium by
oxide-fluoride electrolysis up to 1115°C has also been
carried out in Reno cells. The metal is produced as
Muthmann et ai.306 were the first to electrolyse a
liquid on Mo cathodes and drops to be collected by
solution of cerium dioxide in molten cerium fluoride
the frozen electrolyte skull in the bottom of the
to prepare cerium metal. Gray267 re-examined the
graphite crucible. The bottom of the cell is 300-500 K
Muthmann process and prepared 99'7-99'80/0 pure
lower than the melting point of the metal. The current
cerium by electrolysing at 880-890°C a solution of
efficiency of these cells: 770/0 for Nd, 880/0 for Pr, and
50/0Ce02 dissolved in a CeF3-LiF-BaF2 electrolyte.
550/0 for didymium - are still higher than those
The cathode was molybdenum and the anode was
achieved in the chloride cells.
graphite. Further development of the process occurred
The highest temperature at which an electrolytic
essentially at the Reno Metallurgy Research Center
cell operated was 1700°C for the preparation of
of the US Bureau of Mines during the 1960s,321-327 326
yttrium by the electrolysis of 50LiF -50YF 3 (mol.-
Table 8. Morrice et ai. showed that by adding rare
%) electrolyte to which Y203 was added. The necess-
earth oxide directly to the fluoride and electrolysing
ary high temperature in the reaction zone of the cell
at 50-60 K above the melting point of the metal, the
was obtained by applying ac to a pair of graphite
rare earth metals can be prepared in a consolidated
anodes. The recovery and yield of the metal depends
form. They prepared liquid La of 99'8% purity by
324 on the temperature of the metal collection zone and
this method and Ce of similar purity was also
325 a lower temperature gives a purer product with higher
obtained. Morrice and Henrie325,326 have also
recovery.323 Gadolinium and Dy have also been
described the requisites of the molten salt medium
prepared 323by such high temperature electrolysis and
for oxide electrolysis and considered an electrolyte
in the case of Gd, the reported current efficiency is
consisting of REF 3 - to increase solubility of the
only 53%. Operating at the highest temperature
oxide, LiF - to increase the conductivity of the melt,
severely stresses the construction materials of the cell,
and BaF 2 - to decrease the melting point of the salt
making the process less attractive.
mixture, to be the most suitable. Unlike these fluor-
Recovery of rare earth metals as alloys
ides, the chlorides are less stable than the rare earth
oxides and an oxide-chloride combination cannot be
used in electrolysis. The early attempted preparation of yttrium and the
The Reno electrolytic cells usually consist of a hea vy rare earth metals by chloride electrolysis was
graphite crucible with graphite anodes and either a frustrated by the formation of metal powder328,329
Mo or W cathode. Contamination of the rare earth dispersed in the electrolyte rendering their separation
metal by the cell material is reduced by collecting the in pure form difficult. A novel way out of this difficulty
liquid metal either in a frozen electrolyte skull or over appeared to be the recovery of rare earth metal as
Table 8 Electrolysis of oxide-fluoride melts

Year Electrolyte Electrodes" Collector Product Ref.
1907 Ce02-CeF3 Carbon Water cooled copper Ce (86-48%) 306
1951 Ce02-CeF3-LiF-BaF2 Graphite (A) Mo crucible Ce (99·7%) 267

Mo (C)
1962 La203-LaF3-LiF-BaF2 Carbon (A) Electrolyte skull La (99·8%) 324
Mo (C)
1964 Ce203-Ce F3-Li F-Ba F2 Graphite (A) Mo liner Ce (99·8%), continuous electrowinning 322
Mo (C)
1966 RE203-REF3-LiF Graphite (A) Electrolyte sku II Dy,Y,Gd nodules (99·8-99·9%) 326
(Dy,Y,Cd) W(C)
1967 Nd203-NdF3-LiF Graphite (A) Electrolyte skull Nd nodules (99·85%) 323
W(C)
*A anode; C cathode.

an alloy which is molten at the electrolysis temper-ature. This the preparation of Mg-49Y and AI-20Y (Re~s.
approach has attracted a number of investigations and 332, 338, 339) alloys using an electrolyte of Y203 In
considerable success was achieved, YF3-LiF. applicable to the whole range of rare
Table 9. Metal is recovered from alloy by pyrovacuum This process,
317
distillation. Trombe used molten Cd or Zn as the earths, yields very pure master alloys and is ~uitable
cathode. During electrolysis, alloys of Cd or Zn with for continuous operation if pure feed matenals are used.
the rare earth metal were obtained which readily
separated from the fused salt bath. The metal was
recovered from the alloy by distillation. This process Current efficiency
has b een app 1Ie · d' In t h e prepara t' Ion 0 f Gd , 335,336 The current efficiency ofcommercial chloride cells is
low usually below 50%. At the electrolysis temper-
Eu,318 and Dy336 with Cd as the alloying eleme~t
atu;e (""900°C) the rare earth metals can react with
and for SC337 with Zn as the alloying element. IshI-
333 O2, H2, CO2, and graphite, forming products ",:ith
kawa et ai. electrolysed an electrolyte of equimolar
low electrical conductivity and high melting pOInt.
SmCI3-NaCl at 500°C using a liquid Zn cathode and
The presence of oxychlorides, either from the starting
obtained a SmZn12 alloy. Murphy334 have el~c-
material or the reaction between the trichloride and
Recently, Chambers and
moisture, is detrimental to the electrolytic process.
trowon neodymium metal from a molten chlonde
Oxychlorides have higher melting points than
electrolyte at 650°C using a molten alloy ca~hode.
the anhydrous halides and limited solubility in the
The electrolyte was a equimolar KCI-RECI3 mIxture.
latter. Their existence causes viscosity increase in
Both binary Mg-Zn and Mg-Cd alloys were used as
the molten salt leading to current losses because of
molten cathodes. Neodymium was electro won into
these alloy cathodes at current efficiencies better than lower ionic mobility and a higher temperature for
80%. Neodymium metal of better than bath operation.
99·9 + %
The presence and accumulation of multivalent
purity was recovered from the Mg-Cd all?y catho~e
elements such as Sm, Eu, and other non-reducible
by vacuum distillation. The removal of ZInc by thIS
components in the electrolyte also leads to lower
treatment however, was not complete.
current efficiency. SmCl3 can easily react with Sm,
The ele~trolytic reduction of rare earth oxide dis-
more readily at higher temperatures, to form soluble
solved in a fluoride melt to yield the alloy directly
divalent chlorides. During electrolysis, the oxidation-
has also been carried out. The temperature of elec- 3 2
reduction reaction of Sm + -Sm + can occur
trolysis is higher than the melting point of the eutectic
cyclically at anode and cathode and cause high
between the cathode and the rare earth metal but
current consumption and low efficiency.
lower than the melting point of the cathode
The current efficiencies of molten fluoride systems
metal. 330,331 The electrolyte comprises rare earth
are better and range from 75 to 95%. 247 T h e fluon ·d e
oxide dissolved in REF 3- LiF - BaF 2 and the cell
electrolysis investigations, however, have been con-
arrangement is the same as for high purity metal
ducted using high pure starting materials in inert
preparation. Instead of Mo, a consum~ble rod of F~,
atmosphere electrolytic cells.
Ni, Cr, or Co is used as cathode. Dunng electrolYSIS
low melting near-eutectic alloys of the rare earth and
Purification of rare earth metals
the cathode metal form and drip off at the working
temperature of 850-1000°C and are collected at the A number of processes are used for refining the as reduced,
cooled bottom of the cell in a solid form. These alloys rare earth metals to different levels of Purity.236 A summary
can be tapped from the bottom spout after he~ting of the sequence of processes has been presented by Jones et
the cell to sufficient temperature. The alloys contaIned 340 d· .
ai. an IS gIven as Fig. 29. The applicable processes
about 80-90 wt_% REM. Even the difficult to reduce
Sm is obtained as Sm-13Fe alloy with about 46% are strongly influenced by the melting points of the metals and
their vapour pressure at the melting point.
current efficiency, principally because alloy formation
effectively prevents the back reaction of samarium Vacuum melting
with the fluoride resulting in the formation of Sm(II). The impurities present in the metallothermi.cally reduced
Molten Al or Mg cathodes have been used in metals contain in addition to reSIdual
Table 9 Electrolytic preparation of rare earth alloys

Year Electrolyte Cathode Product Ref.
1935 GdCI3-KCI-LiCI Liquid Cd Gd-6Cd alloy; distilled to Gd (98-4%) 317
1968 RE203-R EF3-LiF-BaF2 Consumable metal rod: Cr, Fe,Co Gd-4Cr 330
Gd-15Fe
Dy-18Co
Sm-13 Fe
1969 Consumable metal rod: Mn,Cr,Fe Gd-34Mn 331
Gd-6 Cr
Dy-16 Fe
Sm-13 Fe
Y-37Mn
1973 Y203-YF3-LiF Liquid Mg Y-46Mg 332
1974 SmCI3-NaCI Liquid Zn SmZn'2 333
1988 NdCI3-KCI Liquid Mg-Cd Nd-Mg-Cd 334
Liquid Mg-Zn Nd-Mg-Zn

4
II I
10
0 2
10 0 0 0 0 0
0... ..
E
9 I I
I II
I I
c::i.
I I I
-0
102 9 9 I I I I
~
~ I I I I
I
:J
If)
If)
4 I I I I
(0 ~ I
~
? I I I I
0-
I I I I I
0
::J
'-
106 1
I I I
I
I
I I
0-
I I I I
~
10
8 9 I
I
I I
I
I I I I
I
I I I
10 I I I I I I I
10 ? I I I I I I I I I
oU•. 1400
-+-
c
I
·0
0..
r
O'l
Ii r
c 1000
-+-
(i)
~ r r
Nd Eu
600 Gd Tb Y Lu Sc Er Ho Dy Sm Yb Tm
Ce La Pr
purest available REMs

29 Processes for purification of rare earth metals
elements present in the starting materials, excess metals can also be induction heated to the melting
reductant and slag and the impurities picked up from point and often slightly above in a 'cold boat' con-
the reaction environment (the atmosphere and the tainer. 340 Vacuum arc melting or electron beam melt-
reactor). For example, the as reduced La, Ce, Pr, and ing also remove the volatile impurities from the
Nd from the fluoride process, just separated from the rare earth metals which have less than 13 Pa vapour
CaF 2 slag contain Ca, CaF 2, and H. These impurities, pressure at their melting points. These include Sc, Y,
which are more volatile than the rare earth metals, La, Ce, Pr, Nd, Gd, Tb, and Lu.
can be removed by melting the metals in vacuum. During the electron beam melting of yttrium the
Although removal of Ca and H occurs by heating the residual fluorine content in the metal falls from 0·06
reduced metal to just above its melting point, the to 0.002% as a result of the evaporation of volatile
341
quantitative removal of fluorine impurity requires oxyfluorides. On electron beam melting, the fluor-
heating to at least 1800 e for 30 min.236 Such heating
0 ine content of electrorefined gadolinium decreased
to a temperature 500-1000 K above the melting point from about 0'20/0 to less than 10 ppm.342,343 Electron
also results in significant purification with respect to beam melting also reduces the hydrogen content in
carbon, oxygen, and nitrogen.34o Vacuum melting of gadolinium to acceptable levels. The oxygen content,
the rare earth metals is done at Ames by induction however, is not significantly affected by this treatment
heating in a tantalum crucible.236 Most rare earth (residual 0'045%). The purification of a reactive rare

metal with respect to oxygen can be achieved during temperatures, and does not decrease much on reduc-
pyrovacuum treatment by sacrificial deoxidation.344 ing the temperature to the melting point and thus the
This involves treatment under conditions where vol- tantalum in solution does not precipitate out. Tantal-
atile metal sub oxides form and evaporate in such a um is removed by distilling off the rare earth metals.
way that the ratio of oxygen concentration in the gas A tungsten crucible and a tungsten lined condenser
348
phase to that in the melt-solid phase is always greater are used in the distillation. The suboxides of the
than unity. The sacrificial deoxidation tendency of a rare earths co-distil with the metal under these con-
metal can be estimated if the vapour pressure of the ditions (1575-1725°C) and there is no significant
metal suboxide and activity of oxygen in the metal purification with respect to oxygen during this step.236
are known. Such data are not available for the rare The sub oxide vaporisation is less significant at tem-
earth metal-oxygen systems. It has been deduced, peratures below 1650°C. The sublimation of Sc, Dy,
however, from experimental observations that several Ho, and Er is done below this temperature principally
rare earth elements do form suboxides345,346 and to remove from them tantalum introduced into
these suboxides affect the metal refining process at the metal during the preceeding vacuum melting
temperatures exceeding 1650°C.236 Their role in metal operation. Tantalum is used for both crucible and
refining either by sacrificial deoxidation or by other condenser as, under the conditions employed for
deoxidation mechanisms has not been evaluated. purification by sublimation, there is no contamination
Deoxidation can also be achieved by distilling off the of the rare earth metal by tantalum. There is also
pure metal leaving an oxygen enriched melt or residue. purification with respect to the common interstitial
This option appears particularly applicable in the impurities nitrogen, carbon, and oxygen, because they
refining of rare earth metals because of their high form stable compounds and remain in the residue. In
vapour pressures at temperatures below that required the case of oxygen, there is also no carryover of
for significant suboxide volatilisation. Besides the oxygen to the condensate by the rare earth metal
pyrovacuum methods, deoxidation can be achieved suboxides. The removal of nitrogen from metals and
by chemical or electrochemical methods such as slag- thus their purification occurs by simple degassing if
ging, gettering, fused salt electro refining, and electro- the partial pressure of nitrogen over the metal-
236
transport. An interesting method of deoxidation nitrogen system at the refining temperatures is of the
has recently been demonstrated for Y, La, Nd, and same order of magnitude or greater than the ambient
Gd metals. These metals, containing 1-5 at.-% dis- pressures achievable during pyrovacuum treatment.
solved oxygen, were reacted with their respective However, because most of the rare earths have high
trichlorides at 730-850°C for 1-2 weeks duration vapour pressures and the nitrides formed by them are
during which time oxygen from the metal was very stable, simple degassing might not be an effective
removed as a result of the formation of the oxychlor- method for nitrogen removal. As in the purification
ide REOCI and its content in the metal fell by about with respect to oxygen, distilling off of the metal
a factor of 10.347 Oxygen from nearly all the rare leaving a nitrogen enriched residue or certain chemi-
earth elements might thus be removed selectively by cal/electrochemical means appear to be possible
such types of reactions. The existence of gaseous methods.
monoxides of several rare earth elements is known Carbon and silicon are the other two impurities
but their role in metal refining either by sacrificial that are avidly taken up by the rare earths and
deoxidation or by other deoxidation mechanisms has removed from them only with difficulty. As these
not been evaluated. 240 elements have low vapour pressures compared with
Tantalum dissolves in rare earth metals ,241 (more the rare earths and their activities in rare earths are
in the heavy than in the light rare earths), and the low, the pure metals can only be distilled off from
solubility increases with temperature. During vacuum the impurity enriched residues. Carbon and silicon
melting in tantalum crucibles, a considerable amount are removable by chemical/electrochemical means.
of tantalum, therefore, is introduced into the refined Tantalum is not the major impurity in the metals
metal. The rare earth metals are further treated by a Sm, Eu, Tm, and Yb produced by the direct reduction
variety of methods (Fig. 29) to remove this tantalum method. These metals do not undergo the vacuum
and prepare them in high purity. The metals prepared melting step. The main impurities in the as distilled
on a commercial scale, however, are not subjected to metal are several hundred ppm of La, as well as
extensive vacuum melting at high temperatures to oxygen and hydrogen. Purification with respect to
prevent excessive corrosion of the crucible. These these impurities is accomplished by sublimation.
metals thus contain residual fluoride and other vol- Because of their high vapour pressure, these metals
atile impurities. could be sublimed at a higher rate than was possible
While at 1800°C, La, Ce, Pr, and Nd dissolve large for Sc, Dy, Ho, and Er.
amounts of tantalum,240,241 the tantalum solubility The removal of dissolved tantalum from the vac-
in these metals at their melting points is low. The uum melted gadolinium is particularly difficult
tantalum taken up at high temperature can be reduced because gadolinium has both a low melting point and
to less than 20 ppm by holding the temperature just a low vapour pressure. There is considerable refluxing
above the melting point of these metals to allow the during the distillation process and this causes con-
tantalum to precipitate out of solution and settle at siderable attack on the W or Ta crucible 236
the bottom of the crucible. These tantalum dendrites used.
are later removed by machining.236 On the other Electrorefining
hand, the solubility of tantalum in the heavy rare Electrorefining of an impure rare earth metal has also been
earths, Gd, Y, Tb, and Lu is higher at vacuum melting studied for the purification of yttrium using

and LiCl (Ref. 349) elec-

KCl- YCl3 (Ref. 319) YCI3- 1000 0 0
trolytes. A reduction in the level of metallic impurities 0 X x
E 0
was observed in this process. More detailed investi- 0.
0.
x X 0
gations have been conducted on the electro refining -; 100 \J

342 0
of gadolinium. ,343 The gadolinium feed material, c £::::,
containing 810 ppm oxygen and 920 ppm tantalum .2
as the principal impurities was electrorefined in a E

C
u
=_ ----~--~--=t--- ~ o
LiF -GdF 3 bath using a He atmosphere electrorefin- g 10
ing cell. Significant reduction in some of the interstitial o
0---
impurities (H, N, 0) and several metallic impurities ---------- .
...........................................
(AI, Fe, Ta) was noted. There was no change in the Q
£::::,
carbon content. The hydrogen and fluorine concen-
6.
trations increased during electrorefining, but could be
6-
eliminated by subsequent electron beam melting of 8 o
the deposit. Electrorefining of gadolinium offers out-
0.1
standing purification with respect to tantalum also I
making it the likely process to replace the distillation I I
step in the metallothermic reduction procedure for B E
preparing high purity gadolinium. ~4
------- 'V W
o 0
-----'- £::::,
Zone refining x C AL
In addition to the pyrovacuum treatments and e1ec- ----- a N _ _ - .._._.. 0 To
trorefining methods which are useful for tantalum ------------------- 0 Fe
removal from vacuum melted rare earth metals, zone 30 Impurity profile in zone refining of
refining can also be considered as a means for reduc- gadolinium: B beginning; E end
ing the amount of Ta or W in a crucible contaminated,
rare earth metal. Basically, zone refining is a step in ured impurity profile obtained by Fort et a1.355 in the
the sequence of purification operations for the pre-
paration of rare earth metals of four or five nines zone refining of gadolinium is presented in Fig. 30.
purity, starting from the as reduced and vacuum As the metallic and interstitial impurities are found
melted metal, Fig. 29. to be transported in opposite directions, no part of
In one of the earliest attempts of zone refining rare the zone refined bar is of greatly improved overall
earth metals in vacuum, Carlson et al.341 refined purity than the starting material. This is also true,
yttrium rod containing 0'052% oxygen and 0'065% generally, for the other rare earths La, Ce, Tb,
fluorine. After two zone passes, no significant change and Nd. 354
in oxygen content was observed while there was a Zone refining, as a technique, is very attractive
decrease in the fluorine content. The decrease in because it is quick and can be readily applied to large
fluorine was, however, attributed to evaporation of a amounts of metal. It is best considered as a step in
volatile compound.350 According to Necker,351 metal- the ultrapurification sequence of the rare earths
lic impurities in yttrium could be reduced from 4300 because of its ability to refine rapidly with respect to
to 1800 ppm after six zone passes but Huffine and metallic impurities. Reduction in metallic impurity
352
Williams noted that zone refining was not a practi- levels by a factor of several hundreds has been
cal purification process for yttrium as the movement achieved though it is rare for interstitials to be reduced
of metallic impurities such as Fe, Cr, Cu, and Zr was by a factor of more than 2 or 3. The technique of
very slight and 0, N, Ni, and Ti did not move at all. solid state electrotransport is, however, particularly
Revel et al.353 attempted zone refining of cerium but effective for the redistribution of interstitial impurities
could not record any purification of Nand O. Jones while it is less effective with the metallic contaminants.
354
et al. ,355 re-examined the potential of zone refining These two techniques therefore appear complement-
355
and successfully established its usefulness as a rare ary. In such a case, Fort et al. noted that 20% I"V
earth purification technique. While less efficient at of the zone refined bar should be amenable for
redistributing interstitial impurities generally present subsequent electro transport as the rest of the bar had
in the metals in larger concentrations, zone refining to be discarded as it contained portions in which
is efficient at moving certain metallic contaminants impurities have concentrated during the zone refining.
and carbon normally present in lower concentrations. The typical processing conditions for zone refining
354
Jones et al. ,355 zone refined La, Ce, Gd, and Tb are 20-30 passes at rates between 2 and 12 em h -1,
under low contamination conditions, by either using to achieve an ultimate redistribution of impurities.
ultrahigh vacuum (UHV) (13 nPa) or argon of equival- With this requirement, the metals La, Ce, Pr, Nd,
ent purity. The use of argon as cover gas reduces the Gd, Tb, and Y have been zone refined in argon but
vaporisation problems associated with volatile metals difficulty is experienced with Dy, Ho, Er, and the
such as terbium. The inert gas also stabilises the other volatile metals as even an atmosphere of argon
molten zone and reduces the experimental difficulties does not suppress volatilisation sufficiently to allow
associated with obtaining a stable molten zone in more than a few controlled zone passes.
UHV for La and Ceo The refining was carried out in In the preparation of very high purity rare earth
water cooled copper boats using rf heating. A meas- metals solid state e1ectrotransport purification

comes last in the sequence of ultrapurification Verhoeven 368 derived a theoretical expression to
procedures. predict the degree of purification attainable in SSE for
Electrotransport a specified set of conditions. However, the major
In solid state electrotransport (SSE), a direct electric limitations in achieving experimentally the theoretical
current is passed through a rod or strip of metal held limit of purity is contamination from the environ-
57
between two electrodes in an appropriate container. mene and when this is avoided by employing UHV
Those impurities amenable to electrotransport or very high purity inert gas, the slow diffusion of
migrate to one end of the sample leaving the remain- impurities from the cooler electrode ends into the
der enhanced in purity. The earliest reported appli- purified region of the rod causes contamination. The
cation of SSE to the purification of a metal was by end effects are minimised in experiments involving
Huffine and Williams352 of yttrium in 1961. The runs two or three processing steps,by removing the impure
of 200 h duration were conducted at 1230°C in an ends after each step, and proceeding further with pure
argon atmosphere with a starting material of rather sections only.
low purity (0 3300, N 510, Si 55, Fe 150, and The degree of purification attainable in SSE
Ni 250 ppm). The results indicated that 0 and N are increases both with an increase in processing temper-
quite mobile in Y. The oxygen content decreased ature and time. The highest possible temperature is
from 3800 to 650 ppm and nitrogen from 500 to obviously limited by the melting point and more
250 ppm. Nickel, iron and silicon showed evidence significantly by the vapour pressure of the metal and
of migrating under these conditions and their contents the volatilisation loss, over the extended time period
decreased by a factor of 3-5. At a higher temperature, required for SSE. When applicable it is beneficial to
1370°C, the mobilities of the impurities are greater process in the bcc phase where the solute mobilities
and the oxygen and nitrogen contents further are considerably higher.365,369,37o Another important
decreased to 340 and 75 ppm, respectively, in the parameter is the current density (CD), an increase of
pure section. which increases solute mobility. The CD and temper-
Murphy et al.356 purified a Y-2Fe alloy by SSE ature of processing are interrelated because the speci-
at 1200°C for only 60 h. The iron content in the men is heated by electrical current. A change in
cathode half of the bar decreased to about 0·01 0/0 Fe. sample shape leading to larger surface/volume ratio,
Generally, the metallic impurities migrate towards permits a higher CD at the same temperature.
the anode and the interstitial impurities such as C, Higher CDs are possible in SSE processing in an
0, N, and H towards the cathode. Most of the inert atmosphere because of the cooling effects associ-
reported investigations on purification by electro- ated with the surrounding gas. The gas atmosphere
transport have been from groups at Ames, and at the also reduces the temperature gradient along the rod
Materials Science Centre, University of Birmingham, and, most importantly, helps in the processing of the
59
UK. A summary of electro transport purification stud- more volatile metals. Fort3 has estimated that to
ies presented by Carlson and Schmidt357 has been allow extended SSE without uncontrollable volatil-
updated with the later works and is given in Table 10. isation, the vapour pressure must be '" 900 JlPa when
In addition to the elements mentioned in the table, processing in vacuum and 133 mPa when processing
SSE purification has been applied to Pr, Dy, Ho, and under argon at 66·5 kPa. The maximum processing
Sc resulting in purification and substantial increase temperature can thus be determined and except for
in residual resistivity ratio (RRR). the extremely volatile metals Sm, Tm, and Yb, SSE
holds promise for purifying all the other rare earths
either under DHV or under very pure Ar IHe at also been produced commercially in Japan by oxide-
359
66·5 kPa. ,360 Generally, there is significant increase fluoride electrolysis.373
in the RRR values after SSE processing. Residual Fused salt electrolysis has been used for the direct
resistivity ratio values can sometimes become mislead- preparation of very pure master alloys of rare earth
ing as indicators of purity. The RRR values of praeso- metals with a number of transition metals. The use
dymium are known to show some dependence on of the alloying elements Cr, Fe, Co, and Ni as solid
crystal orientation. The RRR values in SSE refined cathodes in electrolysis results in the formation of
neodymium do not exceed 20 even with high chemical low melting eutectic type alloys with Y, La, Ce, Pr,
purity. This is attributed to scattering from low temper- Nd, Sm, Gd, Dy, and some of their mixtures.330,374
ature magnetic transitions. The electrolyte contains about 2-4% RE203 dis-
Solid state electro transport has established itself to solved in a REF 3- LiF melt. The cells work between
be a viable method of turning good quality rare earth 850 and 1000°C, which is above the melting point of
metal into very good quality rare earth metal but has the alloys but below that of the cathode metal. The
not been successful in improving the purities of poorer liquid alloys are collected in a consolidated form. The
quality starting metals. Two important reasons have alloys of yttrium with magnesium or aluminium have
been cited in support of this, Jones et al.340 have noted also been prepared but using molten magnesium or
332
that in SSE only the impurities in solution are trans- aluminium as the cathode. ,338,339 Rare earth-
ported directly and the effective transport of precipi- aluminium alloys containing about 10% RE have
tates occurs very slowly. Like zone refining SSE works been reported to form37s when rare earth carbonate
essentially by redistributing the impurities and these was added to a commercial aluminium electro winning
are concentrated at the cathode and anode ends. Fort cell. In direct electrolytic alloy preparation, the ratio
et a1.359,360 have reported failure of the rods (of La of the transition metal to rare earth metal cannot be
and Pr) at the anode end during runs with relatively accurately predicted. However, the electrolytic rare
impure starting materials. The rod failed at points earth-cobalt alloys have been satisfactory for the
where impurity precipitation occurred. The melting production of RECos permanent magnet materials.
occurred either because of increase in the electrical Better composition control of the alloys is possible
resistance or decrease in the melting point of the by the other methods of rare earth alloys preparation
matrix, caused by these impurities. The high pure such as melting the alloy components together in a
starting materials for SSE are prepared either by Ca protected environment and casting. Arc melting,
reduction of pure REF 3 - the 'Ames' metals or after induction melting, levitation melting, and resistance
refining the commercial metals by zone melting or melting have all been used in preparation.
sublimation or electron beam float zone melting. 367 Rare earth-transition metal alloys can be prepared
Starting from Ames metals, Fort et al.3s9,360 used zone either in cold crucibles by means of high frequency
refining followed by SSE to obtain the highest purity induction heating or in crucibles such as boron nitride
gadolinium, 99·94 at.- %, with respect to all impurities. or alumina.376 The later, however, is slowly attacked
Preparation of rare earth alloys by the melt. A survey of the state of technology of
preparing rare earth-cobalt alloys has been given by
Herget and Domazer.377 For melting a mixture of
The first rare earth alloy to be produced in commer- samari urn or other rare earth and cobal t, either small
cial quantities was mischmetal. Directed by the initial ready made ceramic crucibles or crucibles which are
efforts of Hillebrand and Norton, and those of rammed and fired in situ using an inner graphite core
Muthmann in the preparation of rare earth metals can be used. If small quantities are to be prepared
by the electrolytic process, Auer von Welsbach suc- the components can be melted in an arc furnace.
ceeded in 1908 in producing pore free mischmetal by Vacuum induction melting, however, remains the
371
fused salt electrolysis. Mischmetal is commercially particularly clean method for preparing these
produced by the electrolysis of anhydrous chlorides alloys.
dissolved in alkali or alkaline earth chloride melts.320 Apart from the melting together of alloy com-
The cells use anodes made of graphite or carbon, iron ponents, several economic methods of alloy pre-
cathodes, and carbon, graphite, iron, or steel vessels paration directly from the component compound
lined with refractory materials to contain the molten intermediates have been investigated. Molden-
7
electrolyte. 24 The electrolyte consists of chlorides of hauer2s9 tried for the first time the simultaneous
the mixed rare earths consti tu ting the mischmetal, reduction of two compound intermediates that led to
together with NaCI, KCl, or CaCI2• The exact electro- an alloy. He reduced a mixture of iron oxide and
lyte composition depends on the producer. The alloy cerium trifluoride with calcium to prepare ferro-
(mp '" 750°C) is molten at the electrolysis temperature cerium. Then followed the method of oxide reduction
between 800 and 900°C and the current efficiency of in the presence of an alloying component.
commercial cells is only about 50%. The cells are Calciothermic reduction of samarium oxide in the
operated continuously until impurities accumulate in presence of cobalt powder yields the desired alloy
the melt and result in poor quality metal or low yield. directly in powder form. Cech 378 used calcium hydride
The preparation of anhydrous chloride for electrolysis as the source of calcium because the hydride is brittle
has been described above in the discussion on the and more readily obtained in powder form than
electrolytic preparation of La and Ce by fused chloride calcium. Samarium oxide mixed with cobalt and
electrolysis. Recently, high-purity mischmetal has been calcium hydride powder was heated at 1200°C under
prepared at Ames by Ca reduction of mixed rare 100 kPa hydrogen pressure to produce the alloy.
372 Since the late 1970s, mischmetal has Later, calcium itself was used in particulate form.
earth fluoride.
carbon
binder
lumps cake
NdCl3
NaCl,
KCl
powder powder
salt mixture
(b)
(a) Sm -Co alloy powder (b) Nd-Fe alloy
a reduction diffusion; b coreductiion

31 Preparation of samarium-cobalt alloy
A flowsheet of the 283 in Fig. 31a. This Fe ,FeB
process is given
NdFe B alloy ingot

type of process, called reduction diffusion by Cech,
has been used for the preparation of near-stoichio- a Ronson process; b Santoku process
metric Co5Sm to Co5(Smo'5Pro'5) and Co5(SmO.6 32 Preparation of neodymium-iron-boron alloys

mischmetalo'25Pro'l5) at about 97% yield. In another
variation of the reduction diffusion process, called
coreduction, Domazer379 and Herget380 used part of have to be crushed to the fineness of calciothermic
the cobalt as oxide and carried out the reaction in products before fabrication to magnets.
vacuum, Fig. 31b. A pelletised mixture of Sm203, Besides the methods described several major alloy
C0304, Co, and Ca, in stoichiometric quantity, was manufacturers follow a variety of processes summar-
heated at 1100-1200°C for 2-3 h. Alloy yield in this ised in Figs. 32, 33.382 The patented process of
process averages 98-99%. A characteristic of the Schmidt et a1.383 involves the preparation of Nd-Fe
reduction diffusion process is that the Sm and Co, and Nd2Fe14B alloys by the thermit reduction pro-
formed rather quickly in the reaction, take time to cess. The fluorides of neodymium and iron are reduced
form the alloy by diffusion, which warrants holding in a bomb by calcium in a CaF 2 lined heavy walled
the charge at the reaction temperature for 2-4 h. The iron crucible. The same process has also been success-
product of this process, the alloy, is obtained as a fully used to prepare terfenol- D, the premier mag-
powder and not as an ingot because the high melting netostrictive material of composition Tbo.3DYo.7Fe2'
point of the CaO slag inhibits the formation of a Alloys such as TbFe2, DyFe2 and Tbo.27DYo.73Fex
molten slag and thus consolidated products. The alloy (x = 1'90-1'975) have been prepared by float zone
384
powder product, however, is a suitable starting mater- solidification.
ial for magnet fabrication. The reduction diffusion Sintered magnets of Nd-Fe-B alloys are made by
process is the method by which most of the 500-600 t powder metallurgy techniques 54 by a process similar
of SmCo5 is produced every year. A basically similar to that used for Sm-Co magnets. When the
process is also used for the production of Sm(Co, Cu, magnet alloy powder is not prepared by coreduction,
Fe, Zrh'5 type permanent magnet materials. the induction melted alloy ingots are milled to pow-
The reduction diffusion process has also been used der. In addition to the powder metallurgy approach,
for the production Nd-Fe-B alloy powders.381 Co- practical permanent magnets are also made from Nd-
reduction may also be used to produce Nd-Fe-B Fe-B ribbons rapidly solidified by melt spinning. In
alloy powders. Both processes have the same advant- the melt spinning procedure molten alloy is ejected
283
ages. Nd- Fe- B alloys are much more reactive through an orifice on to the surface of a substrate
towards oxidation than SmCo5 and a proprietary disc rotating at high velocity.272 The alloy melt is
leaching procedure is used for the separation of the made by melting together the components and the
alloy and CaO. For the preparation of Nd-~e-B procedures for powder preparation are not relevant
alloys, the reduction diffusion process at ambient here.
pressure under argon is used in China. If the N d- In addition to the preparation of pure rare earth
Fe-B alloys are prepared by the melt route, the ingots metal and permanent magnet alloys, metallothermic

aq. HF
CaCL2, NaCl
salt mixture
Co
cake
Nd2 Fe 14 B alloy
powder
(a) (b) (c) (d) (e)
a Molycorp process; b Ames process; c Comurhex process; d General Motors process; e Goldschmidt process
33 Preparation of neodymium-iron-boron alloys
reductions are also used in the preparation of rare branches of rare earth extractive metallurgy - has
earth alloys used as steel additives. occurred since the 1940s.
Apart from mischmetal, rare earth-silicon alloy is The precipitation of rare earth oxalates is a very
an important form of addition of rare earth metals effective and, in principle, a simple method for the
to steel. 385 Commercially, rare earth silicides are separation and determination of rare earths but the
prepared by smelting mixed rare earth oxides with conditions of precipitation demand careful atten-
390
coke, iron scrap, and silica in a submerged arc fur- tion. ,391 Rare earths are also separable from non-
86
nace.3 The product of this process contains 30% rare earth impurities by precipitation as hydroxide
REM which accounts for only 60% recovery. In a or fluorides, or by organic precipitants.390,392 Besides
process involving the preparation of rare earth- the gravimetric methods, the total rare earth content
silicon-iron alloy by metallothermic reduction, 387,388 can be determined by titrimetry. The rare earths are
products containing more than 50% REM corres- titrated as a group with a polydentate complexing
ponding to over 80% rare earth recovery were poss- agent such as EDT A using any of the large number
ible. Mixed rare earth oxides were reduced with a of metallochromic indicators.391 For the determin-
mixed ferro silicon and aluminium reductant in the ation of individual rare earths, gravimetry and titri-
presence of a CaO- Mg or CaO-CaF 2 flux which metry have been of value only for the multivalent
389
prevented the loss of rare earth into the slag phase. elements cerium and europium. ,391 Cerium is
The smeltings were carried out at 1500-1550°C in an precipitated as Ce(IV) iodate or as Ce(IV) periodate
induction furnace. and thus separated from other rare earths in a thorium
free, rare earth solution. The most widely used titri-
metric method for individual rare earth determination
Analysis of rare earths is the titration of Ce(IV) with a standard solution of
The importance of reliable techniques for the chemical Fe(II). In the determination of europium, the trivalent
characterisation of rare earth materials at various rare earth element is reduced by passing a solution
stages of their extraction and processing cannot be of Eu(III) in HCl through a column packed with
overemphasised. The analysis of rare earth materials Jones reductor (amalgamated zinc) and the Eu(II) in
includes the major categories: (a) the determination the effluent is caused to reduce Fe(III) to Fe(II), which
of total rare earths in other materials such as minerals, is determined by titration with a standard solution
concentrates, and compound intermediates, (b) the of potassium dichromate.
determination of individual rare earth contents in a Chemical methods are limited in their application
mixture of various rare earths, and (c) the determin- to the analysis of rare earths. The chemical similarity
ation of non-rare earth metallic and non-metallic of the rare earth group of elements precludes the
impurities in rare earths. As observed by Banks and determination of individual group members by chemi-
Klingman,389 routine rare earth analysis was essen- cal methods. However, the various rare earth elements
tially confined to the first category until the early exhibit uniquely different spectroscopic and nuclear
1940s. The rare earths were isolated from their host properties and these havebeen exploited in the instru-
materials and determined as a group by gravimetric mental methods of rare earth analysis, particularly
methods. Much of the development in the analytical the determination of concentration of individual rare
characterisation of rare earths - as with many other earths in a rare earth mixture.

The spectrophotometric methods of rare earth 396

emphasised by Fassel et al. ,397 Once the free atoms are
determination are based on the absorption spectra of formed they can be detected and determined quantitatively at
rare earth ions in solution.393 All the rare earths the trace level by atomic flame emission (FES) and atomic
absorb in the spectral region 200-1000 nm with the absorption spectrometry
exception of scandium, yttrium, lanthanum, and lutet- (AAS). Flame emission spectrometry detection limits
ium. Each of the rare earth elements has a character- are generally superior to those observed in AAS; FES
istic absorption spectrum and this has been useful in techniques can be used in the analysis of rare earth
the analysis of rare earth mixtures. The rare earths mixtures and the determination of low concentration
are determined in moderately acidic solutions of the of the rare earth elements. 397,398
chlorides or perchlorates.391 Spectrophotometry has For the determination of other rare earth im-
proved useful in the direct determination of the purity purities in a rare earth, the dc arc excitation is a
of the rare earth oxides and also in the precise simple approach which provides good analysis.399
400
determination of selected rare earths in alloys.391,393 Gschneidner has noted that the high vapour
The reaction of the rare earths with chromogenic pressures of europium and ytterbium adversely affect
reagents has been used for the spectrophotometric the precision of results obtained for these elements
determination of rare earths as a group as the spectra in matrices of other rare earths using dc arc excited
of different rare earth complexes are almost identical. emission spectroscopy. In any case arc excited
The high molar extinction coefficients of coloured optical spectroscopy is slow because of the need to
complexes make the method very sensitive. The record and analyse very complex spectra.
powerful oxidising power of Ce(IV) is also made use The commercial development of atomic emission
of in selectively determining cerium in the presence spectroscopy (AES) using argon plasma as the excit-
of other rare earths or even other quadrivalent metals. ation source has permitted detection limits up to
Several metal ions such as trivalent iron, aluminium, three orders of magnitude lower than those obtained
chromium, and quadrivalent titanium and zirconium by other methods, linear response over a concen-
strongly interfere with the spectrophotometric deter- tration range several orders of magnitude, reduced
mination of rare earths with organic reagents. Ligand matrix effects, good precision, and also rapid analy-
401
buffer masking of metal chelates has been applied in sis. Two types of plasma sources are available -
such cases to increase the tolerance of various interfer- an inductively coupled plasma (ICP) and a direct
ing elements from microgram to milligram quantities current plasma jet (DCP). Broekaert et al.402 have
and this in some cases eliminates the need for a determined all the rare earth elements in standard
394
separation procedure. Hassan and Mahmoud 392 mineral samples using inductively coupled plasma
have suggested the use of the chromogenic reagent atomic emission spectroscopy (ICP-AES). Sensitivity
peridihydroxynaphthindenone, for the spectrophoto- and reproducibility have made ICP-AES a very
metric determination of rare earths. Several impurity attractive technique in the determination of rare
403
ions naturally occurring or commonly associated with earth elements. Johnson and Sisneros401 have
the rare earths do not interfere in these determin- demonstrated accurate determination of rare earth
ations. Dual and three wavelength spectrophotometry distribution in ore concentrate samples using a DCP-
techniques have been applied to the analysis of rare echelle spectrometer system. Yoshida and Hara-
404
earth mixtures by a method involving the formation guchi used ICP-AES interfaced with high perform-
of asymmetrical diazo derivatives of chromotropic ance liquid chromatography (HPLC) for the
395
acid. determination of rare earth elements. The ICP-AES
Iron has been determined in pure rare earth oxides was used as an element selective detector for HPLC.
and metals by a spectrophotometric procedure, based The separation of rare earth elements with HPLC
on the coloured complex bathophananthroline forms helps to avoid erroneous analytical results arising
with Fe(II). Many of the non-rare earth impurities from spectral interferences and greatly enhances the
such as AI, Co, Cr, Fe, N, Ni, Si, Ta, and Ti have analytical limits of ICP. Using such a chemical ICP-
also been determined by spectrophotometry. Fluorine AES method, Li et al.405 have determined 13 rare
is also determined by this technique based on the earth trace impurities in 99'999% pure Gd203.
bleaching effect of fluoride on a zirconium SPADNS In addition to optical emission, the other major
269
complex. methods used to determine all of the rare earths in a
Optical emission spectroscopy has been one of the mixture are X-ray fluorescence, mass spectrometry,
most useful analytical tools for the chemical analysis and neutron activation analysis.
of rare earth mixtures at the trace, minor, and major X-ray fluorescence (XRF) has been a rapidly
constituent levels. Flames, ac or dc arcs, and spark developing analytical technique and is based on the
discharges have been used as the excitation sources measurement of the intensities of fluorescent X-rays
of optical emission spectra.393 Flame atomic emission emitted when a sample is irradiated with hard X-rays.
spectra are strikingly simple compared with arc or Minimal sample preparation and simpler spectra are
spark spectra, which are characterised by an extremely some of the advantages of XRF and the technique
large number of lines. All the rare earths exhibit line has been used for the determination of individual rare
spectra of sufficient intensity to possess analytical earth elements in rocks, minerals, rare earth concen-
utility. The group of rare earth elements which evade trates, process solutions, and pure products, and
detection by spectrophotometry are readily observed almost any material that contains rare earths.397,406
in the flame spectra. The importance of flame chemis- X-ray fluorescence is usually limited to concentrations
try in the production of free atoms of rare earth greater than 100 ppm407,408 and is applicable to the
elements and so the atomic line spectra, has been whole concentration range up to 100%. It is a rapid

and precise method. X-ray fluorescence determination are generally minimal. The sample is irradiated in a
of the rare earth elements in rocks using synchrotron flux of neutrons. Isotopes of various elements absorb
radiation has also been reported.409 The detection neutrons, forming radioactive products, the activity
limit in a direct instrumental determination is of these are measured and related to the amount of
5% 6
5 x 10- • This limit would be reduced to 10- 0/0 the element present. Radiochemical neutron acti-
by using chemical preconcentration. In addition to vation analysis ismore sensitive and requires radio-
XRF, X-ray absorption spectroscopy (XAS), has also chemical separation of the elements after irradiation.
been used to determine the relative amounts of rare Instrumental neutron activation analysis (INA A) has
410
earths in mixed rare earth oxides. a lower sensitivity but is easier to use and is amenable
420
For the determination of rare earths in trace and to automation. ,421 Besides determination of rare
ultratrace levels a method known as X-ray excited earth impurities, NAA is the most effective method
optical luminescence spectroscopy has been for the precise determination of oxygen in rare earth
411
used. ,412 Optical luminescence is exhibited by some metals, particularly in the volatile europium and
of the rare earth complexes and ions in solids and ytter bi urn. 400
has been used both for the detection and determin- Lasers have also been used in the analysis of rare
ation of rare earths. Although the optical lumin- earths. A technique called selective excitation of probe
escence can also be excited by flame, UV or visible ion luminescence (SEPIL) has been applied to the
radiation, electron beam, accelerated protons, y radi- trace determination of rare earth elements. The rare
ation, the X-ray excited optical luminescence (XEOL) earths are quantitatively coprecipitated in CaF 2 and
of the rare earth ions has been used more extensively their 4f electron solid state luminescence is excited
than other methods. by a tuneable dye laser.422 A cw dye laser has been
Spark source mass spectrometry (SSMS) is another used for the observation and quantitative analysis of
techniq ue used to detect and determine all rare earth europium and samarium.423
elements at the trace and ultratrace levels.413,414 This In the analytical determination of rare earths, it is
technique is characterised by wide elemental coverage often convenient to separate the rare earth group as
and high sensitivity and does not require chemical a whole from other constitutents in the sample when
separation of the sample. Taylor415,416 used SSMS it is required to determine small amounts of rare earth
for trace element analysis (down to 0·01 ppm) of rare impurities in other materials. The constitution of the
earth elements in geological samples. Conzemius414 separated rare earths is then determined by the var-
has used SSMS for the analysis of rare earth metals, ious techniques outlined above. Rare earths can be
oxides, fluorides, other salts, and alloys. separated as a group and also from one another by
417
Lichte et al. have developed a method of analy- solvent extraction procedures. The solvent extraction
sis called inductively coupled plasma mass spectro- separation of rare earths from one another involves
metric technique (ICP- MS) for the determination of multistage operation and is too cumbersome to be of
rare earth elements in geological materials. Samples practical importance. Similarly, the other major
are analysed directly following acid digestion without method of individual rare earth separation, ion
need for preconcentration or separation. This method exchange, is not widely used for the analytical deter-
has detection limits in the range 2-11 ng/g and rivals mination of rare earths.
the accuracy of inductively coupled plasma emission In rare earth metals, particularly the high purity
spectrometry and instrumental neutron activation rare earth metals, carbon, oxygen, and nitrogen con-
analysis. stitute the major fraction of the impurities present.
Quantitative ion microprobe analysis or secondary The determination of carbon in rare earths is by
ion mass spectrometry (SIMS) is a highly sensitive combustion of the sample in a stream of oxygen. The
technique that has been recently used418,419 for the carbon dioxide liberated is determined by a con-
determination of rare earth element abundances in ductometric method, infra red (IR) radiation absorp-
most minerals. For example, in allanite the europium tion, or by thermal conductivity measurement.
and the heavy rare earth concentrations are below Oxygen, carbon, and nitrogen are determined by
the electron microprobe detection limits, but ion vacuum or inert gas fusion'.269 Highly sensitive instru-
microprobe analysis has enabled the complete rare ments are commercially available for these determin-
earth element abundance pattern to be determined.418 ations. Oxygen has also been determined by neutron
Ion microprobe analysis enables determination of all activation analysis and nitrogen by the Kjeldahl's
the rare earth elements down to the level of 100 ppb. 424
So far this method does not appear to have been method.
applied to ultratrace impurity determination in highly
purified rare earth intermediates or finished products. Applications of rare earths
Among all the analytical techniques, the record for The end uses of rare earths come under two broad
425
the lowest rare earth detection limit is held by neutron categories. Those using mixed rare earths: either
activation analysis (NAA), or more specifically, radio- naturally occurring mixtures or mixtures enriched
chemical neutron activation analysis (RNAA).420 with respect to a particular rare earth element or
Using this method as little as 1·6 x 10-17 g of elements, and those using individual rare earths in
europium or just about 60 000 atoms of europium various levels of purity. These uses are summarised
have been detected in a matrix. Neutron activation in Figs. 34 and 35. Rare earths consumption in mixed
analysis is a highly sensitive technique for the quanti- form constitutes, on a volume basis, about 95% of
tative determination of rare earths particularly at low the total rare earths consumed. However, the separ-
concentrations. The sample preparation requirements ated rare earths, which account for only 50/0 in terms
34 Applications of rare earths: metallurgical
of quantity, constitute 500/0of the financial value of material in the manufacture of arc light carbons and this
total rare earth consumption. The major rare earth ranks third in the list of the early uses of rare earths.371
consuming countries are the USA and Japan.
Together they accounted for two-thirds of total world While these early applications accounted for the
rare earth consumption in 1986. The non-communist continued consumption of rare earths, in later years
world market for rare earths has been discussed in a several new applications emerged, and the rare earths
recent publication.426 became increasingly important in various of branches of
The first and a few early commercial applications technology.
leading to the industrial consumption of rare earths The rare earths played a leading part in the dis-covery
and the birth of the rare earth industry were due to and commercialisation of nodular iron. Nodu-lar iron
Auer von Welsbach.371 He patented in 1891 the has properties similar to mild steel and results when the
production of incandescent lighting mantles com- graphite flakes in cast iron are converted to nodules.
% Morrough427 discovered in the 1940s that spheroidal
posed of 99% Th02 and 1 Ce02• A few years later
graphite could be routinely produced in the laboratory
in 1903 he invented a pyrophoric metal alloy called
'flintstone' to ignite his mantle. The flintstone
%
in irons containing 0·02 Ce. The rare earth elements
contained 700/0 mischmetal and 30%Fe. These cleanse the melt of elements which prohibit spherical
lighter flints are still very common and account graphite growth and the com-pounds they thus form
for the consumption of about half of the total provide heterogeneous sub-strates for graphite
mischmetal produced. The mixed rare earth fluorides, nucleation. The good physical properties of nodular iron
were found to be an excellent radiant light material. coupled with its good foundry properties have
Rare earth fluorides have been used as core filling established nodular iron as
35 Applications of rare earths: non-metallurgical
an engineering material, particularly in the auto- improvements in the toughness characteristics of

motive industry. HSLA steels, rare earth additions improve fatigue,
The deletrious effect of sulphur on the mechanical creep, and several other mechanical prop~rties.429,43o
properties of freshly cast steel is well known. Iron The rare earths react quite efficiently with hydrogen
sulphides form and concentrate at the boundaries in steel and also lower the hydrogen diffusion
between the grains of steel formed on solidification. coefficien 1.
Such steels are very brittle and fracture on working. Rare earths are added to steel as mischmetal, rare
Addition of rare earths to steel causes the sulphur earth silicides (RE content 30%), alloys such as Fe-
content to be captured in the form of very stable Si-l0RE and Mg- Fe-Si-0·1-0·2RE. The effect of rare
compounds such as RE2S3 or RE2S20 that tend to earth metals, introduced by whatever means, is the
form globular or spherical inclusions which do not same. The amount of mischmetal added to ferrous
concentrate at the grain boundaries, thus greatly alloys is about 0·1-0'20/0. Both in nodular iron and
enhancing ductility. These sulphides or oxysulphides in steels considerable effects are achieved with small
of rare earths are stable at steelmaking temperatures additions. A few kilograms of mischmetal was added
and, unlike other sulphides such as those of mangan- to each tonne of special steel used in the manufacture
ese, they neither deform nor elongate under processing of pipe for the Alaska oil pipe line;431 mischmetal
428
conditions. As the rare earth concentration improves the physical properties of steel under Arctic
increases MnS inclusions are displaced by rare earth conditions. The practice of adding rare earths to steel
oxysulphides or sulphides. The stability of granular has been reviewed by Wauby.385 In spite of the fact
rare earth sulphides alleviates the detrimental effects that the major consumption of rare earths is in the
of elongated MnS inclusions on toughness. Besides iron and steel industry the annual tonnage of that

industry that is currently treated 32 with lanthanides AI-Fe-Ce alloy retains good strength even up to
is very small. The use of rare earths in the form of 340°C. Rapid solidified titanium alloys (the rare earth
rare earth silicides or mischmetal additions in steels addition, particularly Y, Nd, Er, or Ce, ranges from
grew explosively in the 1970s and peaked around 1 to 2%) show improvements by orders of magnitude
1975.3 Since then the market for rare earth products in high temperature yield strength, stress rupture life,
dropped off, following the development of desulphur- and creep resistance.438
432
isation processes. Long range ordered alloys such as (Fe,Co h V,
Rare earths also playa significant role as alloying (Fe,Nih V, and (Fe,Co,Nih V are potential materials
elements in a variety of other alloy compositions. for high temperature applications. Addition of a small
Essentially, the rare earth elements are added to alloys amount of Ce « 0·1 %) together with titanium doubles
to enhance their oxidation resistance. Yttrium is the the rupture ductility, substantially lowers the creep
active component in the M-Cr-AI- Y (Fe-Cr-AI- Y, rate, and considerably improves the rupture life of
Ni-Cr-AI- Y, Co-Cr-AI- Y) family of alloys rec- some of these alloys.438 In another application, oxide
ommended for use in high temperature oxidising mixtures containing Zr, Ce, and Y oxides of controlled
environments. The stability of the alumina-chromia particle morphology are plasma sprayed on to metal
skin is enhanced by traces of yttrium. Lanthanum surfaces to create barrier coatings for the protection
and cerium playa similar role in certain Ni and Co of the metal substrate against high temperature
438
superalloy compositions. Mischmetal, in small con- degradation.
centrations (0'03-0'05%) added to electrical resistance The largest single use of rare earths, in which the
alloys such as Ni- 20Cr, causes the formation of dense naturally occurring rare earth mixture is useful, is in
and more adherent surface oxides, leading to increase the manufacture of rare earth containing, zeolite
in service life typically from 1025 to about 10000 h.433 cracking catalyst required in the petroleum refining
In what is perhaps the first major industrial use of process.439-441 In the early 1960s it was discovered
cerium metal, it is added to the new Cu 78 high that incorporation of small amounts of zeolite in
temperature aerospace alloy (AI-8Fe-4Ce) of Alcoa a silica-alumina matrix resulted in considerable
for enhancing its oxidation resistance. 54 enhancement in the performance of the catalyst in
Oxide dispersion strengthened alloys utilise the gas-oil cracking. From then on zeolite cracking cata-
high thermal stability of rare earth oxides (e.g. Y203, lysts have largely replaced the amorphous silica-
Ce02), to impart properties such as high temperature alumina catalysts used previously. Zeolites are made
creep resistance to superalloys.434 catalytically active and thermally stable at operating
Magnesium alloys containing about 3% misch- temperatures by replacing sodium ions by rare earth
metal and about 1% Zr show enhanced creep strength ions. Rare earth exchanged zeolites are prepared by
at high temperatures compared with conventional many methods and the rare earth content of the
Mg alloys.435 Significantly higher strength at all tem- catalyst may vary from 0·5 to 5%. The rare earth
peratures is obtained by using Di (Nd + Pr) in place starting material used commercially for the manufac-
of mischmetal as the alloying constituent. The rare ture of these catalysts is usually a mixture of rare
earth improves high temperature strength owing to earth chlorides. Rare earth usage in commercial pet-
local precipitation hardening, while the zirconium roleum cracking catalysts started in 1964 and it is the
grain refines. These new generation Mg alloys are single largest volume application of the rare earths.
useful at about 300°C and find applications as jet An early and continuing application of the rare
engine castings.433 earths is in the glass industry. As early as in 1896
Mischmetal additions have been used to improve: Dressback patented and manufactured a mixture
(a) Al alloys for electrical conductor applications, containing Ce and other rare earth oxides for decol-
(b) the quality of products made by deep drawing of lead orising glass.442 This was the first commercial use of
bearing bronzes, (c) the wear resistance of highly loaded cerium. Iron oxide is always present as an impurity
bronzes, and (d) the corrosion resistance and in glass and causes a yellow-green colour. This is
strength of Co-base superalloys.433 A small amount overcome by a decolorisation process involving the
of yttrium (100 ppm) in combination with Zr has addition of cerium. In 1912 Crookes found cerium to
been found to increase (by 50%) the conductivity of be excellent for UV absorption, a feature useful in
Al transmission lines.436 Mischmetal is a constituent eye protective glasses. Crookes absorptive sun glasses
in the alloy Galfan (Zn-5%AI-0'05% mischmetal) contain the natural ratio of Nd/Pr together with high
used as a corrosion resistant coating for steel and amounts of Ce to give a good UV cut off. Glasses
wire. Galfan is superior, with respect to corrosion with 2-4% Ce203 (or Pr, Nd oxides) absorb UV and
resistance and permeability, to standard galvanised IR radiation and are used for the production of glass
steel sheet and wire of equal coating thickness blowing and welding goggles. Didymium oxide has
and has comparable paintability and weldability long been used in welders goggles because of the high
properties. 437 concentration of Nd and Pr which effectively absorb
The new generation of metallic materials; the rapid yellow sodium light.443 While small amounts of Ce02
solidification (RS) alloys under development (AI-Fe- decolorise glass, '" 1%Ce02 makes glass yellow and
Ce, Ti-Er) rely on the rapid gettering of oxygen by larger amounts of Ce02 make glass brown. Neodym-
lanthanides. The stability of dispersed oxide particu- ium colours glass bright red, praseodymium colours
lates thus formed, improves the high temperature glass green, and their mixture colours glass blue.
performance of the alloys.434 Compared with heat Neodymium, praseodymium, and also erbium oxides
treatable ingot metallurgy products whose elevated are used for colouring glasses. Cerium is used only
temperature capability is limited to 175°C, the RS in conjunction with other colouring oxides. The

practical application of the optical properties of transparent ferroelectric ceramic materials which have
materials containing rare earth elements (Nd, Pr, Ce, increasing application in practical devices in ceramics
and Er) began. in the early 1930s. Nd203, together and industry.446 An optically transparent ceramic
with V2°3, is used for making optical glass for composition having high temperature applications
photometers, nicol prisms, etc. A recent new develop- contains yttrium oxide mixed with 10% thorium
443
ment is the use of Nd oxide for TV face plate glass. 54 oxide. Y-Si-N-O has been considered as the high
Cerium acts as stabiliser against browning/fogging of technology ceramic for turbine blade applications.
glass under nuclear radiation (y and cathode rays). The materials under development include Si3N4
Most CRT face plates use Ce-stabilised glass. As a doped with Y203 and Si3N4-A1203 (known as
result of work in the 1950s and 1960s cerium is used Sialon) doped with Y203.447 The mechanical and
in radiation shielding windows. Cerium in container oxidation properties of Y203-doped Si3N4 are far
glass prevents solarisation caused by UV radiation. superior to those of undoped Si3N4. in the
Lanthanum was first used in the optical glass Rare earths have become very important
industry in 1935 by Morey.442 Low silica glasses design of new zirconia ceramics. For example, yttria
containing lanthanum oxide possess a high index of and ceria are added to transformation toughened
refraction and low dispersion, and are extensively zirconia: partially stabilised zirconia (PSZ) and tetra-
used in the manufacture of lenses.371 Lanthanum gonal zirconia polycrystals (TZP), which are high
oxide does not impart colour to the glass. It is very performance ceramics with superior toughness and
important that the rare earth materials introduced in strength properties at low and intermediate temper-
the optical glass must be of 99'9-99'9950/0 rare earth atures. The increase in. toughness of zirconia is
oxide purity,442 and that no radiation absorbing achieved by the transformation of the metastable
oxides are present. In Japan, the world's largest tetragonal phase to the more stable monoclinic phase.
manufacturer of optical glass, consumption of La203 Applications for these ceramics include components
has been rising 72 in recent times because of the high for adiabatic diesel engines, cutting tools, wire draw-
production of autofocus SLR cameras and video ing dies, and furnace elements for use up to 2000°C
cameras. The rare earth elements act as activators in in oxidising atmosphere.448 Japanese researchers have
laser glasses. A well known example is the neodymium built prototype automobile engines composed of
371
laser. Glasses doped with rare earths such as Nd, yttria based ceramics.448 Yttria stabilised zirconia,
Vb, Er, and Ho could possibly find future technologi- which becomes conductive at high temperatures,
cal applications in the areas of luminescent solar serves as an electrode in the high temperature
concentrators and light sources for fibre optics in electrolysis of water.371 A ceramic composition
444
addition to use as laser materials. Certain new LaO.84SrO.16Cr03 (Ref.449) has found commercial
laser materials are based on Er + and H03 +. Lumin-
3
application as a heating element in oxidising environ-
escent solar concentrators have been prepared using ments up to 1900°C; more than 5000 h of service life
a combination of Nd 3+ and Yb3 + with UO~ + or has been claimed. Addition of about 1% each of
3
Cr +. Fluoride glasses for fibre wave guide sources cerium and lanthanum to titanium carbide abrasives
contain Er3 +. has been found to improve dramatically the surface
Ce02 or the natural mixed rare earth oxides make finish of high carbon chromium steel.450 The solid
excellent abrasives for glass polishing in the manufac- solution of titanium carbide and scandium carbide is
ture of CR Ts, optical glass, mirrors, photomasks, an extremely hard material and a potentially useful
451
plate glass, lenses, and cut glass. During polishing, in cutting material. Addition of up to 20/0 mischmetal,
addition to mechanical abrasion, extensive chemical Ce, or Y to the binder alloys in cermets improves
reactions occur on the surface of glasses which work their properties.433 Laferty452 found that LaB6 has
to remove the material. 371 Even in mixed oxides superior thermionic properties.' It has an extremely
Ce02 represents the active element in the polishing high melting point (> 2500°C), low vapour pressure,
media. low work function, and excellent thermionic emission
Approximately 350 t of rare earth oxides are used current; it is a better electron emitter than tungsten.
annually for glassmaking. Cerium concentrate This material is currently being used in the electron
(880/0Ce02, 12%La203 + Pr6011 + Nd203) consti- guns of electron microscopes, TV s, and CRTs where
tutes the biggest share of the market. La203 has the enhanced brightness and high electron emission are
next largest market followed by 95-99'90/0 pure Ce required.
oxide, Nd oxide, and a small amount of Er oxides. The first application of rare earth elements in a
The rare earths have a variety of applications in sophisticated technology came in the early 1960s
ceramics. Praseodymium incorporated in the Zr sili- when a material consisting of Eu doping of an yttrium
cate lattice is used in theproduction of very beautiful containing host Eu3 +. YV04 was introduced as the
high temperature resistant, lemon yellow pigments red phosphor in colour TV picture tubes replacing
for the ceramic industry.371 In the closed loop emis- the previously used Ag activated, CdS red phosphor.
sion control systems in automobiles, yttria stabilised, At present, YV04 has been replaced by either Y203
zirconia electrolytes find use.445 In another appli- or Y202S, Each colour TV screen requires about
cation in automobiles several percent of Ce oxide 5-10 g yttrium oxide and 500-1000 mg europium
371
added to y-alumina supports, stabilises them against oxide and since 1964 the TV industry has been
degradation during use in automotive catalytic con- using highly purified Y and Eu oxides in tonne
54
verters. Hundreds of kilograms of La203 are quantities. The purities required exceed 99'9% and
consumed annually in the manufacture of lanthanum many individual impurities in excess of 100 ppm may
modified, lead zirconate-titanate (PLZT) optically 443 Thus, though the oxides (of Y and
be deleterious.
Eu) sold for this purpose represent less than 1% of valuable for the use of europium for control rods in compact
the annual tonnage of rare earths used, they account 371
453 nuclear reactors such as submarine power reactors.
for about 25% of sales. Yttrium has low capture cross-section for thermal neutrons
A number of rare earth phosphors have been and could be a material for tubing
developed for conversion of X-radiation into visible in molten salt reactors. Because of their high hydrogen
light. These phosphors, which consist of atom density and high temperature stability, Ce
3
Tb +:Gd202S or Tb3 +:La202S, have allowed sig- and Y hydrides are useful as neutron moderators.
371
nificant reduction in the X-ray dosage required for The (n, /3) reaction characteristic of Gd and Dy
medical radiographic data. A. Tb-activated gadolin- and their availability in thin foils has also greatly
ium oxysulphide phosphor enables up to 80% lower benefited the non-destructive technique of neutron
X-ray dosage to patients. Other X-ray phosphors for radiography.436
medical radiography include Eu-activated barium Among the applications of the rare earths, one of
orthophosphate,454 BaFCI:Eu, and LaOBr:Tm. A the most spectacular has been their use in the new
number of rare earth phosphors have also been generation permanent magnet materials. In the late
developed for colour contrast radiography. Rare earth 1960s Strnat et al. discovered the remarkable perman-
phosphors based on europium and scandium have ent magnet properties of the RC05 series of materials,
established themselves as superior to any other phos- first with YC05 (Refs. 461,462) and then with several
phor for use in commerciallamps.436,455 Luminescent light lanthanides, by especially SmC05 (Ref. 463), which
materials activated by europium and scandium is characterised high induction, very high intrinsic
deposited on the glass have been particularly useful coercivity, and high magnetic energy. Rare earth
in providing energy efficient illumination which also cobalt magnets were the culmination of the efforts
ranks high in visual efficiency. directed towards combining the giant magnetic
An application for the rare earths which was ident- moments of the rare earth atom with the high Curie
ified in 1970 concerns the hydrogen energy system. temperature of the transition elements. This develop-
Solid state storage of hydrogen offers advantages in ment grew rapidly in the 1960s and 1970s. The energy
volume, weight, pressure, energy savings, and safety product (MGOe) is a measure of the useful strength
over cryogenic and compressed gas storage.456 The of a permanent of magnet. SmC05 magnets have mag-
compound LaNis has been found to absorb and netic energy up to 20 MGOe compared with 5
desorb large amounts of hydrogen gas in unde- MGOe for AlNiCo magnets.72 The rare earth magnets
manding conditions, making it an excellent candidate can be extremely short and still provide adequate
material for hydrogen storage,457,458 and related tech- magnetising force.464 They have allowed miniaturis-
nological applications. The world's largest hydrogen ation of devices that use permanent magnets. There
storage vessel has been made by Kawasaki Heavy are applications in microwave technology, clocks and
Metal Industry.459 The vessel has a capacity of wrist watches, small and horse power size electric
3 motors, portable ultrasmall loud speakers for sound
175 Nm and carries a total 1000 kg charge of La
rich mischmetal-nickel alloy for hydrogen storage, reproduction, and computer line printers.376 A prod-
and is operated at 700 kPa (at 30°C) storage pressure. uct made possible by the unique characteristics of
Compared with high pressure hydrogen storage of rare earth magnets is a new type of permanen t magnet
same capacity the vessel is 30% lighter and occupies stepping motor providing up to 200 steps/revolution,
'" 14% of the volume. Besides, in one cycle of absorp- formerly available only through the use of a so called
tion-desorption hydrogen gas is upgraded in purity hybrid stepping motor.464
from 99'99% to 99'99999%. The Japanese have also Compared with SmC05, the 2: 17 alloys such as
been developing hydrogen fuelled cars and have even Sm2 Co 17 provide enhanced magnetic properties in
successfully road tested one.54,459 While LaNi5 is addition to savings on raw materials costS.436 The
most efficient in terms of both capacity and kinetics, use of mischmetal in place of samarium offers signifi-
it also remains more expensive than the majority of cant cost reduction particularly for large volume
its rivals. applications such as in electric machinery. The theor-
Rare earths have also found a variety of appli- etical energy product of PrC05 is 30% higher than
cations in nuclear energy. One of the largest uses of that of SmCos but PrCos has a substantially weaker
Gd oxide is in the nuclear power industry, used in anisotropy compared with SmC05.465 Praesodymium
General Electric's boiling water reactors (BWRs) as which is more abundant than samarium can signifi-
a burnable poison, mixed directly with uranium to cantly replace Sm in Sm-Co materials.434 The use of
achieve a uniform neutron flux during the life time praesodymium in magnets would give it application
of a fuel element. About 2200 kg of Gd oxide are in a quantity it has never had before.466
estimated to be in use in 26 US operational BWRs. The discovery of a new ternary phase Nd2Fe14B
A gadolinia burnable poison system for pressurised reported in 1984 by Sagawa et al. at Sumitom0467,468
hot water reactors has also been under development and Croat et al. at General Electric469,47o ushered in
at Babcock and Wilcox.46o Besides gadolinium, the a new era for the rare earth-transition metal based
elements Eu, Sm, and Dy have high capture cross- permanent magnets. Nd- Fe- B magnets are high
section for thermal neutrons. Europium is almost strength magnets with a magnetic energy of 50
unique because, like hafnium, it exhibits a high cap- MGOe, which is a factor 2·5 times greater than that
ture cross-section of the natural isotopes combined of SmC05 magnets. There is a large potential for these
with an uninterrupted series of five isotopes all of magnets as iron which is cheap and available in
which arise on capture of a neutron and all of which abundance (unlike the scarce and costly cobalt)
have a high capture cross-section. This property is is present as the main constituent (82·4 at.- %).

Neodymium is also in ample supply being the third In magnetic bubble domain memory materials for
most abundant rare earth and constituting 13% of information storage, the non-magnetic GGG (garnet)
72
is used as the substrate on which the magnetic garnet
I
bastnasite and 18'50/0 of monazite ores.
Nd-Fe-B magnets have already begun to penetrate films composed of the rare earths Y, Lu, Sm, and
commercial markets. In Japan these magnets have other elements such as Ge and Fe are deposited. The
been used in data processing and audiovisual equip- substrate consumes a larger volume of rare earth than
ments in non-extreme thermal environments. The first the deposit and the annual use of Gd203 for making
large scale application of these magnets is linked to GGG substrates is estimated to be 20-40 t. Yttrium iron
the substitution of ferrite magnets by Nd- Fe- B mag- garnets (Y3FeS012 - YIG) have found important
nets in the small electric motors of automobiles, an uses in radar and communication devices. Yttrium
application being pioneered by General Motors. and gadolinium are also used in garnets for micro-
443
Another potential use of Nd magnets lies in the wave applications. Besides use as microwave filters
medical applications such as in the magnetic reson- yttrium aluminium garnet (Y3Als012 - YAG) crystals
ance imaging equipment.69 when doped with small quantities of Nd or Er can
It is likely that 72 Nd magnets could capture be used as lasers. A frequency doubled 532 nm
35-65% of the total magnet market by 1995. With neodymium doped YAG (Nd:YAG) laser with a green
neodynium in ample supply, the Nd magnet cost beam has been approved for medical use by the Food
would drop to a level when they will replace not only and Drug Administration.49 Rare earths such as Pr,
the Sm-Co magnets but also AlNiCo. The main Nd, Ho, Er, and Tm used in a variety of hosts
limitation of Nd- Fe- B magnets is their lower Curie such as CaW04, YAG, and LiFY4 are materials for
temperature (125-150°C). This leaves the field open optically pumped or activated solid state lasers with
for Sm-Co magnets for uses where this property is a wide variety of wave lengths. Rare earths have also
of major importance. S4 been used in the miniaturisation of capacitors and
32
Gadolinium metal is unique in that it looses its the production of thermistors.
ferromagnetic behaviour at temperatures close to One of the most exciting topics in science today is
ambient. Cycling gadolinium above and below this high critical temperature Tc superconductivity. Until
temperature (the Curie point) in conjunction with the recently all the known high Tc materials contained
associated transfer of energy provides a means of either yttrium or one of the elements of the lanthanide
434
operating a refrigeration cycle,471 called 'magnetic series. A ceramic compound of Y, Ba, Cu, and 0,
refrigeration'. Alloys of gadolinium are used for lower exhibits zero resistance at 90-100 K making it poss-
434
temperatures. Applying the magnetocaloric effect ible to replace expensive liquid He by cheaper liquid
where materials held in a magnetic field cool down N 2 as a refrigerent for a superconductor. The new
when the field is removed, researchers at the Los superconductors including yttrium have already been
Alamos National Laboratory in New Mexico have fabricated in thin films, the form used in electronic
been developing a magnetic refrigerator which is 2-4 circuits, on a laboratory scale in the USA. Commercial
times more energy efficient than conventional refriger- use of these superconductors will depend in whether
ation equipment.49 The intermetallic PrNis has been these materials can sustain the high currents necessary
called the low temperature record setter147 to signify in applications such as electricity pylons, power gener-
its use as refrigerent in obtaining extremely low ators, electric storage units, and electric motors.
temperatures (down to 27 JlK) by nuclear magnetic Another potential market lies in computers where
cooling. power losses are usually significant but currents are
Iron alloys of rare earths such as Tb, Sm, and Dy small. A question raised by Fjellvag et al.472 recently
exhibit properties of very high magnetostriction and is on the possibility of using rare earth oxide-hydrox-
find particular application as transducers for the ide mixtures for the synthesis of 123 (REBa2Cu307_cS)
conversion of magnetic energy to mechanical energy. superconductors. A process based on such materials
The Laves phase alloy Tbo.3DYo.7Fel.9 ('terfenol-D') would prove for more economical than that starting
in particular shows outstanding magnetostrictive from the pure oxide. The major developments in the
properties and is presently the focus of field have been comprehensively reviewed.473-476 As
development,147,384,4s9 far as the rare earths are concerned, the practical
The destruction of ferromagnetism by heating realisation of commercial superconductors would
above the appropriate Curie points is at the heart of mean an unprecedented demand for several of the
a new magnetic recording technology - 'magneto- rare earths.
optics', which offers repeated read and write capabili-
ties. Thin alloy films of Fe- Tb and other lanthanides
such as Tb-Co, Dy-Fe, Gd-Fe, and Gd-Co capable Summary
of supporting magnetic domains are deposited on a Rare earth extractive metallurgy has so far been
rigid substrate and the erase and read operations are confined essentially to the mining and processing of
434
done by laser beams. The perpendicular magneto- bastnasite, monazite, and xenotime ores to pure mixed
optical disc has an excellent storage capacity which and separated rare earth compound intermediates,
is a factor of almost 100 that of the conventional metals, and alloys. As far as the technical feasibility
video disc and could soon be entering the commercial of the entire operation is concerned, present develop-
4s9
market. ments in the extractive metallurgy of rare earths
While the nuclear power industry has been a major partly satisfy the conclusion of Powell and Spedding
consumer of pure gadolinium, the largest use of that '... no rare earth is beyond the reach or purse
gadolinium has been in magnetic bubble 46o of the scientist who wishes to study them'. But the
devices.
rare earths, more specifically the heavy rare earths, the high cost of calcium, the expensive reactor, and batch
have remained expensive. Among the many reasons nature of the process make it very expensive and during all
for this, the most important is the inherent low these years the search has been to discover effective but
concentration ofthe heavy rare earths in the ores inexpensive processes. In metal-
presently used as starting materials for rare earth lothermy, lithium vapour reduction of rare earth
production. An increase in the amount of rare earth chlorides and also recovery of high melting rare earths
production from heavy rare earth enriched resources as low melting magnesium alloys have provided some
such as xenotime, gadolinite, uranium, and phosphate solutions. The recovery of reduced rare earth metal
leach solutions would perhaps ease this constraint. as magnesium alloys has been essentially confined to
At present, however, there is no sign of any commer- the extraction of yttrium and does not appear to have
cial processing of these ores on a scale that would been tried for other heavy rare earths. The metallo-
have significant impact on prices. Apatites will become thermic alloy process has recently been successfully
increasingly important because of their yttrium and tried and neodymium oxide was reduced by sodium
also heavy rare earth enrichment and wide avail- in a molten CaCI2-NaCI salt bath and the reduced
ability. An interesting aspect of the rare earth industry metal was extracted with a zinc alloy. This process
is that during the past 50 years, discovery of new rare combines the advantages of inexpensive starting
earth reserves has constantly outpaced the evolution materials and low temperature of operation. The
of any large growth in their consumption. The dis- choice of an appropriate metal that forms a low
covery and exploitation of the Mountain Pass bast- melting alloy with the rare earth that can be distilled
nasite deposit, the discovery of the huge Bayan Obo to produce the pure rare earth metal would make the
rare earth reserves, and the recent discovery of a large process worth trying for the other rare earth metals.
heavy mineral sand deposit near Horsham in South Difficulties have been found with the complete
Australia, all come in this category. removal of zinc. Another process that has been dem-
Several new sources of rare earths have been ident- onstrated for reactive rare metals such as uranium
ified in Australia 67 and in Canada. Significant quantit- and titanium involves carbothermic reduction of the
ies of yttrium and heavy rare earths probably occur oxides in the presence of molten tin to recover the
in the multimineral deposits near Hall's Creek in the metal in the alloy from which the metal is sub-
Kimberley range, Western Australia. A new rare earth sequently separated. This also comes under the cate-
source near Alice Springs, Northern Territory, Aus- gory of an intermediate alloy process and could be
tralia has also been reported. Considerable quantities tried for the rare earths.
of rare earths occur at the Mount Weld deposit near The electrolytic production of the three rare earth
Laverton, Western Australia. The Horsham deposit metals La, Ce, and Pr is uncomplicated in that they
in Victoria contains 580000 t of monazite and can be recovered continuously as molten metals at
170000 t of xenotime reserves. About 150 Mt of cell temperatures less than 1POO°C and there is a
reserves grading 4% heavy rare earths occur at West choice of chloride as well as oxide-fluoride baths.
of Eneabba operations. Rare earths, probably The use of oxide-fluoride baths is very attractive
enriched in the heavier elements, occur associated technically except for the high operating temperature,
with beryllium minerals in the Thor Lake deposit corrosion, and low solubility of oxide in molten
near Yellowknife, North West Territories, Canada fluoride. The cell throughput is severely curtailed
and near Schefferville on the border areas of Quebec because of the need to restrict current density to
and Labrador, Canada. avoid the onset of anode effect. For rare earth metals
Several new rare earth reserves in many parts of other than those mentioned above the electrolytic
the world are probably only awaiting exploration and process through the intermediate alloy route on lines
identification. An example is the identification of outlined recently by Chambers and M urphy334 looks
feldspar metasomatites as a new source of rare earths. attractive. The alloy processes also circumvent the
Another unexplored region is the ocean floor. Pyro- difficulties associated with the large scale preparation
chlore is another promising source of yttrium. Rare of pure rare earth metals as, for example, neodymium
earth extraction from these and many other sources for use in the preparation of Nd- Fe- B compositions.
would need considerable metallurgical process devel- Ultra purification of rare earth metals by zone
opment to isolate the rare earth concentrate from refining followed by electro transport has developed
other constituents. to a level where metals 99·99 at.-ojQ pure with respect
In the separation of rare earths further develop- to all elements in the periodic table can be prepared
ments would most likely be in solvent extraction in the case of low vapour pressure rare earth metals.
separation: both in the use of new extractants, use The maximum attainable purity for other rare earth
of synergists, and in better controlled process metals is limited mainly by the vapour pressure
implementation. of the metal at the processing temperature and
As regards rare earth metal reduction processes, by environmental contamination. By continuous
the question of a technically perfect reduction process improvement to eliminate environmental contamin-
for rare earth metal preparation was answered more ation, increasingly higher levels of purities have been
than 25 years ago with the development at Ames of achieved during the past three decades.
the inert atmosphere calciothermic reduction of rare The applications of rare earths have grown very
earth fluorides in tantalum crucibles and the La- considerably in number during the past 25 years.
reduction distillation for the preparation of multi- There is much interest to substitute a more abundant
valent volatile rare earth metals. The high cost of rare earth for a less abundant rare earth to effect
fluorine chemicals that end up as low value CaF 2, resource conservation. This is exemplified by attempts

to substitute praseodymium or mischmetal for sam- 24. K. A. GSCHNEIDNER, Jr and L. EYRING (eds.):'Handbook on the
arium in the permanent magnet alloys. Efforts in this physics and chemistry of rare earths', Vols. 1-11; 1978-88,
Amsterdam, North-Holland.
should continue because in the absence of significant 25. 'Papers presented at 16th rare earth research conf.', Talla-
shifts in processing of resources for rare earths from hassee, FL, Apr. 1983, J. Less-Common Met., 1983, 94.
bastnasite and monazite the relative availability of 26. H. B. SILBER, L. R. MORSS, and L. E. DELONG (eds.): 'Papers
different rare earths would remain the same. The presented at 17th rare earth research conf.', Hamilton, Ont., June
1986, J. Less-Common Met., 1986, 126.
anticipated major consumption of rare earths for oxide 27. H. B. SILBER, L. R. MORSS, and L. E. DELONG (eds.): 'Papers
superconductors is perhaps only a decade away, by presented at 18th rare earth research conf.', Lake Geneva, IL,
which time the problems of current density and Sept. 1988, J. Less-Common Met., 1989, Part 1, 148; Part 2, 149.
fabrication of these superconductors may be solved. It is
28. c. K. GUPTA and T. S. KRISHNAN (eds.): 'Rare earths - appli-cations
then that the rare earths would perhaps shed the label and technology', Mater. Sci. Forum, 1988,30.
rare and become common both in the board rooms of 29. R. G. BAUTISTA and M. M. WONG (eds.): 'Rare earths'; 1988,
large corporations and also for the man in the street, as Warrendale, PA, The Minerals, Metals and Materials Society.
so hopefully predicted by Bautista.446
30. C. DEMAYO: in 'Handbook of chemistry and physics', (ed. R. C.
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Extractive Metallurgy of Rare Earths: C. K. Gupta and N. Krishnamurthy

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Extractive metallurgy of rare earths

C. K. Gupta and N. Krishnamurthy

oped for mixed or simply separated rare earths. The

International Materials Reviews 1992 Vol. 37 NO.5 197

availability is very small in comparison. Hence, the presence

International Materials Reviews 1992 Vol. 37 NO.5

crusta l distri bution

International Materials Reviews 1992 Vol. 37 NO.5

International Materials Reviews 1992 Vol. 37 NO.5

International Materials Reviews 1992 Vol. 37 NO.5

earth reserves is also indicated in Fig. 3. The major minerals

byproduct of wolframite. Scandium content in wolf- c MALAYSIA

USA. The only mineral that contains a large percent- o

found in the elements formed in the fission of uranium

World rare earth production 4 World rare earth production

western world cumulative

5 Quantities of individual rare earths

International Materials Reviews 1992 Vol. 37 NO.5

metallurgy of rare earths beach sands (1-4

non mag mag: ilmenite

non cond cond: ilmenite non cond cond

magnetic separa tion ilmenite ,rutilE: ,garnet,

ilmenite, leu coxene

monazite zircon monazite zircon monazite zircon

International Materials Reviews 1992 Vol. 37 NO.5

garnet, quartz non-magne tic tailings

C mixed bastnasite, monazite: 56 % REO)

monazite monazitel xenotime turmaline bastnasite monazite

metallurgy of rare earths monazite

residue: unreacted monazite

solution: RE, Th, U sulphates, phosphates

solution evaporation/ Na3P04

crystallization (by product)

by product: Na2C03~ RE nitrate

12 Monazite processing by alkali treatment

bastnasite (7-10 % REO)

volatile chlorides -10

crude RECl3 TBP

NaOH solution: extract:

14 Chemical processing of xenotime RE oxalate RE sulphate

to separate rare earths, titanium, niobium, and tantal-

mixed RE hydroxide by selective precipitation. The precipitation of even

( 0.5 - 0.7% Eu) ( Ce free)

18 Separation of europium by selective neodymium and the double magnesium nitrates

Fractional precipitation yttrium and gadolinium could be purified by adsorp-tion on

International Materials Reviews 1992 Vol. 37 NO.5

bastnasite concentrate rare earth chloride feed

acid scrub Y concentrate

21 Flowsheet of rare earth separation by solvent

20 Flowsheet of recovery of eu ropi um from

International Materials Reviews 1992 Vol. 37 NO.5

( La, Pr ,Nd ,Sm nitrates)

Reduction and selective precIpItation purifies extraction

International Materials Reviews 1992 Vol. 37 NO.5

Another important interstitial impurity is carbon.

International Materials Reviews 1992 Vol. 37 NO.5

RE metal ingot RE metal ingot RE metal ingot

to 300°C in the presence of under reduced