J. Sustain. Metall.

(2015) 1:29–38
DOI 10.1007/s40831-014-0005-1

RESEARCH ARTICLE

Rare Earths and the Balance Problem

Koen Binnemans • Peter Tom Jones

Published online: 8 January 2015

Ó The Minerals, Metals & Materials Society (TMS) 2015

Abstract Maintaining the balance between the demand Introduction

by the economic markets and the natural abundance of the
rare-earth elements (REEs) in ores constitutes a major The global annual production of rare earths or rare-earth
challenge for manufacturers of these elements. This is the elements (REEs) is typically expressed in tonnes of rare-
so-called balance problem (or balancing problem). The earth oxides (REOs). At present, the estimated yearly total
ideal situation is a perfect match between the demand and production of REOs is about 125,000 tonnes, although
(production) supply of REEs, so that there are no surpluses accurate production numbers are very difficult, if not
of any of the REEs. The balance problem implicates that impossible, to obtain. However, these total production
the rare-earth industry has to either find new applications numbers give no indication about the availability of the
for REEs that are available in excess, or needs to search for individual REEs. First of all, not the total amount of REE
substitutions for REEs that have limited availability and ores mined is of importance, but rather the total amount of
that are high in demand. Different solutions are proposed to REE concentrate separated in the different individual REEs.
solve the balance problem: diversification of REE resour- For some applications, such as mischmetal, no separated
ces, recycling and urban/landfill mining, substitution, REEs are required. Secondly, the REEs are not present in
reduced use and new high-volume applications. No single equal amounts in the REE ores, due to differences in the
solution can solve the balance problem, but a combination natural abundances of these elements. The general trend in
of different strategies can. It is illustrated that the issue of the natural abundance of the rare earths is that the elements
thorium in REE ores is also directly related to the balance become scarcer with increasing atomic number Z; as the
problem: presently, thorium is considered as radioactive abundances decrease over the lanthanide series, the heavy
waste, but this waste could be turned into a valuable rare-earth elements (HREEs) are much less abundant than
resource by using thorium in a thorium-based nuclear fuel the light rare-earth elements (LREEs) [1]. Additionally,
cycle. elements with an even atomic number Z are more abundant
than elements with an odd atomic number (Oddo-Harkins
Keywords Lanthanides
Permanent magnets
Rare rule). For example, cerium (Z = 58) is more abundant with
earths
Recycling
Substitution
Thorium respect to its neighbours lanthanum (Z = 57) and praseo-
dymium (Z = 59). Cerium is the dominating rare-earth
element in LREE-rich ores (bastnäsite and monazite), while
yttrium is the main rare-earth element in HREE-rich ores
(xenotime and ion-adsorption ores).
K. Binnemans (&)
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, The availability of the individual REEs is of concern for
P.O. Box 2404, 3001 Heverlee, Belgium applications that require the use of pure REEs, such as
e-mail: [email protected] phosphors and permanent magnets. If the REEs that are
required for high-volume applications have a low natural
P. T. Jones
Department of Materials Engineering, KU Leuven, Kasteelpark abundance, the minimum quantity of REE concentrate that
Arenberg 44, P.O. Box 2450, 3001 Heverlee, Belgium needs to be processed and separated is that quantity that

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will produce at least the amount of REEs required for these bastnäsite ore of the Mountain Pass mine in California. In
critical applications. As a consequence, some REEs will be fact, the Mountain Pass mine was in that period operated
produced in larger quantities than required by the REE mainly for the production of europium. The bastnäsite of the
market and, subsequently, these elements need to be Mountain Pass mine contains only about 0.1 wt% europium.
stockpiled, which comes at a cost. The balance between the The low concentrations of europium implied that large sur-
demand by the economic markets and the natural abun- pluses of the LREEs were produced and needed to be
dances of the REEs in ores is a major problem for manu- stockpiled: to obtain 1 tonne of Eu2O3 from bastnäsite, one
facturers of these elements [2]. This is the so-called had to excavate an amount of REE ores that contained 300
balance problem (or balancing problem) [3, 4]. The ideal tonnes of La2O3, 450 tonnes of CeO2, 38 tonnes of Pr6O11,
situation is a perfect match between the demand and 118 tonnes of Nd2O3, 7.3 tonnes of Sm2O3, 1.4 tonnes of
(production) supply of REEs, so that there are no surpluses Gd2O3 and 0.9 tonnes of Y2O3 [5]. In this context it should be
of any of the individual REEs. This would result in the mentioned that it is possible to selectively remove europium
lowest market price for any of the REEs, because the from mixtures of REEs by reduction of europium(III) to
production costs are shared by all rare-earth elements. europium(II), for instance by chemical reduction with zinc
Unfortunately, a market in balance is very difficult to amalgam or by electrochemical reduction.
achieve, because of changes in demand due to technolog- In the 1970 and 1980s, samarium was the most critical
ical evolutions in applications. The result is a sometimes REE because of its use in samarium-cobalt permanent
very high demand of a REE that is a minor constituent in magnets. At that time, the production of samarium-cobalt
the ore (such as dysprosium), while the demand of the magnets was limited by the availability of Sm2O3 on the
major constituent (such as yttrium) is much lower. The size market. However, the share of samarium-cobalt magnets in
of the REE market is different in terms of value and vol- the permanent magnet market is at present \2 %, and an
ume. For instance, phosphors are a very important appli- excess of samarium is being produced. Before 1985, there
cation of REEs in terms of value (1/3 of the REE market), were no industrial applications for dysprosium, and neo-
but they are a rather modest application in terms of volume dymium metal was not produced on an industrial scale. At
(about 7 %). The balance problem is related to the volumes that time, it could not be predicted that less than 30 years
of the individual REEs consumed. later, neodymium and dysprosium would be high in
For the REE industry the balance problem is a more demand for neodymium-iron-boron magnets. With respect
important issue than the availability of REE resources, not to holmium, thulium, ytterbium and lutetium no high-vol-
to say that it is the most important issue facing the REE ume applications currently exist.
industry. This paper gives an in-depth analysis of the bal- Due to the balance problem, there has also been a shift
ance problem and offers several possible mitigation options. in the types of REE ores used. Until the 1960s, monazite
was the main ore (monazite era). For a long time the REEs
were just a by-product of the production of thorium which
History of the Balance Problem was used for the manufacturing of incandescent gas man-
tles. In the 1960s, bastnäsite became the most important
The balance problem became an issue as soon as purified REE ore, with the Mountain Pass mine in California as the
REEs started to being used in applications. In contrast, main production site (Mountain Pass era). Bastnäsite was
older applications of REEs consumed mixtures of REEs ideal to cover the increasing needs of lanthanum and cer-
and separation into pure single elements was not required. ium, as well as to fulfil the demand of europium. Gradu-
A good example is mischmetal, which is an alloy of ally, monazite was favoured again because of its higher
LREEs, with the REEs appearing in the same atomic ratios content of HREEs and yttrium. The steadily increasing
as they occur in the REE ore minerals. Also for other older demand of yttrium (mainly for its use in lamp phosphors
applications such as polishing powders or fluid cracking and yttria-stabilised zirconia) implied that also the yttrium-
catalysts no pure REEs had to be used. Hence, all REEs rich phosphate xenotime was processed as a REE ore. From
that were produced could be fully consumed. the end of the 1980s onwards, the HREE-rich ion-adsorp-
The first application of pure REEs was the use of euro- tion ores (laterite clays) from southern China became the
pium as active component of the red cathodoluminescent most important resource for yttrium and the HREEs.
phosphors in colour television screens (first YVO4:Eu3?,
later Y2O2S:Eu3?). In the mid-1960s and the early 1970s,
europium was the most critical REE because it has a low Current Market Situation and Evolution in the Future
natural abundance and it was high in demand for the pro-
duction of these red phosphors. In that period, nearly all of At present the LREE market is driven by the demand for
the global supply of europium was produced from the neodymium for neodymium-iron-boron (NdFeB) magnets

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[6]. This means that sufficient quantities of REE ores have Y2O3:Eu3? (YOX), the green lamp phosphors LaPO4:-
to be mined to meet the demand of neodymium. Since the Ce3?,Tb3? (LAP), (Gd,Mg)B5O12:Ce3?,Tb3? (CBT),
natural abundance of neodymium in the LREE ores is (Ce,Tb)MgAl11O19 (CAT) and the blue phosphor BaM-
relatively low, cerium, praseodymium and samarium are gAl10O17:Eu2? (BAM) in fluorescent lamps and compact
produced in excess, and have to be stockpiled. The lan- fluorescent lamps (energy-saving lamps) [10]. However, the
thanum market is in balance, thanks to its use in nickel fluorescent lamps market is rapidly shrinking due to the
metal hydride batteries and optical glasses. A few years increasing success of the light-emitting diodes (LEDs).
ago, it was nevertheless predicted that there would be a Y3Al5O12 (YAG) doped with about 0.003 % Ce3? is still
sharp decline in the use of nickel metal hydride batteries heavily in use as a yellow phosphor for white-light LEDs [11],
due to the increased use of lithium-ion batteries. However, but many types of LEDs do not contain rare earths at all; they
there are still many safety issues related with these lithium- produce white light by a combination of red, green and blue
ion batteries; overheating of the organic electrolytes can LEDs standing in close proximity to each other, similarly to
cause ignition of lithium-ion batteries. For these reasons, it the red–green–blue pixels in old-fashioned cathode-ray tubes.
is likely that nickel metal hydride batteries will continue to This change from fluorescent lamps to LEDs will make the
be used for several years to come in high-power applica- conventional lamp phosphors largely obsolete. The lamp
tions such as electric vehicles. phosphor Y2O3:Eu3? is by far the most important application
The HREEs are produced in much smaller quantities of europium. Smaller quantities of luminescent europium
than the LREEs, so that the balance problem is a more compounds are used in safety markers, for instance in the
important issue for the LREE market than for the HREE luminescent inks of EURO banknotes. As a consequence of
market. At present, the HREE market is driven by the the reduced demand for europium, one may expect an over-
demand for dysprosium, which is used to increase to high- supply of this element. However, an oversupply of europium
temperature performance and resistance to demagnetisation is less of an issue than an oversupply of cerium, since the
(i.e. the intrinsic coercivity) of NdFeB magnets. The supply global production volumes of europium are much smaller than
equals the demand for europium, yttrium and erbium. those of cerium. LED lighting systems driven by an alternat-
There is a shortage of terbium, but this problem can still be ing current (AC) source that are currently produced in Taiwan
solved by the use of stockpiles. Gadolinium, holmium, and China use phosphors with long decay times based on
thulium, ytterbium and lutetium are produced in excess and europium (either Eu3? or Eu2?). These AC LEDs are 25 %
are stockpiled. This stockpiling is not a major issue in more efficient than conventional LEDs. It might be antici-
terms of volumes, but it causes a loss of potential profit for pated that they will replace to a large extent the conventional
the REE producers. LEDs within 5–10 years, leading to a renewed demand for
It is evident that the REE market is a rapidly changing europium. Long-persistence phosphors containing Eu2? and
market. New applications as well as the sudden disappear- Dy3? are being used for security marking and road marking.
ance of well-established applications could bring the REE This could create a novel demand for europium (and dys-
market out of balance. Although the present REE market is prosium). For terbium, it is much easier to find alternative
driven by the demand for neodymium and dysprosium, this applications than europium because applications of terbium
could rapidly change, as shown by the historical evolutions are not restricted to luminescent materials. Terbium can
in the REE markets. Although there is currently an over- substitute for dysprosium in NdFeB permanent magnets (vide
supply of gadolinium, this global excess could turn into a infra). Likewise, other applications than lamp phosphors are
shortage if magnetic refrigerators would be mass-produced possible for yttrium, since yttrium is a very useful element for
[7, 8]. It must be admitted that present research activities in the preparation of high-tech ceramic materials, for instance,
the field of magnetic refrigerators are focusing on the yttria-stabilised zirconia. Remote-phosphor LEDs form an
development of REE-free materials with a large magnetoc- emerging application of yttrium and cerium. In these LEDs,
aloric effect [9]. Given the fact that kilogramme quantities of the phosphor in the form of the yellow phosphor Y3Al5O12:-
gadolinium are required for the construction of one magnetic Ce3? is located at a distance from the LED [12], and they can
refrigerator, it is not realistic to assume that such devices contain an amount of phosphor that is comparable with
would be mass-produced; there is simply not enough gado- compact fluorescent lamps or fluorescent lamps.
linium available in the world to achieve this goal.
It is very likely that within the next years a dramatic change
will occur in the lamp phosphor market that might cause an How to Solve the Balance Problem?
imbalance of the HREE market. At present, europium, ter-
bium and yttrium are considered as three of the five most Increasing the overall REE production to meet the highest
critical rare earths (the other two being neodymium and dys- demand of any REE and to stockpile the other REEs with
prosium) because of their use in the red lamp phosphor lower demand, seems to be an obvious solution for the

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balance problem. However, this will increase the overall A complementary diversification strategy is to valorise
price of the REEs, due to the extra costs for separating the (see top part in Fig. 1) previously landfilled stocks and
REE mixtures and stockpiling the REEs produced in excess freshly produced flows of rare-earth-containing industrial
of the demand. Adjusting the overall REE production to process residues [16]. In general, although these secondary
optimise the REE producer’s operational margins will resources typically contain much lower REE concentra-
create surpluses of some REEs and shortages of other tions with respect to end-of-life consumer goods (see
REEs. Shortages of a minor constituent lead to dramatic Solution 3), the volumes of these residues are enormous so
price increases of this REE due to its (very) high price that the total amounts of rare earths locked in these residues
inelasticity. Preferentially, the REE market is driven by the are also very large and may secure an independent source
demand for elements that are very abundant (cerium and of rare earths as well as shield REE resource-poor countries
lanthanum), since this will create less problems with from export quotas and price fluctuations. These secondary
stockpiling of the elements that are available in excess. The resources include residues from both primary and second-
unbalanced use of a single REE in a high volume appli- ary metal production (as shown in Fig. 1)—phosphogyp-
cation has to be avoided, especially if this element has a sum, bauxite residue (red mud), mine tailings,
low natural abundance, because this will cause a serious metallurgical slags—and industrial process residues from
imbalance of the market. There are different solutions that thermal treatment facilities (coal ash, incinerator ash). As
can help to alleviate the balance problem. These will be previously shown by the authors, the most promising
each discussed in some detail. Since the REE markets are resources are bauxite residue and phosphogypsum [16].
rapidly changing, it is very difficult to extrapolate the Bauxite residue (red mud) is a by-product of the aluminium
future demand of individual REEs on the basis of data for production and is quite rich in scandium [17], whereas
the present demand of these elements. Long-term predic- phosphogypsum is a by-product of the phosphoric acid
tions (for 25 or more years) should be interpreted with production from phosphate rocks [16]. Table 2 provides an
caution [13]. overview of typical REE concentrations in these secondary
resources [18, 19]. Through the development of (zero-
Solution 1: Diversification of REE Resources waste) flow sheets for the recovery of REE metals from
these large volume streams, it is possible to partially mit-
At present, the global REE supply is produced from a igate the balance problem, in a similar way as is the case by
limited number of ore types: bastnäsite, monazite, xeno- combining various primary ores.
time and ion-adsorption clays. Bastnäsite and monazite are
rich in LREEs, whereas xenotime and ion-adsorption ores Solution 2: Recycling
are rich in HREEs and yttrium. The composition of these
ores can show some variation from deposit to deposit, but Recycling and closing the materials loop are very impor-
these variations are rather limited. Table 1 gives an over- tant activities for bringing the REE markets in balance [20,
view of the main minerals in REE deposits [14]. New REE 21]. As shown in the bottom part of Fig. 1, different forms
deposits contain often less conventional REE minerals such of recycling can be distinguished. The first type involves
as eudialyte, euxenite, parisite, synchisite, churchite, gad- the direct (preconsumer) recycling of REE-rich metal scrap
olinite, fergusonite, loparite and steenstrupine. and swarf generated during the production of REE-based
Phosphate rocks (mainly apatite) used for the production (intermediate) products (as for instance NdFeB or SmCo
of phosphoric acid and phosphate fertilisers are an impor- magnets). Concurrently, the (postconsumer) recycling and/
tant potential REE resource, and were already used in the or urban mining of, respectively, flows and stocks of
past for the recovery of REEs [15]. Even though phosphate complex, multi-material, REE-containing products (as for
rocks contain only small REE concentrations, the exca- instance a hybrid electric vehicle) and the landfill mining
vated volumes are enormous. of REE-rich historic urban solid waste can deliver addi-
By combining the REE concentrates obtained from tional REE streams [22].
different REE resources, it is possible to compose a mixed Volume-wise it is especially the recycling of end-of-life
concentrate with a composition that is reflecting much REE-based products that can help addressing the balance
better the needs of the individual REEs by the market than problem. Indeed, recycling of neodymium and dysprosium
in the case when only one single or just a few types of REE from end-of-life NdFeB magnets implicates that, all other
ores are used. By combining the REE concentrates from things being equal, less primary REE ores have to be
different ores, it is also possible to create a mixed REE feed excavated to meet the global demand of neodymium and
solution of constant composition. This is beneficial for the dysprosium. Less mining of REE ores implies less over-
optimisation of solvent extraction processes for the sepa- production of cerium and samarium. Additionally, recy-
ration of mixtures of REEs. cling of europium, terbium and yttrium from lamp

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Table 1 Typical REE minerals, Mineral Chemical formula Total REO (wt%)
their chemical formula and total
REE content (expressed as total Bastnäsite REECO3F 53–79
rare-earth oxide, REO)
Monazite (REE,Th)PO4 38–71
Xenotime YPO4 43–65
Eudialyte Na15Ca6(Fe,Mn)3Zr3(Si,Nb,REE)Si25O73(OH,Cl,H2O)5 \10
Euxenite (REE,Ca,U,Th)(Nb,Ta,Ti)2O6 \30
Churchite REEPO4
2H2O 43–56
Fergusonite (REE,Th)(Nb,Ta,Ti)O4 43–52
Gadolinite REEFeBe2Si2O10 \52
Loparite (Na,REE,Ca)(Ti,Nb)O3 28–38
Parisite CaREE2(CO3)3F2 58–63
Steenstrupine Na14REE6Mn2Fe2(Zr,Th,U)(PO4)7Si12O36(OH)2
3H2O \31
Synchisite CaREE(CO3)2F 48–52

Fig. 1 Recycling of REE-containing resources can take many forms, the REE recovery from REE containing tailings and fresh/landfilled
from mining of primary ores, to direct (preconsumer) recycling, industrial residues generated during primary and secondary metal
recycling, urban mining and landfill mining of end-of-life products, to production

phosphors also helps to keep the HREE market into bal- several challenges remain to be solved, especially the
ance [23]. Thus, by recycling REEs that are essential for recovery of permanent magnets from shredded waste [24,
high-volume applications, an oversupply of REEs that are 25].
less in demand can be avoided. The REE concentrate To estimate the possible impact of recycling on the REE
obtained by recovery of REEs from end-of-life consumer markets, it is of importance to get a clear idea of the global
products can be used to adjust the composition of the feed inventory of the different REEs in use, of the life cycle of
of solvent extraction batteries. Recycling is industrially REEs in various applications and of the life span of REE-
relevant for the most valuable applications: permanent containing devices. Recently, several research groups
magnets, lamp phosphors and NiMH batteries. However, started to address this issue [13, 26–31]. Recycling of ceria

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Table 2 Typical REE content of industrial process residues (in ppm) samarium. Part of the dysprosium in NdFeB magnets can
REE Phosphogypsum [18] Bauxite residue (red mud) [19]
be replaced by terbium. This is not often done at present
because terbium is a very critical element due to its use in
La 1,450 149.0 the green lamp phosphors. However, it can be anticipated
Ce 2,310 418.0 that more terbium will become available for use in NdFeB
Pr 235 25.8 magnets, as it is expected that the fluorescent lamps will
Nd 899 115.0 increasingly be replaced by LEDs (vide supra).
Sm 163 28.9 What about the replacement of neodymium-iron-boron
Eu 34.9 5.0 magnets by samarium-cobalt magnets? As described
Gd 98.7 23.3 above, SmCo magnets are in use for a longer time than the
Tb 7.45 n.d NdFeB magnets and for a long time samarium was the
Dy 45.5 12.8 most critical REE element in so far that the production of
Ho 7.37 4.3 SmCo magnets was limited by shortages in the supply of
Er 15.7 17.2 samarium, with very high samarium prices as a result.
Tm 1.36 n.d. However, after 1985 SmCo magnets have been rapidly
Yb 5.6 15.6 replaced by NdFeB magnets. NdFeB magnets have a
Lu 0.568 2.4 higher energy density than SmCo magnets, but, more
Y 180 93.9 importantly, NdFeB magnets are less expensive than SmCo
Sc 1.21 127.9 magnets. More than 70 % of the mass of NdFeB magnets
consists of cheap iron, while the natural abundance of
neodymium is much higher than that of samarium. Fur-
(from polishing powders and car exhaust catalysts) could thermore, the SmCo magnets contain also the rather
be recommended from a sustainability point of view, but it expensive cobalt. SmCo magnets have some advantages
will—in contrast to permanent magnets and lamp phos- compared to NdFeB magnets: they are much more resistant
phors—not help to solve the balance problem due to the to demagnetisation at higher temperatures and they are
oversupply of cerium on the market [32]. much more resistant to corrosion (SmCo magnets do not
need to be coated by an anticorrosion layer, in contrast to
Solution 3: Substitution NdFeB magnets). Therefore, SmCo magnets are used in
high temperature applications and in applications where
One type of substitution involves the replacement of one corrosion can be an issue. Typical markets for SmCo
REE element by another one in a given application. magnets are the aircraft industry and the military industry.
However, the different REEs have very different electronic Still, the market of SmCo magnets is very small compared
and magnetic properties so that one REE cannot simply be to the huge market of NdFeB magnets. As indicated above,
replaced by another REE in the same application. For the share of SmCo magnets in the permanent magnet
instance, europium is the only REE that can be used in red market is less than 2 %. Given the criticality of neodym-
lamp phosphors. In fact, europium is unique for its line ium/dysprosium and the oversupply of samarium, one can
emission in the red spectral region. In this case, substitution ask the question why no larger quantities of SmCo magnets
of europium by another REE is not an option. In other are produced? The reason for this is twofold. First of all, as
cases a more critical REE can be replaced by a less critical discussed above, SmCo magnets are more expensive than
one or, even better, by a non-critical REE. The NdFeB NdFeB magnets due to the large quantities of cobalt they
magnets are a good example of an application where this contain. Cobalt has suffered from its own supply risks in
type of substitution can play a role [9]. Part of the neo- the past and it is a rather expensive element. Cobalt is also
dymium (up to 25 %) can be replaced by praseodymium used in lithium-ion-batteries, in the form of lithium cobalt
without significantly changing the magnetic properties of oxide (LiCoO2) in cathode materials. Secondly, the safety
the material. This is a very good opportunity to consume a regulations for working with samarium in an industrial
large part of the praseodymium supply (which is less environment have become more strict. Samarium has two
abundant than neodymium, but has also less specific naturally occurring radioisotopes, which are long-lived a-
applications) and to help bringing the LREE market in emitters: 147Sm (t‘ = 1.07 9 1011 years; natural abun-
balance. This also means that there is no need to use very dance = 15.01 %) and 148Sm (t‘ = 7 9 1015 years; nat-
high purity neodymium in NdFeB magnets; didymium (the ural abundance = 11.22 %) [33, 34]. Working with bulk
old name used for the mixture of neodymium and praseo- samples such as in SmCo magnets or with samarium-
dymium) can be used as well. However, it is not possible to containing solutions is not a problem, but working with
replace part of the neodymium in NdFeB magnets by Sm2O3 powder (which is a precursor for samarium alloys)

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is restricted by safety regulations due to the dangers protect the magnetic material against demagnetisation at
associated with possible inhalation of powders of a-emit- higher temperatures, are a good example. By grain
ters. Nevertheless, SmCo magnets have some untapped boundary diffusion, the dysprosium is concentrated near
potential for use in high-end applications that require the grain boundaries of a sintered NdFeB magnet [36–38].
strong magnets that remain operational at high tempera- As a consequence the required total dysprosium concen-
tures and that have a good resistance against corrosion. For tration can be decreased by more than 50 %. It is even
example, hybrid and full electric vehicles could make use possible to make dysprosium-free NdFeB magnets for use
of SmCo magnets in the drive and stop-start motors. in electric motors [39–41].
Substitution can also mean replacement of REEs by It is important not to waste critical REEs in applications
non-REEs, even though this can lead to products with poor, that do not require purified REEs. In the past, no efforts
yet still acceptable, performance. Examples include fluid were made to remove neodymium from the concentrate
cracking catalysts based on zeolites without REEs. NdFeB that was used to prepare mischmetal, although the presence
or SmCo magnets can be replaced by ferrite or alnico of neodymium was not essential for applications of mis-
magnets, but these magnets have much lower energy chmetal. At present, neodymium is very valuable (e.g. for
densities. Therefore, REE magnets are unlikely to be use in permanent magnets) and is, therefore, removed prior
replaced in applications where miniaturisation is of to mischmetal production.
importance. Major research efforts are directed to the
development of cerium-based magnetic materials. Until Solution 5: New High-Volume Applications
1975, mischmetal was often used for nodularising graphite
in cast iron and for desulphurising steel, but these metal- Compared to the other REEs, lanthanum and especially
lurgical applications became largely obsolete due to better cerium are very abundant and cheap. For western REE
production methods and replacement of mischmetal by mining companies, the lanthanum and cerium content of
calcium or magnesium [35]. Ceria in polishing materials their ores often have a negative effect on the REE basket
could be replaced by alumina or iron oxide, but this is at value and, subsequently, these elements are a nuisance for
present not a favourable option since there is an oversupply these companies, who look for new separation technologies
of cerium. NiMH batteries, containing large quantities of that can deliver a lanthanum- and cerium-free concentrate.
LREEs and especially lanthanum, could be replaced by The oversupply of lanthanum and cerium can be partially
lithium-ion batteries. Likewise, the LaNi5 alloy in NiMH overcome by developing new high-volume applications for
batteries could be replaced by a REE-free titanium-iron these elements. Research in this area must be encouraged.
alloy. However, there is little incentive to replace rare An example of an emerging high-volume low-tech appli-
earths in polishing powder and NiMH batteries because cation is the use of chlorides of lanthanum, cerium or
cerium and lanthanum are so cheap and abundant. mixtures thereof in water purification technology for
Sometimes, substitution can be more than simply removal of dissolved phosphate ions from water. The tri-
replacing one element by another. Indeed a more radical valent REE ions have a high affinity for phosphate ions,
form of substitution takes place when a totally new tech- resulting in the formation of poorly soluble and readily
nology is introduced to the market, making the older filterable REE phosphates. This application is commer-
technology based on REEs obsolete. Until about cialized by Molycorp (SorbX-100Ò and PhosFIXÒ). Cer-
10–15 years ago, europium was an important component of ium is being investigated as active component in redox
red cathodoluminescent phosphors used in cathode-ray flow batteries, for instance the zinc-cerium redox flow
tubes (CRTs) for colour television screens and computer battery [42]. Other applications of cerium include [43, 44]:
monitors. The CRTs screens were replaced by plasma use for the destructive total oxidation of toxic organic
displays (still containing REE phosphors) and LCD screens compounds [45, 46], as a redox mediator in organic elec-
(using REEs in the phosphors of the backlight fluorescent trosynthesis [47], as photocatalyst [48] or to enhance the
lamps), but modern OLED screens do not contain REEs at photocatalytic activity of titanium oxide [44, 49]. Another
all. A similar evolution is taking place by the replacement new application of rare earths is in perovskites for use as
of fluorescent lamps by LEDs. electrocatalysts in lithium-air batteries [50–52]. However,
an important new high-volume application of lanthanum
Solution 4: Reduced Use and cerium is as thermal stabiliser of PVC [53–57]. Sta-
bilisers are added to PVC to protect the polymer against
By clever engineering, it is possible to reduce the con- thermal decomposition during processing at temperatures
sumption of critical REEs in a given application, without above 200 °C, and to protect PVC against heat and UV
compromising the performance of the REE-containing irradiation during use. At present lead, cadmium, zinc, tin,
devices. The NdFeB magnets, which contain dysprosium to barium and calcium salts are added as stabilisers to PVC.

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The use of lead and cadmium stabilisers is phased-out in product. However, the transition to a thorium-based
many countries due to toxicity issues. The safest of the nuclear fuel cycle could lead to zero-waste valorisation of
presently used stabilisers are the calcium and zinc salts. thorium-containing REE ores, so that both REEs and tho-
Lanthanum and cerium salts (for instance stearates or other rium can be considered as valuable resources. In case that
salts of fatty acids) have a stronger stabilising effect on nuclear power plants burning thorium fuel will become
PVC than calcium and zinc salts at the same dose. About operational in the future, no thorium mines need to be
3 kg of rare-earth stabilisers can be added to 1 tonne of opened, since the quantity of thorium obtained through
PVC. Given the very large volumes of PVC produced processing of monazite and other thorium-containing REE
globally each year ([40 million of tonnes), it is evident that minerals will probably be sufficient to cover the future
the PVC industry could be a very large consumer of (light) global demand of thorium.
rare earths.

Conclusions
Thorium
The balance problem is an intrinsic problem of REE mar-
The thorium issue is related to the balance problem as well. kets and is caused by the imbalance between the demand of
Nearly all REE ores contain the radioactive elements tho- individual REEs and their natural abundance in REE ores.
rium and uranium. Although the uranium content of typical Keeping the REE markets in balance is of strategic
REE ores is low, the thorium content of some REE ores is importance, not only to secure the supply of all REEs
rather high. For instance, monazite can contain more than required for technological and other applications, but also
15 wt% of ThO2 [58, 59]. Natural thorium is a mono-iso- to avoid dramatic price shocks for critical REEs. Different
topic element: all but some traces of natural thorium con- solutions have been proposed to solve the balance problem:
sist of the isotope 232Th, an a-emitter with a half-life of diversification of REE primary ore and secondary process
14.05 billion years. Due to the safety regulations associated residues, recycling, substitution, reduced use and new high-
with the handling of naturally occurring radioactive volume applications. There is no straightforward solution
materials (NORM), the thorium content of REE ores is a for this issue. However, by combining different strategies
major issue for REE producers [60]. At present, there are the balance problem can be mitigated. It was shown that
no large scale applications of thorium. Furthermore, tho- the presence of thorium in most of the REE ores is also
rium is considered as radioactive waste and its disposal can related to the balance problem: thorium is now considered
be very expensive. The thorium content of monazite is the as an expensive radioactive waste, but this waste could be
reason why Rhône-Poulenc (now Solvay) stopped pro- turned into a resource by using thorium in a thorium-based
cessing monazite at the REE production plant of La nuclear fuel cycle. Finally, it is crucial to stress that at
Rochelle in France in 1994. The thorium content of the present there is too much focus on the figures with respect
REE ore of Bayan Obo is causing environmental issues in to the total REE ore reserves and/or the total REOs pro-
Baotou (PR China) [61]. As long as thorium is considered duction numbers. It must be realised that most of the cur-
as radioactive waste, it will increase the production costs of rent high-tech applications of REEs require the use of
the rare earths. The costs of thorium waste disposal need to purified individual REEs rather than mixtures of REEs.
be shared by the different REE applications. However, Therefore, It cannot be emphasised enough how important
thorium could be used as a nuclear fuel instead of uranium. it is to effectively deal with the balance problem.
Thorium can be used in conventional light-water nuclear
reactors, although in that case ThO2 has to be mixed with Acknowledgments The authors thank KU Leuven for financial
support (projects GOA/13/008 and IOF-KP RARE3).
plutonium oxide [62]. Canadian CANDU reactors can burn
thorium as well [63]. A much better approach is to use
specially designed nuclear reactors such as the molten salt
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