Hydrometallurgy 113-114 (2012) 67–78

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Hydrometallurgy
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Aqueous stability of thorium and rare earth metals in monazite hydrometallurgy:

Eh–pH diagrams for the systems Th–, Ce–, La–, Nd– (PO4)–(SO4)–H2O at 25 °C
Eunyoung Kim, K. Osseo-Asare ⁎
Dept. of Materials Science and Engineering and Dept. of Energy and Mineral Engineering, Penn State University, University Park, PA 16802, USA

a r t i c l e i n f o a b s t r a c t

Article history: Potential vs. pH or Eh–pH diagrams for the systems Th–, La–, Nd–, Ce–, (PO4)–(SO4)–H2O at 25 °C were gen-
Received 13 July 2011 erated using the HSC5.0 software. The thermodynamic data available in the HSC software were supplemen-
Received in revised form 15 November 2011 ted with additional data for the rare earth metal phosphates. The diagrams for the M–H2O systems show that
Accepted 12 December 2011
rare earth hydroxides, such as Nd(OH)3, La(OH)3, and Ce(OH)3 form in alkaline solutions (i.e. pH > 7.5); in
Available online 20 December 2011
contrast ThO2 is stable down to relatively low pH (pH ≈ 1). For the Th–, Nd–, Ce–, and La–PO4–H2O systems,
Keywords:
the size of the stability region of a given REPO4 solid is highly dependent on the degree of crystallinity of the
Monazite material, as reflected in the value of the corresponding solubility product. The more crystalline the RE phos-
Eh–pH diagrams phate, the larger the stability field. Addition of sulfate ions to the M–PO4–H2O systems introduces soluble
Rare earth (RE) metals metal–sulfate complexes and insoluble sulfates in the relatively acidic regions of the Eh–pH diagrams. The
Th trends revealed by the diagrams are related to monazite hydrometallurgy.
Acid digestion © 2011 Elsevier B.V. All rights reserved.

1. Introduction Eh–pH (or Pourbaix) diagrams for selected RE metals, with emphasis
on monazite hydrometallurgy. It is well established that aqueous sta-
The rare earth (RE) metals are increasingly establishing themselves bility diagrams, such as Eh–pH or Pourbaix diagrams (Pourbaix,
as crucial industrial materials, with unique applications in numerous 1966), provide powerful and comprehensive visual summaries of sol-
fields, such as the optical, permanent magnet, electronics, superconduc- ubility relations in aqueous process systems. Previous work from this
tor, hydrogen storage, medical, and nuclear technologies, as shown in laboratory presented such diagrams for several metals, e.g., the sys-
Table 1 (British geological survey, 2010; Gupta and Krishnamurthy, tems Cu–, Ni–, Co–, Mn–, Fe–NH3–H2O (Osseo-Asare, 1981a, 1981b;
2005; Habashi, 1997; Jones et al., 1996). Recently China, which controls Osseo-Asare and Fuerstenau, 1978), Au–, Ag–, Cu–, Fe–, Ni–, Zn–CN–
97% of world trade in RE metals, announced a cutback in export H2O (Osseo-Asare et al., 1984; Xue and Osseo-Asare, 1985), Ca–,
(manufacturing.net, 2009). Worldwide demand for RE metals is, there- Mn–, Fe–W–H2O (Osseo-Asare, 1982), Ag–Se–H2O, Ag–Te–H2O, and
fore, expected to exceed supply by 40,000 tonnes annually for several Ga–As–H2O (Osseo-Asare, 1989), and Si–F–H2O (Osseo-Asare et al.,
years (Reuters, 2009). The minerals monazite ((RE,Th)PO4) and bastne- 1996).
site (RE(CO3)F) are the main sources of RE metals in nature (Gupta and In the pioneering work of Pourbaix (1966), which included Eh–pH
Krishnamurthy, 2005). The lighter rare earth metals (e.g., La, Ce, Pr, Nd) diagrams for the RE metals, the primary concern was with reactions
occur in both minerals; however, bastnesite tends to be poor in of metals in the presence of water only. Later, the chemical stability
the heavier rare earths (e.g., Ho, Er, Tm, Yb, Lu, Y) (Gupta and of rare earth elements in aqueous carbonate systems was investigated
Krishnamurthy, 2005). Typically monazite contains about 70% rare by Brookins (1988). However, this work did not consider systems of
earth metal oxide (REO), with the rare earth fraction constituted by direct relevance to monazite hydrometallurgy, such as those contain-
20 to 30% Ce2O3, 10 to 40% La2O3 and significant amounts of neodymi- ing phosphate and sulfate species; moreover, the thermodynamic
um, praseodymium, and samarium. Thorium content is in the 4 to 12% data of rare earth elements used by Pourbaix (1966) were not
range (Gupta and Krishnamurthy, 2005). updated. To properly predict the equilibrium relationships among
As industry confronts the new challenges in the global rare earths solid compounds and dissolved species in a given system, it is neces-
market, greater efficiencies in the corresponding extractive and recy- sary to have reliable thermodynamic data for the relevant species. Re-
cling technologies will be required. This paper seeks to contribute to trieving and assessing the pertinent data from literature sources can
the search for this new rigor in process technologies by presenting be a challenge. Monazite dissolution has received some attention in
relation to the aqueous geochemistry of RE phosphates (Kerdaniel
et al., 2007; Poitrasson et al., 2004; Wood, 1990; Ziya et al., 2005)
⁎ Corresponding author. Tel.: + 1 814 865 4882; fax: + 1 814 865 4718. and Th mobility in natural water (Langmuir and Herman, 1980).
E-mail address: ako1@psu.edu (K. Osseo-Asare). Also, stability constants for RE and Th phosphates were calculated

0304-386X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.12.007
68 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

Table 1 The aim of this paper, therefore, is to provide a reliable collection

Applications of RE metals. of thermodynamic data for selected RE metals (Nd, La, Ce) and Th and
Application RE technology Required RE Materials Consumption to use these data to construct Eh–pH diagrams that permit rational
(%) exploration of the solubility constraints that underlie hydrometallur-
Catalysts -Petroleum La, Ce, Pr, Nd RE oxides 19 gical extraction of RE metals from monazite. The emphasis here is on
refining the relevant dissolution and precipitation processes involved in the
-Catalytic decomposition of monazite and the subsequent metal recovery from
converter
solution.
-Diesel
additives
-Chemical 2. Thermodynamic data
processing
-Industrial
The thermodynamic data used in this work are listed in Table 2.
pollution scrubber
Ceramics -Capacitors La, Ce, Pr, RE oxides, 6 Most of the data were taken from the HSC 5.0 software database
Nd, Y, Eu, LaCl3:Ce, Eu: (HSC chemistry, 2002); the sources for the HSC database are provided
Gd, Lu, Dy (Y,Gd)2O3, in Appendix I. Additional data not available in HSC 5.0 were adopted
Pr,Ce:Gd2O2S from various sources as shown in Table 2. In the case of the phosphate
-Sensors
systems, the RE data from different sources have values with over one
-Colorants
-Scintillators order of magnitude difference for the same species (Cetiner et al.,
-Refractories 2005; Firsching and Brune, 1991; Liu and Byrne, 1997). Some re-
Magnets -Motors Nd, Pr, Alloys e.g. 21 searchers reported that the differences may be due to variations in
Tb, Dy SmCo5,
the crystallinity and aged condition of the materials used by the var-
Nd2Fe14B
TbxDy1-xFe2 ious investigators (Cetiner et al., 2005; Liu and Byrne, 1997). There-
(x ~ 0.3) fore, for each RE metal two different solubility products were used,
-Disc drives
-MRI
-Power
Table 2
generation
Thermodynamic data for RE-PO4-SO4-H2O systems at 25 °C.
-Microphones
and speakers Species ΔGof,298 Species ΔGof,298
-Magnetic (kcal/mol) (kcal/mol)
refrigeration
Metallurgical -NiMH batteries La, Ce, Intermetallics, 18 H3PO4 − 267.428 [1] Nd(HPO4)2− − 692.500 [6]
alloys Pr, Nd, Y e.g. 1Lm(Ni3.6 H2PO4− − 270.126 [1] NdH2PO42+ − 433.510 [6]
Mn0.4Al0.3 HPO42− − 260.296 [1] Nd2(SO4)3(s) − 847.843 [1]
Co0.7), CeCoIn5, PO43− − 243.364 [1] NdSO4+ − 343.500 [1]
YBa2Cu3O7 H2SO4 − 164.894 [1] Nd(SO4)2− − 523.379 [1]
-Fuel cells HSO4− − 180.609 [1] Nd2(SO4)3·8H2O(s) − 1335.000 [1]
-Steel SO42− − 177.907 [1]
-Lighter flints H2O − 56.678 [1] Ce 0 [1]
-Superalloys Th 0 [1] CeO2(s) − 244.900 [1]
-Aluminium/ ThO2(s) − 278.330 [1] Ce2O3 − 407.800 [1]
magnesium Th(OH)4(s) − 382.263 [1] Ce(OH)3(s) − 303.490 [4]
Phosphores -Display Eu, Y, Tb, Nd, RE oxides, dopants, 7 Th4+ − 167.800 [1] Ce2(OH)24+ − 413.410 [4]
phosphors Er, Gd, Ce, Pr e.g. Ce2O2S:Tb3+, ThOH3+ − 220.069 [1] Ce3(OH)54+ − 719.496 [4]
(CRT, LPD, LCD) SrGa2S4:Eu2+, Th(OH)22+ − 272.693 [1] CeOH3+ − 178.580 [4]
Tb: 2YAG, Tb: Th2(OH)26+ − 441.241 [1] CeOH2+ − 205.960 [1]
(La,Ca)PO4 Th4(OH)88+ − 1099.168 [1] Ce(OH)22+ − 235.670 [4]
9+
-Fluorescent Th6(OH)15 − 1811.602 [1] Ce2(OH)26+ − 362.070 [4]
4+
lighting Th4(OH)12 − 1312.614 [2] Ce2(OH)35+ − 419.430 [4]
10+
-Medical Th6(OH)14 − 1747.287 [2] CePO4(s) − 439.796 [5]
imaging Th2(OH)35+ − 495.755 [2] − 421.750[9]
-Lasers ThH2PO43+ − 446.150 [1] CeH2PO42+ − 433.904 [1]
-Fiber optics ThH2PO42+ − 723.550 [1] Ce(SO4)2(s) − 506.366 [1]
Glass and -Polishing Ce, La, Pr, Nd, RE oxides 22 ThH3PO44+ − 444.030 [1] Ce2(SO4)3(s) − 861.115 [1]
polishing compounds Gd, Er, Ho Th(H3PO4)(H2PO4)3+ − 722.489 [1] CeSO4+ − 344.627 [1]
-Decolorisers/ Th(HPO4)2·4H2O(s) − 952.667 [1] Ce(SO4)2− − 523.878 [1]
colorisers Th2(PO4)2(HPO4)·H2O(s) − 1230.166[3] Ce2(SO4)3·8H2O(s) − 1322.620
-UV resistant Th(SO4)2(a) − 537.701 [1] [7, 8]
glass ThSO42+ − 354.099 [1] La 0 [1]
-X-ray imaging Th(SO4)32 − − 713.840 [2] La3+ − 164.010 [1]
Others -Nuclear Eu, Gd, Ce, Gd2O3, Er2O3, 7 Th(SO4)2·9H2O(s) − 1045.540 [2] La2O3(s) − 407.700 [1]
Y, Sm, Er EuB6, CeH2, YH3 Nd 0 [1] La(OH)3(s) − 305.745 [1]
-Pigments Ce, Y Y2O3, CeO2 Nd2O3(s) − 411.436 [1] La2(OH)24+ − 416.286 [4]
Nd(OH)3(s) − 305.308 [4] La3(OH)54+ − 721.350 [4]
1
Lm: lanthanum-rich misch metal (≈ 50 wt.% La). Nd(OH)2+ − 250.800 [4] LaH2PO42+ − 437.575 [1]
2
YAG (Yttrium aluminum garnet, Y3Al5O12). NdOH2+ − 206.410 [1] LaPO4(s) − 441.887 [5]
Nd3+ − 160.100 [1] − 425.785[1]
Nd(OH)4− − 336.610 [4] La2(SO4)3(s) − 859.291 [1]
Nd2(OH)24+ − 415.451 [4] La2(SO4)3·9H2O(s) − 1399.880 [7]
by analyzing experimental solubility product data (Byrne and Kim,
NdPO4(s) − 439.200 [5] LaSO4+ − 346.908 [1]
1993; Cetiner et al., 2005; Firsching and Brune, 1991; Liu and Byrne, − 423.461[1] La(SO4)2− − 526.596 [1]
1997). However, even though there is a large number of published NdHPO4+ − 427.460 [6] La2(SO4)3(a) − 877.762 [1]
thermodynamic data for RE phosphates, the reported values for the [1] HSC 5.11 database and Appendix I, [2] Malcolm et al., 2009, [3] Kerdaniel et al.,
same element may differ by several orders of magnitude (Cetiner 2007, [4] Baes and Mesmer, 1976, [5] Liu and Byrne, 1997, [6] Poitrasson, et al., 2004,
et al., 2005; Firsching and Brune, 1991; Liu and Byrne, 1997). [7] Dean, 1999, [8] Wagman, et al., 1982, [9] Byrne and Kim, 1993.
 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78 69

Monazite

Concentrate (Physical beneficiation)

(H2SO4, 98% 1)Acid 2)Alkaline (NaOH, 60-75%

digestion decomposition
200 – 230oC) 120 – 150oC)

3)Water dissolution Filtration Na+, PO43-

4)RE, Th hydroxide
residue Filtration

5)RE, Th sulphates, phosphates 6)Acid dissolution Th recovery

Neutralization/ Neutralization/
Precipitation Precipitation

Th recovery Separation (IX, SX) Separation

RE recovery RE recovery
Fig. 1. Flowsheet for hydrometallurgical treatment of monazite for recovery of RE metals and Th.

þ 3−
representing the less crystalline phases (and also the most frequently Th3 ðPO4 Þ4ðsÞ þ 6H2 SO4 →3ThðSO4 Þ2ðsÞ þ 12H þ 4PO4 ð2Þ
reported data) and the most stable species (of higher crystallinity and
with more negative log K values). Accordingly, the diagrams involv-
3þ 2−
ing RE phosphate species considered two different sets of thermody- ðREÞ2 ðSO4 Þ3  nH2 OðsÞ →2RE þ 3SO4 þ nH2 O ð3Þ
namic data. The Eh–pH diagrams were plotted with the aid of the HSC
5.0 software. 4þ 2−
ThðSO4 Þ2ðsÞ →Th þ 2SO4 ð4Þ

3. Background
3.3. Alkali (NaOH) treatment of monazite
3.1. Hydrometallurgical processing of monazite
The alkali decomposition of rare earth phosphates with hot, con-
Well established hydrometallurgical methods for leaching of mon-
centrated alkali (50–75% NaOH) proceeds as follows (Habashi, 1997):
azite and the related metal recovery processes are described in the lit-
erature (Gupta and Krishnamurthy, 2005; Habashi, 1997; Hart and þ 3−
REðPO4 ÞðsÞ þ 3NaOH→REðOHÞ3ðsÞ þ 3Na þ PO4 ð5Þ
Levins, 1988; Koch, 1987; Mackey, 1986). After physical beneficiation
the chemical processing of monazite follows two main paths, i.e., acid
þ 3−
treatment by sulfuric acid and alkaline decomposition by NaOH, as Th3 ðPO4 Þ4 ðsÞ þ 12NaOH→3ThðOHÞ4ðsÞ þ 12Na þ 4PO4 ð6Þ
shown in Fig. 1 (Gupta and Krishnamurthy, 2005; Habashi, 1997).
Neutralization and precipitation rely on such reagents as ammonium
hydroxide, sodium sulfate, oxalic acid, and hydrofluoric acid. Separa-
Table 3
tion and purification processes often include solvent extraction or ion Considered M-(Ligand)-H2O systems and their relation to monazite hydrometallurgy.
exchange.
System Application Processes in
Fig. 1
3.2. Acid treatment of monazite
M–H2O - Dissolution of metal oxides resulting from -Step 2, 4
alkaline treatment of monazite
In the acid digestion step monazite is treated with 98% sulfuric - Th/RE separation via precipitation after -Step 3
acid (weight ratio of solid to liquid ~ 1:1) at 200–230 °C, yielding a water dissolution
grey-colored metal sulfate solid product (Eqs. (1) and (2)). The - Th/RE selective dissolution after alkaline -Step 6
solid sulfates thus produced are dissolved with cold water (S/L ratio treatment
M–SO4–H2O - Dissolution of metal sulfates resulting from -Step 1, 3
~ 1:7; Eqs. (3) and (4)) (Fernelius et al., 1946). The metal sulfate solu-
sulfuric acid digestion of monazite
tion obtained by filtration goes to neutralization and separation pro- - Dissolution and separation of RE metal scrap
cesses for recovery RE and Th. e.g. Nd–Fe–B magnet
M–PO4–H2O - Acid and alkaline decomposition of monazite -Step 1, 2
M–PO4–SO4–H2O - Acid decomposition of monazite -Step 1, 5
þ 3−
2REPO4ðsÞ þ 3H2 SO4 →ðREÞ2 ðSO4 Þ3ðsÞ þ 6H þ 2PO4 ð1Þ (M: La, Nd, Ce, Th)
70 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

This process is carried out at high temperature (~ 150 °C) in au- hydrometallurgy are listed in Table 3. Future work will extend this in-
toclaves (~ 60% alkali, weight ratio of solid to liquid ~ 1:1), or with vestigation to elevated temperatures.
more concentrated alkali (~ 75%) at lower temperature (~ 120 °C)
and normal pressures. After filtration the trisodium phosphate is 4. Results and discussion
recovered as a by-product, which can be used as a fertilizer. The
solid hydroxide product from alkaline decomposition is dissolved 4.1. Th–, Nd–, Ce–, and La–H2O systems
in various acids (HCl, H2SO4, HNO3) depending on the subsequent
separation process to release rare earth metals while Th remains Th and RE (hydr)oxides are encountered as reaction products fol-
undissolved. lowing alkaline decomposition of monazite (Fig. 1). These materials
are also involved in Th/RE metals separation processes associated
3.4. Monazite processing and aqueous stability diagrams with both the acid and alkaline decomposition flowsheet (Table 3).
In order to predict the decomposition behavior of Th and RE (hydr)
For all the above processing steps, the ability to predict reaction con- oxides the systems Th–, Nd–, Ce–, La–H2O were considered.
ditions (as captured in Eh–pH diagrams) favoring dissolution or precip- Potential-pH diagrams for the Th–, Nd–, Ce–, and La–H2O systems at
itation of RE metal oxides as well as the corresponding complexes with 25 °C are shown in Fig. 2. Except for Ce, the speciation of the other
phosphate and sulfate ions, can help in selecting appropriate separation metals is similar to that of Pourbaix (1966). The difference between
schemes. Also, in order to treat and safely recover radioactive elements Ce speciation here concerns the predominant region of CeO2 and dis-
such as Th contained in monazite, it is helpful to have some quantitative appearance of Ce(OH)22+ compared to the diagram in Pourbaix
information on the speciation and stability of these elements during the (1966); this is attributable to the different thermodynamic values
recovery process for RE metals. The discussion below focuses on such is- used for Ce(OH)3, CeO2, and the other species in the Ce–H2O system.
sues. As mentioned above, the decomposition reactions of monazite as- The Nd–, Ce–, La-hydroxides after alkaline decomposition easily dis-
sociated with acid and alkaline treatment are carried out at high solve as RE(III) in acidic to neutral pH while Th is stable as ThO2
temperatures. However, subsequent separation processes, such as even in acidic conditions (pH 1).
water dissolution (in acid treatment), neutralization, and precipitation It can be seen from Fig. 2 that rare earth hydroxides such as
typically involve lower temperatures. Therefore, for this first report ex- Nd(OH)3, La(OH)3, and Ce(OH)3 appear under relatively alkaline con-
ploring monazite hydrometallurgy via aqueous stability diagrams, the ditions (pH > 7.5), while ThO2 is stable even at relatively low pH
emphasis is on low temperature (25 °C) Eh–pH diagrams. The consid- (down to pH ~ 1). This indicates that mixed RE–Th (hydr)oxides
ered Metal–(Ligand)–H2O systems and their relevance to monazite may be separated by selective dissolution. Thus, the Nd–, Ce–, and

Fig. 2. Eh–pH diagrams for the Th–, Nd–, Ce–, La–H2O systems at 25 °C: (a) {Th} = 10− 3 M, (b) {Nd} = 10− 3 M, (c) {Ce} = 10− 3 M, (d) {La} = 10− 3 M.
 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78 71

La-hydroxides resulting from alkaline decomposition of monazite can

readily dissolve as RE(III) species in acidic to neutral pH solutions,
leaving Th in a stable solid phase as ThO2 even under relatively acidic
conditions (pH ~ 1). Conversely, Th and RE metals, initially present as
dissolved species in acidic solution, may be separated by pH adjust-
ment; as pH is raised, ThO2 is expected to form first. Also, it is likely
that the early formation of (hydr)oxide (as ThO2 and/or RE hydrox-
ides) on the surface of monazite may produce a passive layer which
may inhibit further alkaline decomposition of the phosphate mineral.
Therefore, decreasing particle size (Gupta and Krishnamurthy, 2005)
or removing the product layer (Abdel-Rehim, 2002) should enhance
alkaline decomposition of monazite.

4.2. Th–, Nd–, Ce–, and La– SO4–H2O systems

Referring to Fig. 1 it can be seen that, following alkaline decompo-

sition of monazite, the resulting hydroxide product is treated with
sulfuric acid. To examine the solution–chemical basis for this process
the systems Th–, Nd–, Ce–, and La–SO4–H2O were considered. The rel-
evant Eh–pH diagrams for various sulfuric acid concentrations are
presented in Figs. 3–6. The stability region of Th(IV) ions in sulfate so-
lution (Fig. 3) is wider than for the Th–water system (Fig. 2a) and in-
creases with increasing {SO4}. This effect demonstrates the important
role of sulfate complexation (as Th(SO4) 2+ and Th(SO4)2(aq)) in en-
hancing Th(IV) solubility. In the case of the RE metals (Figs. 4–6),
the introduction of sulfate ions produces ionic and solid sulfate com-
plexes. The predominance areas of the solid sulfate complexes of Nd

Fig. 4. Eh–pH diagrams for the Nd–SO4–H2O system at 25 °C, {Nd} = 10− 3, 10− 1 M:
(a) {SO4} = 10− 2 M, (b) {SO4} = 1.0 M.

(Fig. 4) and La (Fig. 6) grow with increasing {RE} and/or {SO4} while
the stability field of cerium sulfate ions also increases. The solid sul-
fates, Nd2(SO4)3·8H2O, Ce2(SO4)3·8H2O, La2(SO4)3·9H2O are rela-
tively soluble at room temperature (~50 to 100 g/L H2O) but the
solubility declines with temperature increase (Fernelius et al.,
1946). Advantage is taken of this solubility behavior in the cold
water dissolution (step 3 in Fig. 1; Eqs. (3) and (4)) for the acid diges-
tion products which contain the RE and Th solid sulfates.
The diagrams also indicate that the stability of RE metal (hydr)
oxides in sulfuric acid solutions decreases in the order Ce > Nd > La;
this is in agreement with trends reported in the literature
(Todorovsky et al., 1993). Furthermore, it can be seen that the stabil-
ity regions of the metal hydroxides shrink drastically at higher sul-
fate concentrations. This tendency to form stable solid RE sulfates
is utilized in the commercial process of crude separation as double
sulfate, RE2(SO4)3·Na2SO4·nH2O, by adding Na2SO4 (Abreu and
Morais, 2010; Gupta and Krishnamurthy, 2005). The formation of
solid Nd sulfate via sulfate fractional crystallization can also be ap-
plied to the separation of Nd from Nd–Fe–B magnet scrap. In high
concentrations of sulfuric acid and elevated temperatures (~80 °C)
Nd(III), which has a lower solubility as Nd sulfate separates out as
a solid sulfate, leaving Fe(III) ion in solution (Gerasimova et al.,
2010; Lee et al., 1998; Wei et al., 1989).

4.3. Th–, Nd–, Ce–, and La–PO4–H2O systems

Fig. 3. Eh–pH diagrams for the Th–SO4–H2O system at 25 °C, {Th}= 10− 3 M: (a) {SO4} = As noted above, monazite is a phosphate mineral. Therefore, when
10− 2 M, (b) {SO4} = 1.0 M. considering its chemical decomposition, it is useful to examine the
72 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

Fig. 5. Eh–pH diagrams for the Ce–SO4–H2O system at 25 °C: (a) {Ce} = 0.2, 10− 3 M,
{SO4} = 0.1 M, (b) {Ce} = 0.2 M, {SO4} = 1.0 M. Fig. 6. Eh–pH diagrams for the La–SO4–H2O system at 25 °C, {La} = 10− 3, 10− 1 M:
(a) {SO4} = 10− 2 M, (b) {SO4} = 1.0 M.

aqueous stability relations in the relevant metal–phosphate–water sys-

tems. Figs. 7 and 8 show Eh–pH diagrams for the Th–, Nd–, Ce–, and La– et al., 2009; Todorovsky et al., 1997; Zhang and Lincoln, 1993;
PO43 −–H2O systems at 25 °C. For each RE metal two different solubility Zhang and Lincoln, 1994) or microwave (Kamel et al., 2010) activa-
products were used, representing the relatively amorphous and most tion. The mechanochemical process uses milling during leaching
crystalline forms of the metal phosphate respectively (see Section 2). and it is known to improve the extraction of metal components
In Fig. 7, which is for (RE)PO4(s) of relatively poor crystalline, RE(III) from minerals (Baláž, 2000). The mechanical action leads to
ions are stable up to pH 6 while solid REPO4 and RE(OH)3 phases appear amorphization of the minerals, and this then enhances their chemi-
as pH increases above this. In contrast, Th(IV) is only stable as dissolved cal decomposition. The microwave-assisted method also enhances
ionic species in very acidic environments (~ pH 0). Thus, in principle, dissolution of phosphate minerals via amorphization (Kamel, et al.,
RE(III) ions originally present in a solid Th–RE phosphate matrix can 2010).
be released selectively into aqueous solution. The corresponding dia-
grams based on the more crystalline RE phosphates are shown in 4.4. Th–, Nd–, Ce–, and La–PO4–SO4–H2O systems
Fig. 8. It can be seen that, in this case, the stability fields of the REPO4
solid phases extend to relatively acidic conditions (pH 0–1). Comparing The decomposition behavior of monazite in sulfuric acid solution
the diagrams depicting the poorly crystalline (Fig. 7) and more crystal- can be interpreted with the aid of Eh–pH diagrams for the systems
line (Fig. 8) phosphates, it may be concluded that typical ore-grade Th–, Nd–, La–, Ce–PO4–SO4–H2O. Figs. 9–12 present the correspond-
monazite must be of the more crystalline phosphate type and therefore ing Eh–pH diagrams for varied sulfuric acid concentrations. The sta-
of high chemical stability. Thus, it is difficult to dissolve such material bility region of Th(IV) ionic species increases with increasing {SO4}
with acid simply by proton attack; instead, there is need for a suitable in Fig. 9. Figs. 10–12 show the RE–PO4–SO4–H2O systems with the
ligand that can form complexes with the RE metals. The sulfate ion is poorly crystalline (Figs. a and b) and highly crystalline (Figs. c
such a ligand, as discussed in Section 4.2 and further discussed below and d) RE-phosphates at two different sulfate concentrations. The sta-
in Section 4.4. bility domains of the solid RE(III)-sulfates are wider for the systems
The fact that the stability fields of the less crystalline RE incorporating the less crystalline phosphates ((a) and (b) of
phosphates are smaller than those of the corresponding crystalline Figs. 10–12) than for the corresponding more crystalline materials
materials suggests that it should be possible to enhance the decom- ((c) and (d) of Figs. 10–12)). This trend is consistent with that
position of monazite by amorphization or size reduction. In fact, noted in Section 4.3 for the RE–PO4–H2O systems.
there are reports of previous research to enhance digestion or It is instructive to compare the diagrams presented in the previ-
decomposition of monazite by applying mechanochemical (Kim ous sections with those for the M–PO4–SO4–H2O systems. Referring
 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78 73

Fig. 7. Eh–pH diagrams for the Th–, Nd–, Ce–, La–PO4–H2O systems at 25 °C, {PO4} = 10− 3 M: (a) {Th} = 10− 3 M, (b) {Nd} = 10− 3 M, ΔGNdPO4 = − 423.46 kcal/mol, (c) {Ce} =
10− 3 M, ΔGCePO4 = − 421.75 kcal/mol, (d) {La} = 10− 3 M, ΔGLaPO4 = − 425.78 kcal/mol.

to Figs. 3–6 (the M–H2O systems), it can be seen that the Th–, RE- with rising temperature or increased sulfate concentration
oxides are more soluble and stable as ionic species than the Th–, (Milanova et al., 2007; Paulenova et al., 2002; Todorovsky et al.,
RE-phosphates at the same conditions (Figs. 7 and 8). The intro- 1993; Wei et al., 1989). The acid digestion process takes advantage
duction of sulfate ions to the M–PO4–H2O systems helps to shrink of these temperature and sulfate concentration effects.
the stability domains of the Th–, RE phosphates, which is the
basis for the commercial process of acid digestion of monazite. 5. Conclusions
Below {SO4} = 10 − 2 M (Fig. 9a), sulfate concentration has no effect
on the dissolution of Th phosphate; the stability regions of the solid In the present work Eh–pH diagrams for the Th–, La–, Nd–, Ce–,
phases Th(HPO4)2·4H2O and Th2(PO4)2(HPO4)·H2O remain the (PO4)–(SO4)–H2O systems at 25 °C were generated using the HSC5.0
same. However, as {SO4} increases above 10 − 1 M (Fig. 9b and c), software with the aid of a critical collection of thermodynamic data.
sulfate complexation of Th increases. In the case of RE metals, as Based on the diagrams discussed above, the stability regions of vari-
shown in Figs. 10–12, the domains of solid sulfates of Nd and La ous species related to monazite hydrometallurgy can be predicted.
(Figs. 10 and 11) increase with increasing {SO4}, while the stability The main findings may be summarized as follows:
of cerium sulfate ions increases. Thus, as shown in Fig. 12, the
Ce(III)/Ce(IV) equilibrium potential decreases with increasing - Th–, Nd–, Ce–, and La–H2O systems: the aqueous stability domains
{SO4}. This indicates that the oxidation of Ce(III) becomes more fa- of Nd and La metals and related species found in this work are sim-
vorable with increasing sulfuric acid concentration and that Ce can ilar to the report of Pourbaix (1966). The difference in Ce specia-
be selectively separated from the other RE metals as Ce(IV) by add- tion from Pourbaix (1966) is due to the different thermodynamic
ing oxidants, such as persulfate, permanganate (Abreu and Morais, values used for Ce(OH)3, CeO2, and other species in the Ce–H2O
2010), and air or by electrochemical oxidation (Paulenova et al., system.
2002). It is noted that Fig. 12 does not show a stability region - Th–, Nd–, Ce–, and La–PO4–H2O systems: For the same RE metal,
for Ce2(SO4)3. This result is in agreement with the experimental the stability region of the solid REPO4 is different, depending on
observation that the solubility of RE metals in sulfuric–phosphoric the source of the thermodynamic data, a result which is attributable
acid solutions decreases in the order Ce > La > Nd at 20 °C to differences in the crystallinity and aged condition of RE-
(Lokshin et al., 2005). The dissolution of most lanthanide sulfates phosphates associated with the relevant experiments. The stability
is reported to be exothermic and their solubility decreases sharply region of the REPO4 is smaller for the less crystalline phosphates,
74 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

Fig. 9. Eh–pH diagrams for the Th–PO4–SO4–H2O system at 25 °C, {Th} = 10− 3, {PO4} =
Fig. 8. E–pH diagrams for the Th–, Nd–, Ce–, La–PO4–H2O systems at 25 °C, {PO4} = 10− 3 M: (a) {SO4} = 10− 2 M, (b) {SO4} = 10− 1 M, (c) {SO4} = 1.0 M.
10− 3 M: (a) {Nd}=10− 3 M, ΔGNdPO4 =−439.20 kcal/mol, (b) {Ce}=10− 3 M, ΔGCePO4 =
−439.79 kcal/mol, (c) {La}=10−3 M, ΔGLaPO4 =−441.88 kcal/mol.

suggesting that amorphization may be an effective method for en- Acknowledgements

hancing the dissolution of monazite.
- Th–, Nd–, Ce–, and La–(PO4)–SO4–H2O systems: The introduction The first author is grateful for support by the National Research
of sulfate ions into the aqueous system diminishes the stability do- Foundation of Korea Grant under the Korean Government (Ministry
mains of the solid metal phosphates, replacing them with solid of Education, Science and Technology, Project No. NRF-2010-357-
metal sulfates and or soluble metal sulfate complexes. This finding D00154). Also, the author wishes to express appreciation to Dr. Lee
clarifies the chemical basis for the commercial process of monazite J.-c., Korea Institute of Geosciences & Mineral Resources (KIGAM)
digestion in sulfuric acid. for reviewing this paper.
 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78 75

Fig. 10. Eh–pH diagrams for the Nd–PO4–SO4–H2O system at 25 °C, {Nd} = 10− 3, {PO4} = 10− 3 M: (a) {SO4} = 10− 2 M, ΔGNdPO4 = − 423.46 kcal/mol, (b) {SO4} = 1.0 M, ΔGNdPO4 =
− 423.46 kcal/mol, (c) {SO4} = 10− 2 M, ΔGNdPO4 = − 439.20 kcal/mol, (d) {SO4} = 1.0 M, ΔGNdPO4 = − 439.20 kcal/mol.

Appendix I. Data references of HSC 5.11 database.

Species References Species References

H3PO4 Barin 89 NdPO4(s) Pankratz 95

H2PO4− Shock 88 Nd2(SO4)3(s) Barin 77
HPO42 − Shock 88 NdSO4+ Haas 95
PO43 − Shock 88 Nd(SO4)2− NBS 82
H2SO4 Barin 93 Nd2(SO4)3·8H2O(s) Lange 85
HSO4− Shock 88
SO42 − Shock 88 Ce Barin 93
CeO2(s) Barin 89
Th Barin 89 Ce2O3 Barin 93
ThO2(s) Knacke 91 CeOH2+ Haas 95
Th(OH)4(s) Philips 88 CeH2PO42+ Haas 95
Th4+ NBS 82 Ce(SO4)2(s) Fabricius 94
ThOH3+ Philips 88 Ce2(SO4)3(s) Barin 77
Th(OH)22+ NBS 82 CeSO4+ Haas 95
Th2(OH)26+ Bard 85 Ce(SO4)2− NBS 82
Th4(OH)88+ Philips 88
9+
Th6(OH)15 Philips 88 La Barin 89
ThH2PO43+ Philips 88 La3+ Barin 93
ThH2PO42+ Philips 88 La2O3(s) Phillips 88
ThH3PO44+ Philips 88 La(OH)3(s) Shock 88
Th(H3PO4)(H2PO4)3+ Philips 88 LaH2PO42+ Haas 95
Th(HPO4)2·4H2O(s) Philips 88 LaPO4(s) Pankratz 95
Th(SO4)2(a) Philips 88 La2(SO4)3(s) Phillips 88
ThSO42+ Philips 88 LaSO4+ Haas 95
La(SO4)2− NBS82
Nd Knacke 91 La2(SO4)3(a) NBS 82
Nd3+ Shock 88
Nd2O3(s) Knacke 91
NdOH2+ Haas 95
76 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

Notes to Appendix I:
Bard 85: Bard A. J., Parsons R., Jordan J., Standard Potentials in Aqueous Solution, Marcel Dekker, New York, 1985.
Barin 77: Barin I., Knacke O., Kubaschewski O., Thermochemical Properties of Inorganic Substances, Supplement, Springer-Verlag, Berlin, p. 861, 1977.
Barin 89: Barin, I. Thermochemical Data of Pure Substances, VCH Verlags Gesellschaft, Weinheim, 1989.
Barin 93: Barin I: Thermochemical Data of Pure Substances, Part II,VCH Verlags Gesellschaft, Weinheim, 1993.
Fabricius 94: Fabricius G., Liukkonen S., Sundholm G. Fysikaalisen kemian taulukoita. Otatieto, Espoo, 1994.
Haas 95: Haas J. R., et al., Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth el-
ements at high pressures and temperatures, Geochim. Cosmochim. Acta 59, pp.4329–4350, 1995.
Knacke 91: Knacke O., Kubaschewski O., Hesselman K., Thermochemical Properties of Inorganic Substances, 2nd ed., Springer-Verlag, Berlin, 1991.
Lange 85: Dean J.A., Lange's Handbook of Chemistry, Thermodynamic Properties, McGraw-Hill, New York, 1985.
NBS 82: Bailey S. M., Churney K. L., Nuttall R. L.: The NBS Tables of Chemical Thermodynamic Properties, Selected Values for Inorganic and C1 and C2 Organic Substances in SI Units, J.
of Phys. and Chem. Ref. Data,Vol. 11, Suppl. No. 2, 1982.
Philips 88: Thermodynamic Tables for Nuclear Waste Isolation. Prepared by S. L. Philips, F. V. Hale, L. F. Silvester, Lawrence Berkely Laboratory M. D. Siegel, Sandia National Labo-
ratories, p. 182, 1988.
Pankratz 95: Pankratz L.B.: Thermodynamic Properties of Carbides, Nitrides, and other Selected Substances. U.S. Dept. of the Interior, Washington, DC, p. 957, 1995.
Shock 88: Shock E., Helgeson H. C., Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: correlation algorithms for
ionic species and equation of state predictions to 5 kb and 1000 °C, Geochim. Cosmochim. Acta 52, pp. 2009–2036, 1988.

Fig. 11. Eh–pH diagrams for the La–PO4–SO4–H2O system at 25 °C, {La} = 10− 3, {PO4} = 10− 3 M: (a) {SO4} = 10− 2 M, ΔGLaPO4 = − 425.78 kcal/mol, (b) {SO4} = 1.0 M, ΔGLaPO4 =
− 425.78 kcal/mol, (c) {SO4} = 10− 2 M, ΔGLaPO4 = − 441.88 kcal/mol, (d) {SO4} = 1.0 M, ΔGLaPO4 = − 441.88 kcal/mol.

References British Geological Survey, 2010. Rare earth elements. http://www.MineralsUK.

com2010.
Brookins, D.G., 1988. Eh-pH diagrams for geochemistry. Springer-Verlag, New York,
Abdel-Rehim, A.M., 2002. An innovative method for processing Egyptian monazite. Hy- USA.
drometallurgy 67, 9–17. Byrne, R.H., Kim, K.H., 1993. Rare earth precipitation and coprecipitation behavior: The
Abreu, R.D., Morais, C.A., 2010. Purification of rare earth elements from monazite sul- limiting role of PO43 − on dissolved rare earth concentrations in seawater. Geochim.
puric acid leach liquor and the production of high-purity ceric oxide. Miner. Eng. Cosmochim. Acta 57, 519–526.
23, 536–540. Cetiner, Z.S., Wood, S.A., Gammons, C.H., 2005. The aqueous geochemistry of the rare
Baes Jr., C.F., Mesmer, R.E., 1976. The hydrolysis of cations. Wiley, New York, USA. earth elements. Part XIV. The solubility of rare earth element phosphates from
Baláž, P., 2000. Extractive metallurgy of activated minerals, 1st ed. Elsevier Science, 23 to 150 °C. Chem. Geol. 217, 147–169.
Amsterdam, Netherlands. Dean, J.A. (Ed.), 1999. Lange's Handbook of Chemistry, 15th Ed. McGraw-Hill, NY, USA.
 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78 77

Fig. 12. Eh–pH diagrams for the Ce–PO4–SO4–H2O system at 25 °C, {Ce} = 10− 3, {PO4} = 10− 3 M: (a) {SO4} = 10− 2 M, ΔGCePO4 = − 421.75 kcal/mol, (b) {SO4} = 1.0 M, ΔGCePO4 =
− 421.75 kcal/mol, (c) {SO4} = 10− 2 M, ΔGCePO4 = − 439.79 kcal/mol, (d) {SO4} = 1.0 M, ΔGCePO4 = − 439.79 kcal/mol.

Fernelius, W.C., et al. (Ed.), 1946. 1st ed. Inorganic syntheses, Vol. II. McGraw-Hill Inc., Liu, X., Byrne, R.H., 1997. Rare earth and yttrium phosphate solubilities in aqueous so-
New York, USA, pp. 38–43. lution. Geochim. Cosmochim. Acta 61, 1625–1633.
Firsching, F.H., Brune, S.N., 1991. Solubility products of the trivalent rare-earth phos- Lokshin, E.P., Tareeva, O.A., Ivlev, K.G., Levin, B.V., 2005. A study of the solubility of hy-
phate. J. Chem. Eng. Data. 36, 93–95. drated orthophosphates of yttrium, lanthanum, cerium, and neodymium in
Gerasimova, L.G., Nikolaev, A.I., Maslova, M.V., Okhrimenko, R.F., 2010. Utilization of sulfuric-phosphoric acid solutions at 20°C. Russ. J. Appl. Chem. 78, 1913–1916.
waste containing rare-earth elements. Theor. Found. Chem. Eng. 44, 818–821. Mackey, T.S., 1986. Recent developments in U.S. rare earth technology. In: Somasun-
Gupta, C.K., Krishnamurthy, N., 2005. Extractive metallurgy of rare earths. CRC press, daram, P. (Ed.), Advances in mineral processing. Society of mining engineering, Lit-
NY, USA. tleton, CO, pp. 509–534.
Habashi, F. (Ed.), 1997. Handbook of extractive metallurgy, Vol. III. Wiley-VCH, Wein- Malcolm, R., Jean, F., Ingmar, G., Volker, N., Dhanpat, R., 2009. Chemical thermodynam-
heim, Germany. ics of thorium. OECD publishing, Paris, France.
Hart, K.P., Levins, D.M., 1988. Management of wastes from the processing of rare earth Manufacturing.net, 2009. China To Limit Rare Earths Exportsavailable at http://www.
minerals, Chemeca. 88: Australia's Bicentennial International Conference for the manufacturing.net/article.aspx?id=2155742009(1 September 2009).
Process Industries, Institution of Engineers, Australia, pp. 82–88. Milanova, M.M., Todorovsky, D.S., Balarew, C.C., Minkova, M.L., Ivanova, K.I., 2007. In-
HSC Chemistry 5.0, 2002. Chemical Reaction and Equilibrium Software with Extensive fluence of complexation on the composition of equilibrium phases in the system
hermochemical Database. ver.5.11, Outokumpu Research Oy, Piori, Finland. of Ce2(SO4)3 – La2(SO4)3. Cent. Eur. J. Chem. 5, 13–19.
Jones, A.P., Wall, F., Williams, C.T., 1996. Rare earth minerals chemistry, origin and ore Osseo-Asare, K., 1981a. Application of acitivity-activity diagrams to ammonia hydro-
deposits. Chapman & Hall, London, UK. metallurgy. 3. Mn-NH3-H2O, Mn-NH3-H2O-CO3 and Mn-NH3-H2O-SO4 systems at
Kamel, N., Remill, K., Arabi, M., Kamel, Z., Zahri, A., Metahri, S., 2010. Effect of the syn- 25°C. Inst. Min. Metall. Trans. 90, C152–C158.
thesis method on the properties of a Pb-bearing (Y-Gd-Ce) rare-earth phosphate Osseo-Asare, K., 1981b. Application of acitivity-activity diagrams to ammonia hydro-
used for the confinement of high-level radioactive waste. J. Nucl. Mater. 401, metallurgy. 4. Fe-NH3-H2O, Fe-NH3-H2O-CO3 and Fe-NH3-H2O-SO4 systems at
104–112. 25°C. Inst. Min. Metall. Trans. 90, C159–C163.
Kerdaniel, E.D.F., Clavier, N., Dacheux, N., Terra, O., Podor, R., 2007. Actinide solubility- Osseo-Asare, K., 1982. Solution chemistry of tungsten leaching systems. Metall. Trans. B
controlling phases during the dissolution of phosphate ceramics. J. Nucl. Mater. 13, 555–564.
362, 451–458. Osseo-Asare, K., 1989. Solution Chemistry and Separation Processes in Precious and
Kim, W., Bae, I., Chae, S., Shin, H., 2009. Mechanochemical decomposition of monazite Rare Metal Systems. In: Torma, A.E., Gundiler, I.H. (Eds.), Precious and Rare Metal
to assist the extraction of rare earth elements. J. Alloys Compd. 486, 610–614. Technologies. Elsevier, New York, pp. 113–135.
Koch, D.F.A., 1987. Rare earth extraction and separation Proc. Rare Earth Horizons Osseo-Asare, K., Fuerstenau, D.W., 1978. Application of activity-activity diagrams to am-
1987, Linfield, NSW, Department of Industry, Technology and Commerce, Canberra monia hydrometallurgy: The systems Cu-NH3-H2O, Ni-NH3-H2O and Co-NH3-H2O at
(1987), pp. 73–85. 25 °C. In: Chapman, T.W., Tavlarides, L.L., Hubred, G.L., Wellek, R.M. (Eds.), Fundamen-
Langmuir, D., Herman, J.S., 1980. The mobility of thorium in natural waters at low tem- tal hydrometallurgical processes: AlChE symposium series, 74, pp. 1–13.
peratures. Geochim. Cosmochim. Acta 44, 1753–1766. Osseo-Asare, K., Xue, T., Ciminelli, V.S.T., 1984. Solution chemistry of cyanide leaching sys-
Lee, J.-c., Kim, W.-b., Jeong, J., Yoon, I.J., 1998. Extraction of neodymium from Nd-Fe-B mag- tems, Process Metals, Mining, Extraction and Processing. In: Kudryk, V., Corrigan, C.A.,
net scraps by sulfuric acid. J. Korean Inst. Met. & Mater. 36, 967–972 (in Korean). Leang, W.W. (Eds.), AIME TMS Conference Proceedings, Los Angeles, Fubruary, 1984.
78 E. Kim, K. Osseo-Asare / Hydrometallurgy 113-114 (2012) 67–78

Osseo-Asare, K., Wei, D., Mishra, K.K., 1996. Dissolution windows for wet chemical pro- Wagman, D.D., et al., 1982. The NBS tables of chemical thermodynamic properties: se-
cessing of silicon and silicon dioxide: Potential-pH diagrams for the Si-F-H2O sys- lected values for inorganic and C1 and C2 organic substances in SI units. J. Phys.
tem. J. Electrochem. Soc. 143, 749–751. Chem. Ref. Data 11 (Suppl. 2) American chemical society and the American insti-
Paulenova, A., Creager, S.E., Navratil, J.D., Wei, Y., 2002. Redox potentials and kinetics of tute of physics for the national bureau of standards.
the Ce3+/Ce4+ redox reaction and solubility of cerium sulfate in sulfuric acid solu- Wei, Y., Sato, N., Nanjo, M., 1989. The solubility of Sm2(SO4)3 and Nd2(SO4)3 in sulfate
tions. J. Power Sources 109, 431–438. solutions: Fundamental study on the recycling of rare earth magnet. Min. Mater.
Poitrasson, F., Oelkers, E., Schott, J., Montel, J.-M., 2004. Experimental determination of Process. Inst. Jpn. (in Japanese) 105, 965–970.
synthetic NdPO4 monazite end-member solubility in water from 21°C to 300°C: Wood, S.A., 1990. The aqueous geochemistry of the rare-earth elements and yttrium: 1.
Implications for rare earth element mobility in crustal fluids. Geochim. Cosmo- Review of available low-temperature data for inorganic complexes and the inor-
chim. Acta 68, 2207–2221. ganic REE speciation of natural waters. Chem. Geol. 82, 159–186.
Pourbaix, M., 1966. Atlas of electrochemical equilibrium in aqueous solution. Perga- Xue, T., Osseo-Asare, K., 1985. Heterogeneous equilibria in the Au-CN-H2O and Ag-CN-
mon, New York, USA. H2O systems. Metall. Trans. B 16, 455–463.
Reuters, 2009. As hybrid cars globble rare metals, shortage loomsavailable at http:// Zhang, J., Lincoln, F.J., 1993. The decomposition of NdPO4 during mechanical milling. J.
www.reuters.com/article/2009/08/31/us-mining-toyota- Alloys Compd. 200, 151–156.
idUSTRE57U02B200908312009(retrieved Aug 31). Zhang, J.-P., Lincoln, F.J., 1994. The decomposition of monazite by mechanical milling
Todorovsky, D.S., Milanova, M.M., Minkova, N.L., Balarev, C., 1993. Solubility of some with calcium oxide and calcium chloride. J. Alloys Compd. 205, 69–75.
lanthanide sulfates in polycomponent systems containing H2SO4. Monatsh. Ziya, S.C., Scott, A.W., Christopher, H.G., 2005. The aqueous geochemistry of the rare
Chem. -Chem. Mon. 124, 673–679. earth elements. Part XIV. The solubility of rare earth element phosphate from 23
Todorovsky, D., Terziev, A., Milanova, M., 1997. Influence of mechanoactivation on rare to 150°C. Chem. Geol. 217, 147–169.
earths leaching from phosphogypsum. Hydrometallurgy 45, 13–19.