See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/265165455

From Neodymium Oxide to NdFeB Alloy: An

Overview on the Reduction Methods

Conference Paper · August 2014

DOI: 10.13140/RG.2.1.3487.0807

CITATIONS READS

2 431

3 authors:

M.F. De Campos Daniel Rodrigues

Universidade Federal Fluminense Universidade Federal Fluminense
169 PUBLICATIONS 762 CITATIONS 68 PUBLICATIONS 271 CITATIONS

SEE PROFILE SEE PROFILE

Jose Adilson De Castro

Universidade Federal Fluminense
163 PUBLICATIONS 382 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Characterization application and fate of nanoparticles in the environment View project

RARE-EARTHS: FROM THE EXTRACTION TO THE APPLICATION View project

All content following this page was uploaded by M.F. De Campos on 30 August 2014.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
Wednesday, 7:00 – 9:00 PM Posters B: Novel Synthesis and Processing REPM2014

From Neodymium Oxide to NdFeB Alloy: An Overview on

the Reduction Methods

JOSÉ ADILSON DE CASTRO1, DANIEL RODRIGUES1,2, MARCOS FLÁVIO DE CAMPOS1
1
PUVR– Federal Fluminense University, Volta Redonda, Rio de Janeiro, Brazil
2
BRATS - Sintered Filters and Metallic Powders, Cajamar, São Paulo, Brazil

Abstract: The main methods for producing metallic neodymium are briefly reviewed. These three methods are
i) electrolysis using fluoride salts, ii) electrolysis using chloride salts, iii) calciothermic reduction. Fused salt
electrolysis using fluoride remain are the most widely used commercial method for neodymium. An interesting
possibility is the reduction of didymium oxide for production of magnets, avoiding the separation between Nd
and Pr oxides. A mathematical model able to simulate the reduction is in development. The model takes into
account parameters as cell size and geometry, distance between the electrodes and rate of carbon anode
consumption.

Keywords: rare earth; reduction, oxides; neodymium; praseodymium

Address: Jose´A de Castro, Universidade Federal Fluminense, Volta Redonda RJ, 27255-125,
Brazil joseadilsoncastro@id.uff.br , marcosflavio@id.uff.br

1. Introduction analogy with the Hall-Heroult process for aluminum

In the rare-earth business, two details are relevant, one
of them is the rare-earth oxide separation in large
scale, and the other is the production of rare-earth
metal, or rare-earth magnetic alloy, from the oxide.
This article is mainly devoted to the later: obtaining
the metallic neodymium from oxide. Some of the main
methods for producing metallic neodymium are
discussed and reviewed, among them: i) neodymium
electrolysis from fused fluoride salts; (ii) neodymium
electrolysis from fused chloride salts; (iii)
calciothermic reduction of neodymium oxide for
production of the Nd-Fe-B alloy.
According Richardson [1], there was no commercial
producer of metallic rare-earth in United Sates, at the
beginning of 2013. The situation is different in Europe,
where LCM [2] announced in mid 2013 the production
of metallic rare-earth using molten salts. Brazil was a
producer of metallic mischmetal in early 1990s, at the
CIF company. However, after 1996, CIF focused on
tantalum production [3], and stopped metallic
rare-earth production. The process employed by CIF
used fluoride molten salts.
The manufacture of metallic rare-earth is of special
relevance for magnet production. In this article, details
of the process for obtaining metallic rare-earth are
reviewed. Calciothermic reduction of are-earth was
very successful for SmCo 5 alloy production, but
presents some difficulties for NdFeB alloy. The
process of reduction using fused salts is discussed in
reduction. Present day technology usually makes use
of fluoride salts for reduction of neodymium oxides.
2. Rare Earth Oxide Separation
The problem of the commercial rare-earth oxide
separation starts in the 1880s when Carl Auer von
Welsbach obtained ship ballasts consisting in
monazitic black sand from Brazilian shore (coasts of
South of Bahia, Espírito Santo and North of Rio de
Janeiro States). An essential step in the rare-earth
business is the rare-earth oxide separation, because
the price of the oxide concentrate without any
separation is very low. The separation method
depends on the chosen ore [4]. In other words, the flow
chart for rare-earth separation has to be optimized for
each specific ore [5]. Rare earths with even atomic
number (Z=60 for Nd) are much more abundant that
their odd next neighbor (Z=59 for Pr). This is the
so-called Oddo-Harkins rule. As consequence, in
many ores, Neodymium and Praseodymium appear
following the approximate proportion 3 Nd : 1 Pr [6].
This couple of elements is known as Didymium (from
the Greek name for twins), after Mosander studies in
the 1840s [7]. Only in 1885 Carl Auer von Welsbach
demonstrated that Didymium was in fact
Praseodymium and Neodymium. For magnet
preparation, it may be better to keep the twins
together. As the anisotropy field of praseodymium is
higher than that of neodymium, a present day trend is
the production of the didymium oxide as a commercial

358
Wednesday, 7:00 – 9:00 PM Posters B: Novel Synthesis and Processing
product, avoiding the separation of the didymium
twins in the flow-chart. Due to recent renewed interest
in rare-earth elements for many different technological
applications, there are a number of recent reviews on
the rare-earth oxide separation subject [8-11]. All of
them emphasize that the separation process has to
adapted or developed for each specific ore.
3. Obtaining the Neodymium Alloy
The focus of this brief review, however, is the
production of the magnetic alloys. According David
Kennedy [12], fused salt electrolysis employing
fluorides remains the main method for metallic
Neodymium as well as Dysprosium or
Iron-Dysprosium production. This is essentially the
same method used for mischmetal production in
Brazil more than 20 years ago [3]. Many studies,
however, have mentioned chlorides [13,14] instead of
fluorides. A disadvantage of chlorides is that they are
hygroscopic. Besides, the chlorides are less stable
thermodynamically than the fluorides, generating Cl 2
and decreasing the current efficiency. Higher
solubility of rare earth oxides and better conductivity
also count in favor for choosing fluorides. Another
interesting possibility is the calciothermic reduction
of the Iron-Neodymium alloy. This was a subject of
several academic studies in Brazil [15,16] and other
countries [17,18]. Whereas a NdFe alloy oxidizes
easily, a SmCo alloy not. Thus, a commercial SmCo 5
powder alloy was produced by co-reduction process
[19] by Goldschmidt in the 1970s, and later by LCM
(Less Common Metals) in North West England [20].
Many difficulties, however, have been found for
production of NdFe alloys using calcium oxide for
reduction. As consequence, reduction by electrolysis
using fluoride fused salts remains dominant as
commercial process up to present day. The
electrowinning of neodymium and other rare-earth
metals was investigated by Morrice and coworkers in
the 1960s [21,22], and these studies remain a relevant
reference up to the present day. The process
employed by Morrice et al [21,22] has much in
common with the process for metallic aluminum
production [12], known as Hall-Heroult process.
Continuing the research of Morrice et al [21],
Dysinger and Murphy [23] discussed the possibility
of increasing the size of the cells used for metallic
neodymium production, and the effect of several
processing variables. There is concern about fumes
produced in the processing of metallic rare-earths [4,
24] and, thus, this detail has to be considered when
designing the manufacturing plant. Several details
359
REPM2014
may affect the reduction process, as for example cell
size and geometry, current density and current
efficiency, which depends on the distance between
the electrodes. Another important detail is the carbon
anode consumption during the reduction. All these
details are being considered in a mathematical model
[25] able to simulate the neodymium reduction
process. The model uses the Navier-Stokes equations
coupled with magnetohydrodynamics [25]. It is
expected that the model may contribute for
optimization of the processing parameters, for
example the electrical energy consumption, which is
usually high in the Hall-Heroult process of aluminum
production.
4. Conclusions
The mines starting rare-earth concentrate or oxide
production need to take into account that the price of
rare-earth concentrate is very small, and that
producing the separate oxides is necessary to increase
the value.
Didymium oxide obtained directly from ore is very
interesting for magnet production, presenting around
¼ Pr and ¾ Nd. Thus, the Didymium twins
Praseodymium and Neodymium do not need be
separated for producing the metallic alloy for magnet
production.
The most used commercial process for metallic
Neodymium production is the electrolysis using
fluoride salts, and this process have similarities with
the old Hall-Heroult process for aluminum
production.
Acknowledgments
The authors would like to thank the National Council
for Scientific and Technological Development
(CNPq).
References
[1] http://www.magneticsmagazine.com/main/blogs
/the-rare-earth-industry-where-do-you-fit/
[2] http://www.proactiveinvestors.com.au/compani
es/news/45536/great-western-minerals-successf
ully-produces-neodymium-metal-from-uk-manu
facturing-unit-45536.html
[3] www.cif.ind.br/historia.html
[4] http://nepis.epa.gov/Adobe/PDF/P100EUBC.pd
f
[5] http://qhxb.lib.tsinghua.edu.cn/myweb/english/2
Wednesday, 7:00 – 9:00 PM Posters B: Novel Synthesis and Processing
006/2006e2/241-247.pdf
[6] Z. Chen: Journal of Rare Earths Vol. 29 (2011),
p. 1–6
[7] F. Szabadvary “The History of the Discovery
and Separation of the Rare Earths”. In:
Handbook on the Physics and Chemistry of
rare-earths, Volume 11. Edited by: Karl A.
Gschneidner, Jr. and LeRoy Eyring, Elsevier,
1988, p. 33
[8] A. Jordens, Ying Ping Cheng, K. E. Waters.
Minerals Engineering Vol. 41 (2013), pp. 97–
114.
[9] A. Golev, M. Scott, P. D. Erskine, S. H. Ali, G.
R. Ballantyne. Resources Policy, Vol. 41 (2014),
pp. 52-59.
[10] http://www.springer.com/earth+sciences+and+g
eography/geology/book/978-3-642-35457-1
[11] Feng Xie, Ting An Zhang, David Dreisinger,
Fiona Doyle. Minerals Engineering, Vol. 56,
(2014) pp. 10-28.
[12] D. Kennedy. In: Strategische Rohstoffe-
Risikovorsorge. Springer Spektrum, Berlin,
2014, pp 201-217.
[13] N. Krishnamurthy, C. K. Gupta: Extractive
Metallurgy of Rare Earths. CRC Press, Boca
Raton Florida, 1st edition (2004)
[14] S. Singh, J. M. Juneja, D. K. Bose. Journal of
Applied Electrochemistry Vol. 25 (1995), pp
1139-1142
[15] http://pelicano.ipen.br/PosG30/TextoCompleto/
Eneida%20da%20Graca%20Guilherme_D.pdf
360
REPM2014
[16] P.F. Nogueira, F.B. Neto: Materials Science
Forum Vols. 299-300 (1999), p. 200.
[17] Chiranjib Kumar Gupta .Chemical Metallurgy:
Principles and Practice, Wiley, 2006
[18] http://www.jim.or.jp/journal/e/31/06/463.html
[19] http://hal.archives-ouvertes.fr/docs/00/21/88/83/
PDF/ajp-jphyscol197940C5100.pdf
[20] http://www.tremcenter.org/index.php?option=co
m_attachments&task=download&id=31
[21] E. Morrice, T A. Henrie. Electrowinning
high-purity neodymium, praseodymium, and
didymium metals from their oxides
[Washington, D.C.] U.S. Dept. of the Interior,
Bureau of Mines, 1967.
[22] E. Morrice, E.S. Shedd, and T.A. Henrie: Direct
electrolysis of rare-earth oxides to metals and
alloys in fluoride melts [Washington, D.C.] U.S.
Dept. of the Interior, Bureau of Mines, 1968.
[23] D. K. Dysinger and J. E. Murphy
Electrowinning of Neodymium From a Molten
Oxide-Fluoride Electrolyte, U.S., Bureau of
Mines
1994. stacks.cdc.gov/view/cdc/10116/cdc_1011
6_DS1.pdf
[24] http://epa.tas.gov.au/documents/lynas%20servic
es%20pty%20ltd,%20didymium%20pilot%20pl
ant,%20ear.pdf
[25] J. A. de Castro, M. F de Campos. Modeling the
neodymium metallic reduction from molten
salts. Unpublished.