JOURNAL OF APPLIED ELECTROCHEMISTRY 23 (1993) 1017-1024
Effect of impurities on the corrosion behaviour of
neodymium
H. BALA*, S. SZYMURA *, G. PAWLOWSKA*
Department of Chemistry* and Institute of Physics ~, Polytechnic of Czestochowa, Al.Armii Krajowej 19,
PL 42-200 Czestochowa, Poland
YU. M. RABINOVICH
Research and Technology Enterprise MIRT, Gospitalnyi Val 5-18 kv.172 105094 Moscow, Russia
Received 13 April 1992; revised 2 February 1993
The corrosion behaviour of neodymium contaminated with up to 0.9% C, up to 15% Fe and about
16% of Tb or Dy was examined in various aggressive environments. It was found that in acid media
the C and Fe additions accelerated the corrosion process of the alloys. The Nd-base alloys were fairly
resistant to corrosion in atmospheric conditions, however, the impurities worsened the corrosion
behaviour in this environment as compared with pure Nd.
1. Introduction
In the early 1980s wide application of new high-per-
formance RE-Fe-B type magnets (where RE = Nd,
more rarely Pr or Dy or their compositions) began
in many countries. The magnets exhibit excellent mag-
netic properties, however, they suffer strongly from
great sensitivity to corrosion in many aggressive
environments. This poor resistance to corrosion
results from the presence of relatively high amounts
of rare earth elements (30-35wt %). The rare earth
elements are among the most electrochemically active
metals, the standard potentials for RE/RE 3+ systems
being -2.6 to -2.0V [1].
The corrosion mechanism of Nd-Fe-B type
magnets consists of the preferential oxidation (dis-
solution) of a Nd-rich phase (chemical formula
Nd4Fe), situated between the grains of a ferro-
magnetic Nd2Fel4B phase. This causes surface
degradation, a worsening of magnetic properties,
and sometimes reduces to pulverization. The
corrosion mechanism of RE-containing permanent
magnets is discussed in [2-6]. The susceptibility of
the Nd-rich phase to corrosion can be reduced by
such alloying additions as Co (about 5 at %) [4, 7]
or 1 at % of Cr, A1, Ti and Zr [6, 7]; these additions
also improve the magnetic properties of the alloys.
In permanent magnet technology a high grade
purity neodymium is used, which increases the price
of the magnet [8]. The separation and purification of
RE elements is a complex process. Especially un-
desirable impurities of RE elements are considered
to be mainly O and C [9] because these impurities
degrade the coercive force of the RE-Fe-B mag-
nets. On the other hand, the presence of decimal
percentages of carbon in the alloy causes a strong
enrichment of the Nd-rich phase (during sintering
inclusions of NdC2 carbide appear [9]), which can
have significant consequences for the corrosion
behaviour.
Taking into account that the corrosion resistance of
sintered Nd-Fe-B type magnets is determined mainly
by the electrochemical activity of the Nd-rich phase
(containing 75-85wt% Nd), it is important to
know the effect of technological impurities on the
corrosion behaviour of RE alloys.
There is little literature concerned with the prob-
lem of corrosion behaviour of pure RE metals
and their alloys. In [10, 11] the corrosion characteris-
tics of pure (99.9%) RE metals (apart from Pm)
are presented, however, they refer mainly to the
metal's behaviour in atmospheric conditions and at
elevated temperatures. Rybakov et al. [12, 13]
noticed the important role of air pollutants (SO2,
H20, CO2) on the corrosion of pure metals:
La (99.9%) and Ce (99.8%). All cited authors believe
that the corrosiveness of air rises sharply with an
increase in relative humidity. Lee and Greene
[11] consider RE-oxides to have protective properties
whereas hydroxides (formed on the surface in the
presence of humidity in the air) do not protect the
surface of the RE-metal against further corrosion
attack.
To characterize the corrosion behaviour of RE
metals in acid media, it is important to consider the
possibility of the creation of RE hydrides as products
of the corrosion process. The great affinity of RE
metals to hydrogen is commonly known. Gaseous
hydrogen reacts with RE elements at room tempera-
ture. In the case of Nd-Fe-B magnets, the creation
of hydrides in both the ferromagnetic and Nd-rich
phases was found. As a result, non-stoichiometric
products, with formulae Nd2FelaBH3. 3 and NdH28,
respectively, are formed [14]. Absorption of gaseous
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