Study of production process of refined rare-

earth alloys and addition alloys

Cite as: AIP Conference Proceedings 1772, 030002 (2016); https://doi.org/10.1063/1.4964540
Published Online: 13 October 2016

Vladimir Sofronov, Alexander Buinovskiy, Yuri Makaseev, et al.

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© 2016 Author(s).
 Study of Production Process of Refined Rare-Earth Alloys
and Addition Alloys
Vladimir Sofronova), Alexander Buinovskiyb), Yuri Makaseevc), Evgeniy
Kartashovd) and Igor Rusakove)

National Research Nuclear University «MEPhI», 31 Kashirskoye Shosse, Moscow 115409 Russian Federation
a)
corresponding author: [email protected]
b)
[email protected]
c)
[email protected]
d)
[email protected]
e)
[email protected]

Abstract. Rare-earth permanent Nd-Fe-B-based magnets are the most promising ones because they have the highest
magnetic and operating characteristics. These magnets are produced from alloys having the respective chemical
composition with the help of the powder metallurgy technology. One of the methods of magnetic alloys synthesis is
fluoride technology which includes the following basic stages: fluorination of raw materials (oxides, metal concentrates,
waste products of magnetic or other productions) by means of elemental fluorine or other fluorinating agent, calcium-
thermal out-of-furnace fluoride reduction with the production of compact ingots of alloys and foundry alloys (magnetic
materials) of the desired composition and the production of magnets with the help of the technology mentioned above.
The paper presents the results of study of the magnetic alloys production with the help of fusion of individual
components. The research results of the refinement of magnetic materials obtained by the out-of-furnace reduction by
means of their induction refining are presented. Modification of magnetic materials with the help of nano-dispersed
powders of refractory compounds during induction refining is also considered. This allows producing materials of higher
quality for the production of high-energy permanent magnets (HEPM).

INTRODUCTION
Methods of rare earth alloys production
The feedstock for the production of rare earth alloys HEPM is alloys produced with the help of the following
techniques:
fusion of individual components principally in induction furnaces [1];
metallothermic furnace or out-of-furnace reduction [2].
Commonly the industrial production of Nd-Fe-B-based alloys is implemented in inert atmosphere with the help
of the induction technique that provides good mixing. Rare-earth metals are placed when the other components are
melted. To produce columnar structured alloys, which have pronounced anisotropic properties, cooling in massive or
refrigerated crystallizers is used. Boron is introduced into the melt either as a fine metal or as a Fe-B alloy with
different boron content. Alundum, boron carbonitride, tantalum, niobium or their alloys are used as the crucible
material. The given processes are complicated by the choice of structural materials for smelting and casting rare-
earth metals owing to their extremely high chemical activity and considerable metal losses during the melting
operation by reason of high vapor tension of these metals at 1300-1500 °С.
Individual rare-earth metals (REM) are produced either by means of the furnace metallurgy technique, while
heating the source furnace charge composed of REM fluorides, chlorides or oxides and a metal-deoxidizer (calcium
and calcium hydride are more frequently used) up to 800-1200 °С, or by means of the halogenide electrolysis at
800-1200 °С [3]. To produce magnetic alloys from these metals, one has to perform primary purification, for

Prospects of Fundamental Sciences Development (PFSD-2016)

AIP Conf. Proc. 1772, 030002-1–030002-7; doi: 10.1063/1.4964540
Published by AIP Publishing. 978-0-7354-1430-3/$30.00

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example, by means of electric refining or vacuum refining in induction, arc, electron-beam, plasma-induction
furnaces or in other types of furnaces.
Thus the purpose of the work is to study the effect of the refining process on quality of magnetic alloys and
foundry alloys obtained by the out-of-furnace metallothermic reduction.

EXPERIMENT

Experimental facility and description

The research has been conducted with the help of the vacuum induction apparatus LК 140-2, presented in fig. 1.
The capacity of its crucible is 140 cm3. The apparatus is a frequency converter with a water-cooled inductor. Inside
the inductor, there is a thermal isolation insertion with a working crucible. A spring mechanism is used for the
bottom pouring of metals. The spring mechanism presses a rod to the tank port of the crucible and raises it if
pressed.

FIGURE 1. Design of the melting chamber and its elements: 1− lifting rod; 2 − binding screw; 3 − armature of rod-140; 4 −
thermocouple for K140; 5 − locking rod; 6 − heat-insulating cover-140; 7 − heat-insulating insert; 8 − graphite crucible; 9 −
safety panel of inductor 140; 10 − heat-insulating insertion; 11 − refractory cardboard insertions; 12 – fireclay bushing; 13 −
lower panel of inductor; 14 – inductor

The following researches have been conducted:

1. The production process of magnetic materials with the help of the individual components melting technique;
2. Refining of addition alloy ingots produced by means of out-of-furnace reduction of metal fluorides [4];
3. Refining of alloy ingots produced by means of out-of-furnace reduction of metal fluorides [4];
4. Refining of alloy ingots and addition alloy ingots with the addition of modifying agents; nanostructured
materials production.

Production of magnet materials (Fe-Nd-B-alloying components) from metal components

Alloy smelting was carried out in a vacuum induction furnace by the following technique:

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 the electrocorundum crucible was filled with metallic iron in concordance with the alloy composition; the
furnace chambers were vacuumized up to residual pressure of 0.1-0.5 Pa;
induction heating was conducted at temperature of (1560 10) °С until the iron was completely melted and
the system was completely degassed;
argon was supplied into the furnace chamber up to pressure of (20-26)·103 Pa in order to decrease the
volatility of rare-earth metals and to eliminate the ebullition of the melt;
neodymium, dysprosium and other alloying components were added and induction heating of the system
was conducted at temperature of (1510 10) °С during 5 minutes until the alloying components were
completely melted; the system was heated up to (1350 10) °С when dysprosium was not added;
ferroboron was added; the ferroboron having completely melted, the melt was exposed at temperature of
(1350 10) °С for 5-10 minutes;
the melt was poured into a cast-iron mold or a copper casting mold;
the ingot cooling was carried out in the argon atmosphere at pressure of (20-26)·103 Pa for 6 hours.
Neodymium (NM-3 TU 48-4-205 (Russian: НM-3, ТУ 48-4-205)), dysprosium (Dim 3 TU 48-4-214 (Russian:
ДиМ 3 ТУ 48-4-214)), iron ZhR-008 (TU 14-1-2033) (Russian: ЖР-008 (ТУ 14-1-2033)), cobalt Co (GOST 123)
(Russian: K0 (ГОСТ 123)), ferroboron FB-10 (GOST 14848) (Russian: ФБ-10 (ГОСТ 14848)), titanium VT1-0
(Russian: ВТ1-0) and aluminum А99 were used as source charge materials for magnet alloy smelting in the
induction furnace.
Magnet materials (alloy ingots) were smelted with the help of the technique mentioned above. The initial
composition of alloys, the induction refining indices and compounds of the produced alloy ingots are presented in
Table 1.
The compositional analyses for calcium, silicon, copper and nickel were conducted according to GOST 23862
(Russian: ГОСТ 23862). The compositional analysis for carbon was conducted according to OST 95 832 (Russian:
ОСТ 95 832). Concentrations of other elements were determined with the help of the inductively coupled plasma
atomic emission spectroscopy (ICP-AES) using the device iCAP-6200. The technique is based on the study of the
emission spectrum of free atoms and ions, when the sample liquor is placed into the plasma. For correction, the
internal standard method was used, i.e. introduction of a certain and fixed amount of the internal standard into the
sample. The cadmium solution with the concentration of 0.5 g/dm3 was used as the internal standard.
When studying the composition of solid samples, they were preliminarily dissolved. If necessary, the microwave
system of sample preparation MARS 6 was used. Application of microwave techniques for dissolving the solid
samples allows intensifying the process through a combination of high thermal capacity of the microwave energy
with the benefits of autoclave decomposition.

TABLE 1. Induction refining (IR) indices of pure components

ingot Rated alloy composition, аt % Rated alloy composition, wt %
No Nd Fe Al Ti B Nd Fe Al Ti B
A1 17.0 76.7 1.0 - 5.3 36.00 62.76 0.40 - 0.84
A2 16.0 76.2 1.0 0.1 5.8 34.45 63.50 0.40 0.72 0.93
A3 15.5 75.6 1.0 1.8 6.1 33.70 63.60 0.40 1.30 1.00
A4 15.5 73.1 1.0 1.8 8.6 34.28 62.58 0.40 1.32 1.42
Continuation of Table 1
ingot Initial load Ingot output after Alloy composition after IR, wt % REM loss
No weight, g IR
g % Nd Fe Al Ti B Impurities g %
A1 500.0 482.5 96.5 34.10 64.33 0.42 - 0.85 0.30 15.5 8.61
A2 500.0 485.0 97.0 33.00 64.60 0.42 0.75 0.95 0.28 12.1 7.03
A3 500.0 485.0 97.0 32.10 64.81 0.42 1.35 1.03 0.29 12.8 7.59
A4 500.0 487.5 97.5 32.50 63.95 0.42 1.38 1.45 0.30 13.0 7.58

The data presented in table 1 show that ingot output is sufficiently high and it equals 96.5-97.5%. Meanwhile,
REM loss is in the range of 7.03-8.61%wt. After induction refining the ingots contained impurities in the range of
0.28-0.30%wt. At the same time all the compounds were evenly distributed in the ingot.

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 In all remelted alloy ingots the content of aluminum was 0.03-0.10 %, the content of silicon was 0.04-0.06 %,
the content of calcium was 0.01-0.02 %, the content of carbon was less than 0.02 %, the content of manganese,
nickel and copper was in the range of 0.03 – 0.07 %.

Induction refining of alloy ingots

Alloy ingots were produced by means of combined out-of-furnace reduction of REM fluorides and Fe fluorides
[4]. An addition alloy with high content of neodymium and other rare-earth elements (REE) can be used for magnet
alloys production by means of remelting with addition of Fe, FeB and other alloying additions. In this case the
foundry alloy, contained in the charge mixture, substitutes for metal neodymium. The main advantage of the foundry
alloy over metal neodymium is its lower cost. The experiments were carried out with the help of the apparatus,
presented in fig. 1, using the technique, described in 2.2, in the induction furnace subject to the fact that the charge
material in the form of unbroken ingots or ingot fragments was directly loaded into the crucible. The chamber was
vacuumized to the residual pressure of 0.1-0.5 Pa and the furnace heating was switched on. The temperature having
reached 900-950 °С, argon was supplied into the furnace chamber up to pressure of 0.08-0.09 MPa and the heating
was continued to 1200-1300 °С. The materials having melted, the same temperature was maintained for 5-7 minutes
in order to average the chemical composition and to refine the material. Then the rod (1) was raised and the liquor
was discharged into the crystallizer.
The experiment results are presented in table 2.
TABLE 2. Induction refining (IR) indices of Nd-Fe alloys
Expe- Temperature, Initial Content of components in source Impurities Ingot output
riment °C weight, g material, %wt after IR
No Nd+Pr Fe
% g % g % g g %
L1 1050 500 73.20 366.0 26.20 134.0 0.6 3.0 462.0 92.4
L2 1150 500 72.80 364.0 26.73 133.5 0.5 2.5 480.0 96.0
L3 1280 500 73.20 366.0 26.30 131.5 0.5 2.5 473.5 94.7
L4 1350 500 73.20 165.9 26.30 59.6 0.6 3.0 477.5 95.5
Continuation of Table 2
Expe- Content of components in an IR ingot Impurities IR wastes REM loss during
riment Nd+Pr Fe refining
No g % g % g % g % g %
L1 336.8 72.9 124.3 26.9 1.25 0.25 38.0 7.6 29.2 8.0
L2 346.1 72.1 132.5 27.6 1.35 0.27 20.0 4.0 17.9 4.9
L3 342.8 72.4 129.4 27.3 1.50 0.30 26.5 5.3 23.2 6.3
L4 157.6 33.0 313.2 65.6 1.50 0.30 27.5 5.5 8.3 5.0
Note. Nd+Pr content was determined at 8 points of marketable ingots by measuring the radius and the height;
variations did not exceed ( 0.2) %.

The data presented in table 2 show that the casting output of alloys (experiments L1-L3) ranges within 92.4-96.0
%, and the amount of waste products that remains on the wall of the apparatus, in the crucible, in the waste funnel is
4.0-7.6 %.
Owing to evaporation out of the reaction system, the loss of rare-earth metals is 4.9-8.0%. The loss increases
with rising temperature of induction refining. The vapour pressure of Nd and Pr at 1050-1280°С is much higher
than the vapour pressure of Fe. Therefore, one can suggest that all metal losses from the melting crucible are related
to rare-earth metals.
Induction refining of foundry alloys taking place, the concentration of rare-earth metals becomes equal in all
over the ingot and its marketable state improves. However, carrying out this operation is not rational due to the large
amount of wastes generation and REM loss, increase in the production costs and price.
During experiment L4 there has been produced the magnetic alloy having the following composition (%wt):
33.0(Nd+Pr)-65.6Fe-1.1B. This magnetic alloy has been produced by means of the induction refining of the foundry
alloy 73.2(Nd+Pr)-Fe with addition of 27.5 g of ferroboron FB-20 (Russian: ФБ-20) and metal compact iron having

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the weight of 245.4 g. At the same time the ingot output was near its maximum and amounted 95.5%, the total
impurity content in the alloy produced was less than 0.3% and the amount of waste products remaining on the wall
of the apparatus, in the crucible and the waste funnel was 5.5 %.
Thus, it is possible to produce magnetic alloys having the desired composition by means of the induction
refining of REM-Fe addition alloys.

Induction refining of magnetic alloys ingots

The experiments were carried out with the help of the apparatus, presented in fig. 1, using the technique,
described in 2.2. The experiment results are presented in table 3.
TABLE 3. Induction refining (IR) indices of magnetic alloys
Expe Initial Content of components in source material, %wt Ingot cast
rime weight, g after IR
nt Nd+Pr Dy Tb ∑REE Fe Co B Impu g %
No rities
A5 500 34.5 - - 34.5 63.6 - 1.2 0.7 470.0 94.0
A6 500 29.8 4.7 - 34.5 59.0 4.5 1.2 0.8 477.5 95.5
A7 500 30.1 - 4.4 34.5 59.1 4.5 1.2 0.7 481.0 96.2
A8 500 26.1 4.3 4.1 34.5 59.1 4.5 1.2 0.7 480.0 96.0
Continuation of Table 3
Expe- Content of components in an IR ingot, %wt IR wastes
REM loss
riment during
No refining
Nd Pr Dy Tb ∑REE Fe Co B Impurities g % g %
A5 34.2 0.3 - - 34.5 64.0 - 1.2 0.3 30.0 6.0 10.4 6.0
A6 27.9 0.4 4.2 - 32.5 61.3 4.7 1.2 0.3 22.5 4.5 17.3 10.0
A7 28.1 0.4 - 4.2 32.7 61.1 4.7 1.2 0.3 19.0 3.8 15.2 8.8
A8 25.0 0.4 4.0 3.9 33.3 60.5 4.7 1.2 0.3 20.0 4.0 12.7 7.4
Note. Nd+Pr content was determined at 4 points of a marketable ingot by measuring the radius and the height;
variations did not exceed ( 0.2) %.

In all remelted alloy ingots the content of aluminum was in the range of 0.05-0.10 %, the content of silicon was
0.05-0.08 %, the content of carbon was less than 0.03 %, the content of manganese, nickel and copper was in the
range of 0.02 – 0.05 %.
The data presented in table 3 show the following: the induction refining of alloys having been carried out, the
total impurity content decreased by more than a half. The ingot output is sufficiently high and it equals 94.0-96.2%.
Meanwhile, REM loss is in the range of 6.0-10.0%. All the alloy compounds are evenly distributed in the ingot.

Production of nanostructured materials

To produce the fine-crystalline (0.5-1.0 micrometers) structure of obtained alloys it is necessary to fulfill one of
the following conditions: either the cooling rate of casting must be not less 10 4 К/min or the crystallization process
must not start near the walls but it must occur directly in the bulk [5]. It is technologically difficult to fulfill the first
condition. In order to fulfill the second condition we used a method which showed itself to advantage in ironmaking,
i.e. the technique of addition of artificial crystallization grains in the form of superdispersed mechanoactivated
powders [6].
In order to start the simultaneous crystallization in the whole bulk of the metal discharged into the casting mold,
the mechanoactivated modifier with particle size of 50-100 nm was placed into the molten material directly before
discharging. It consisted of iron-clad REE oxides. The modifier was a surface-active material and it ensured the
initiation of active crystallization grains in the whole bulk of the solidifying material. It allowed producing the
identical microstructure in the bulk of the ingot and facilitating the subsequent process of hydrogen comminuting
when the material hydrogenation took place along the boundaries of grain space [7].

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 2

FIGURE 2. The scheme of mixing the modifier and the magnetic alloy: 1 - metal melt; 2 - platform with modifier; 3 – crucible

In practice it was as follows:

mix material was put onto a small platform with the modifier; the platform was placed at the inducer edge;
the inducer was heated and the material under study was melted;
then the modifier was added into the molten material;
it took 0.5-1.0 min to mix the modifier and the melt; then the melt was discharged into the copper casting
mold.
The produced ingot was crushed by means of a press, the central sample of the ingot was flank-grinded and it
was studied with the help of the electron microscope Philips SEM 515 (fig. 3).

(a) (b)
FIGURE 3. Micrographes of a chip of a standard high-neodymium alloy without the modifier (a) and with the modifier (b)

Micrographes show that the surface of the modified alloy is composed of particles having smaller sizes (0.1 – 1.0
micrometers).

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 SUMMARY
The following researches have been conducted with the help of the vacuum inductive apparatus: the study of the
production process of magnetic materials with the help of the individual components melting technique; the study of
the refining of alloy and addition alloy ingots produced by means of the out-of-furnace reduction of metal fluorides;
the study of the refining of alloy and foundry alloy ingots with the addition of modifying agents and the production
of nanostructured materials.
It is demonstrated that the ingot output is sufficiently high, it equals 92.4-97.5% and it is maximal for metal
components. REE loss is in the range of 4.90-8.61 %wt. The induction refining of alloys being conducted, the total
impurity content decreases by more than a half. At the same time the even distribution of all the compounds in the
ingot is achieved.
When the modifier was used after the induction refining, the surface of the produced alloy was composed of
particles having the size of 0.1 – 1.0 micrometers.

ACKNOWLEDGMENT
This work was supported by the Federal Target Program “Research and development on priority directions of
scientific-technological complex of Russia for 2014-2020” (RFMEFI57814X0002).

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