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Production of Permanent Magnets for Magnetically Hard Alloys Using Rare-

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Article in Metallurgist · October 2019

DOI: 10.1007/s11015-019-00846-3

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DOI 10.1007/s11015-019-00846-3

Metallurgist, Vol. 63, Nos. 5-6, September, 2019 (Russian Original Nos. 5-6, May–June, 2019)

PRODUCTION OF PERMANENT MAGNETS FOR MAGNETICALLY HARD ALLOYS

USING RARE-EARTH METALS

S. S. Shumkin,1 P. A. Prokof’ev,2 and M. Yu. Semenov3 UDC 669.018.582

A requirement for improving powder metallurgy technology of alloys for permanent magnets containing
rare-earth metals based on the use of secondary resources and a replacement of rare-earth metals and fi-
ne control of the semifinished products chemical composition is demonstrated. These approaches are
realized successfully in the preparation of Nd–Fe–B system magnetically hard materials by a binary
mixture method using rare earth metal hydrides and their alloys. Analysis of the magnetic properties of
Sm–Co–Cu–Fe–Zr system permanent magnets according to the results of the primary ingot chemical
composition control minimizes production costs.

Keywords: permanent magnets, rare-earth metals, samarium-cobalt system, neodymium-iron-boron sys-

tem, powder metallurgy, secondary resources.

Permanent magnets (PM) made of powder alloys using rare-earth metals (REM) have found extensive ap-
plication in electrical engineering objects, UHF electric vacuum instruments, defectoscopes, separators, magnet-
ic systems for treating liquids, use for transferring a torsional moment, magnetic systems of acoustic converters,
magnetic systems of medical engineering, magnetic systems of fastening, fixing and positioning, and also in na-
tional consumers wears, for example in meters for water, electrical energy, gas consumption, etc.
The main problems for producing PM are connected with a lack of domestic REM, and also the volatility
of the world price for REM. In 2010–2012 there was a brief increase in the price for the main REM as a result
external economic policy the PRC, i.e., the main producer country of REM, and in 2016–2018 a worldwide
brief increase in the price of cobalt, being alongside REM a main raw material for magnetically hard materi-
als (MHM). The world producers of PM, being in a complex economic situation, in order to maintain profitabil-
ity of production and their own competitive positions in the market needed to reduce sharply the production
expenditure and introduce innovative solutions. In addition, within the Russian enterprises technology for pro-
ducing many PM has not changed markedly over the last decade.
MHM are materials whose coercive force H c is within the limits 5 ⋅10 3 −5 ⋅10 6 А/м (60–60 000 Oe),
and the maximum energy production BH max is within the limits 1–400 kJ/m 3 (1–50 МG·Oe). In addition,
contemporary MHM, containing REM, may have even better magnetic properties. In PM based on alloy of the
system Nd–Fe–B values are achieved of BH max = 451 kJ/m 3 (56.7 МG·Oe) [1], and individually taken speci-
mens of MHM for this system this value has been exceed [2].

The aim of research is development of scientific bases of resource saving technology for preparing contem-
porary MHM containing REM.

1
AO Spetsmagnit, Moscow, Russia; e-mail: shoomkin@s-magnet.ru.
2
AO Spetsmagnit, Moscow, Russia; Baikov IMET RAN, Moscow, Russia; e-mail: pav3387@yandex.ru.
3
FGBOU VO I. P. Bardin TsNIIchermet, Moscow, Russia; e-mail: semenov.m.yu@bmstu.ru.

Translated from Metallurg, Vol. 63, No. 5, pp. 37–42, May, 2019. Original article submitted November 28, 2018.

462 0026-0894/19/0506-0462 © 2019 Springer Science+Business Media, LLC

PRODUCTION OF PERMANENT MAGNETS FOR MAGNETICALLY HARD ALLOYS USING RARE-EARTH METALS 463

Materials

The Russian PM market based on neodymium (Nd) and neodymium oxide ( Nd 2O 3 ) is almost entirely sup-
plied by PRC produced magnets [3]. Production of MHM based on alloys of the Sm–Co system in the PRC is
significantly lower, and at the same time the raw material cost is higher. In addition, the advantages of MHM
based on alloys of the Nd–Fe–B system with respect to magnetic properties is balanced by the following ad-
vantages compared with alloys of the Sm–Co system: a broader working temperature range, good thermal sta-
bility, and also a lack of a tendency towards corrosion in oxidizing atmospheres and resistance to the action of
hydrogen sulfide media.
In the present work MHM have been considered containing REM based on both the Nd–Fe–B, and also
Sm–Co–Cu–Fe–Zr systems.

The Production Process for Manufacturing Permanent Magnets from Alloys Containing REM. PM of
MHM based on REM alloys cannot be performed without special equipment, which is due to the chemical and
physicochemical properties of the components entering into them.
A traditional production process for manufacturing PM by powder metallurgy methods includes the follow-
ing operations: synthesis of alloys from pure components; crushing, grinding, and fine milling; compaction in
a magnetic field (preliminary molding of powders is sometimes accomplished); sintering; heat treatment (ho-
mogenizing annealing, quenching, and tempering); machining (multiple blade, skelping, hydro-abrasive or elec-
tro-erosion cutting, diamond wheel grinding); magnetization, and monitoring of the magnetic parameters.
A feature of this production process is accomplishment of almost all operations within a vacuum, and also
use of protective and inert atmospheres. This is connected with the strong pyrophoricity of the REM used,
as a result of which it is necessary to provide protection for alloy powder and alloys from contact with an air
atmosphere.
Taking account of the development of contemporary engineering devices and expansion of the fields of ap-
plication of PM there is a constant requirement for creating MHM with increased values of coercive force and
residual induction.
A classical method for preparing high coercivity alloys includes synthesis of precision alloy in the melting
stage with increased content of heavy REM and reduced residual magnetization.
An OA Spetsmagnit device is presented in Fig. 1 for induction vacuum melting making it possible to con-
duct synthesis of precision alloys.
The main innovative solutions introduced by AO Spetsmagnit are a reduction in the requirement for expen-
sive REM, including replacement of them by cheapest analogs and introduction of technology of binary systems,
including addition to Nd–Fe–B powder of heavy REM (Tb, Dy) hydride powders including use of scrap from
components of electrical engineering objects.
In addition, in the technology for producing permanent magnets from MHM base on alloys of the Sm–Co–
Cu–Fe–Zr system in АО Spetsmagnit monitoring has been introduced for the chemical composition of the origi-
nal alloys by means of an atomic emission spectrometer with a microwave plasma [4–6]. Traditional technology
does not specify similar control operations in view of the fact that alloys of the binary system Sm–Co have been
considered and aimed at pure charge materials and a limited range of objects.
Alloys of the Sm–Co–Cu–Fe–Zr exhibit the best magnetic properties due to an optimum structure (solid so-
lution) obtained after homogenizing alloy at a temperature of about 1200°C, isothermal ageing at 800–900°C
for 4–20 h, subsequent slow cooling (about 1°C/min) to 400°C, and rapid cooling (≈ 200°C/min) to room tem-
perature.
464 S. S. SHUMKIN, P. A. PROKOF’EV, AND M. YU. SEMENOV

Fig. 1. Induction vacuum melting unit.

(a) (b)

(c) (d)

Fig. 2. Sintered semiproducts of Sm–Co–Cu–Fe–Zr alloy (a) prepared PM and MHM based on Sm–Co–Cu–Fe–Zr alloy (b); sintered
semiproducts of alloy Ni–Fe–B (c) of finished PM and PHM based on Ni–Fe–B (d).
PRODUCTION OF PERMANENT MAGNETS FOR MAGNETICALLY HARD ALLOYS USING RARE-EARTH METALS 465

Fig. 3. Typical MHM microstructure based on alloy Nd15 Fe 77 B8 (SEM) [9].

Table 1
Values of Anisotropy and Saturated Induction Field for Intermetallic Compounds
of the Type R 2 Fe14 B [7]

Intermetallic compound (alloy)

Property
Nd 2 Fe14 B Pr2 Fe14 B Dy 2 Fe14 B Tb 2 Fe14 B
На, kA/m 5600 7200 11200 16800
B s, T 1.60 1.55 0.70 0.70

Research Results and Discussion

Semiproducts of MHM and PM based on them have been obtained (Fig. 2).
The greatest values of anisotropy field properties H a , and consequently potential possibilities for improv-
ing coercive force with respect to magnetization j H c are exhibited by alloys containing dysprosium (Dy) and
especially terbium (Tb), and in this case their saturation induction Bs is less by a factor of 2.3 than for alloy
containing Nd (see Table 1). The rate of increase of j H c for magnets of these alloys is considerably higher
than the growth rate of H a , which makes it possible to synthesize MHM with a high level of hysteresis charac-
teristics. Normally this is connected with a less defective structure of boundary phases. For example for the
alloy Nd15 Fe 77 B8 introduction of one atomic percent of Dy or Tb leads correspondingly to an increase in j H c
by 260 or 480 kA/m.
The efficiency has been established of using Nd, Pr, and Dy hydrides in powder mixtures in order to prepare
alloys for permanent magnets [8]. After traditional heat treatment of (Pr, Nd) 30.5 Cu 0.2 Fe 68.3 alloy the following
magnetic properties were obtained: j H c = 950 kА/m and BH max = 331 kJ/m 3. It is apparent that the increase
achieved in hysteresis properties is connected both with features of the structure formed, and also with the high
coercivity of alloys obtained from mixtures containing hydrides. The typical microstructure of a permanent
magnet made from sintered MHM based on alloy of the Nd–Fe–B system is shown in Fig. 3.
466 S. S. SHUMKIN, P. A. PROKOF’EV, AND M. YU. SEMENOV

The microstructure is characterized by presence of grains of the main magnetic phase ( Nd 2 Fe14 B ) of the al-
loy, layers of magnetized (Nd-rich), presence of readily melting eutectics, nonmetallic inclusions (carbides, ox-
ides, borides), and also some phases based on Nd (see Fig. 3, phase NdFe 4 B4 ). Presence throughout the whole
cross section of a specimen of layers of nonmagnetic phase, isolated grains of the main magnetic phase, prevent
processes of remagnetization, connected with nucleus-formation of domains with a reverse magnetization sign.
Use of technology of binary mixtures (REM substitution) makes it possible to have a favorable effect on the ex-
tent and completeness of the boundaries of nonmagnetic intergranular phase and to optimize hysteresis charac-
teristics of an MHM based on alloy of the Ni–Fe–B system due to creating a “core-shell” structure, which is
characterized by presence of regions within a grain of the main magnetic phase of the type (R, Nd)2 Fe14 B,
where R id added heavy REM (Tb, Dy).
It is well known that replacement of part of Nd by a heavy REM such as Dy and Tb effectively increases the
value of magnetic crystallization of R 2 Fe14 B (R is REM) isotropy [10]. However, in this case there is an irre-
versible reduction in residual magnetization. On the other hand, addition of powder enriched with heavy REM
(fluoride, hydride, oxide, or nitride) during sintering of the main materials (iron) makes it possible to avoid
a strong reduction in residual magnetization [11]. It has been established that the concentration of these metals
in areas around grain boundaries makes it possible to increase the coercive force of specimens of these MHM
without markedly reducing residual magnetization [12].
In view of this some versions have been proposed for introducing these elements in the form of compounds
concentrated at grain boundaries: diffusion annealing of magnets with coatings of metallic Dy (in this case the
possibility of an increase in coercive force comprises 4–6 kOe) or use of binary mechanical mixtures. Use of
Nd, Pr, Dy hydrides is promising, although alloying of hydrides of pure REM, alloying of heavy REM alloys
(Dy and Tb) and diffusion annealing of sintered powder, on which there is spray coating of heavy REM are
expensive due to significant use of REM. The promising direction in binary technology is use of various inter-
metallic compounds based on heavy REM. All of the R 3Co compounds form in the course of peritectic trans-
formation, and in this connection their preparation in a single phase condition is difficult. REM compounds of
the R 3Co type have an orthorhombic lattice of the Fe 3C type (spatial group Pnma) and maximum REM content
among compounds of the type Ri M j [13, 14], where M is transition metal, and R is REM.
The possibility of using hydrated compounds R 3 (Co, Cu) as additives to any Ni–Fe–B powder mixtures in
order to improve hysteresis properties of permanent magnets has been demonstrated in [15]. Use of REM
hydrides containing copper also leads to a significant increase in hysteresis characteristics with a reduction in
Dy content due to adding Cu [16]. Use of compounds containing Co and Cu simultaneously simplifies introduc-
tion of REM alloy. It is well known that alloying with Co leads to an increase in Curie temperature for the com-
pound R 2 (Fe, Co)14 B [17], and also makes it possible to control the thermal induction coefficient. Therefore,
introduction of Co and Cu into alloy may facilitate achievement of the required level of hysteresis properties for
magnets. Introduction of R 3 (Co, Cu) compounds, were R is heavy REM (Tb or Dy in the form of hydrides) into
powder of the main alloy makes it possible to control grain boundary diffusion processes and thereby increase
hysteresis properties [17]. Also, addition of heavy REM in the grinding stage does not lead to a strong reduction
of residual magnetization.
Use of these approaches for alloying material with REM hydrides and alloys based on them has also made it
possible to reduce the cost of charge materials due to saving up to 3.8 wt.% Tb. Use of technology for control-
ling grain boundary diffusion processes (binary mixture technology) makes it possible to reduce the requirement
for expensive heavy REM (Tb, Dy) with loss of residual magnetization.
Greater thermal and corrosion stability is exhibited by alloy of the Sm–Co–Cu–Fe–Zr system, КS25
(GOSТ 21559–76). After treatment within it there is formation of a cellular structure, i.e., ordered precipi-
tates of rhombohedral phase Sm 2Co17 (or “2:17 R” phase) within a matrix of hexagonal SmCo 5 phase (or “1:5”
PRODUCTION OF PERMANENT MAGNETS FOR MAGNETICALLY HARD ALLOYS USING RARE-EARTH METALS 467

(a) (b)

(c) (d)

Fig. 4. TEM pictures of alloy of the Sm–Co–Cu–Fe–Zr system after isothermal exposure at 1108 K and slow cooling to 673 K:
(a) microstructure with cells of Sm 2Co 2 (2.17 R) alloy and cell boundaries of SmCo 5 (1:5) phase (cell size 150–200 nm);
(b) dark field image of Z-phase passing through many cells; (c) secondary Zr–Fe–Co, Sm 2O 5 phases; (d) enriched copper inclu-
sions (Cu rich).

phase) (Fig. 4a). Cells of the Sm 2Co12 phase formed have a size of the order of 10 − 7 m, and the SmCo 5 wall
surrounding them has a thickness of the order of 10 −8 m. The cellular structure is additionally lamellar, formed
by precipitates if hexagonal Sm 2Co17 phase, which is often designated as Z-phase (see Fig. 4b). The thickness
of Z-phase precipitates is of several inter-atomic distances, and the lattice spacing of Z-phase is much greater
than the lattice spacing of the matrix. Layered (lamellar) precipitates are coherent with rhombohedral Sm 2Co17
phase, twinning axes are parallel to precipitates, and the twinning width is the actual distance between two
Z-phase plates. The Z–Fe‒Co phase (see Fig. 4a) has the composition 23Zr–17Fe–60Co, аt.%, and a crystal lat-
tice structure Zr6 (Fe, Co)23 .
Based on the dependences indicated for magnetic properties on chemical composition of alloys of the Sm–
Co–Cu–Fe–Zr system introduction of monitoring operations for chemical composition of an original ingot have
made in possible to accomplish quality control for the whole production process without previous use of addi-
tional certification of the MHM obtained [5].
468 S. S. SHUMKIN, P. A. PROKOF’EV, AND M. YU. SEMENOV

CONCLUSIONS

1. A requirement has been established for changes in the traditional manufacturing technology for perma-
nent magnets made from MHM based on REM alloys: use of secondary raw material and also introduction of
binary mixture technology (REM replacement) and analysis of the semiproduct chemical composition.

2. Existing traditional technology for synthesizing precision high-coercivity alloy of the Ni–Fe–B system is
not profitable due to use of expensive starting materials, i.e., heavy REM (Tb, Dy), providing a highly coercive
condition. In OA Spetsmagnit technology has been successfully introduced for producing PM of MHM based
on alloys of the Ni–Fe–B system by a method of binary mixing using hydrides of pure REM and alloys based on
them, which corresponds to the contemporary world trends in the industry.

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