BHT 2016 Technische Universitt Bergakademie Freiberg

11 Freiberg St. Petersburger Kolloquium junger Wissenschaftler

THE METALLOTHERMIC PROCESS RESEARCH OF

MAGNESIUM-YTTRIUM MASTER ALLOYS
SAVCHENKOV S.A., BAZHIN V.Y.
Saint-Petersburg Mining University, Russia

Abstract
In the article the prospects of using of yttrium in the systems of alloying and modification of
magnesium alloys are discussed. It was found that the most effective way for alloying is using of
master alloys derived by metallothermic reduction of salts containing yttrium. For the experiments
focused on obtaining master alloys, the thermodynamic probability of the recovery process of the
compounds of yttrium is considered. The thermodynamic probability metallothermic reduction was
investigated by using computer program HSC. The microstructure and components process of the
master alloy were investigated by optical microscopy and X-ray diffraction. The results show that the
master alloy is composed of Mg24Y5 Mg2Y and metallothermic reduction method can be used to
fabricate Mg-Y master alloy. The proposed method of metallothermic obtaining master alloys based
on magnesium under controlled temperature is the most promising for the treatment of industrial
waste containing yttrium.

Keywords
Mg-REM, Mg-Y, master alloys; metallothermic reduction.

1 Introduction
Cast magnesium alloys have gained more popularity in recent years due to their ability to maintain
high strengths at light weights. Magnesium possesses unique properties that can open the door to
important markets for structural applications and has gained widespread use in automotive
components [1]. Currently the increased attention is paid to the rare-earth metals (REM) and
intermetallic compounds. It is known that the REM use as alloying and modifying additives allows
to significantly increase the strength of magnesium alloys at room and elevated temperatures.
Research in the field of light alloys is currently being focused on the improving the existing and
developing new REM alloys through the development of technologies for the production of ultrafine
powders of metals and nanostructured compounds. There are some achievements in the creation of
new construction materials and methods of their treatment in the aircraft industry, rocket production,
mechanical engineering. Therefore, the areas of their applications have become wider: the product
resource for various purposes like aviation, space, mechanical engineering and other industries, has
increased 3-5 times.
A typical practice involves the addition of MgY grain refiner into molten magnesium on its way to
the casting station. The uniform, fine, equiaxed grain structure thus obtained not only yields superior
mechanical properties but also provides alloy homogeneity. The MgY master alloys are produced
commercially by a melt reaction method that which involves adding pure rare earth metals to molten
magnesium. However, pure metals in particular, are expensive compounds which add greatly to the
raw material and alloys costs. But there is methods of synthesis of magnesium master alloys, which
are hardenable with refractory micrometric dimensions particles of yttrium, can be carried out by
vacuum metallothermic reduction of yttrium. As a result of chemical interaction in the melt under
certain technological parameters the microscale particles of intermetallic phases are formed [2].

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11 Freiberg St. Petersburger Kolloquium junger Wissenschaftler

Hence, the present work was undertaken to replace pure yttrium with Y2O3, YF3, YCl3 in the
production of MgY grain refiners. Metallotermic reduction processing has received much research
interest in recent times for materials synthesis Mg - based with transition and rare metals. This method
is a very promising preparation way for many materials because it is fast, energy efficient and does
not suffer from the disadvantages of the classical preparation technique. In this paper, a novel MgY
master alloy is prepared using a melt reaction method by metallotermic reduction synthesis. Since the
price of the raw materials is low and the technology is simple, the processing technique appears to
reduce the cost of the master alloy. The results obtained seem to be very interesting and stimulate
further research in this direction.

2 Thermodynamic probability
On the first stage of theoretical studies the thermodynamic evaluation of the recovery of yttrium from
its oxide, fluoride and chloride was carried out . In the research the software package HSC Chemistry
6 was used [3]. The thermodynamic evaluation of the magnesium-thermal recovery of yttrium from
its oxide, fluoride and chloride according to the reactions:
1/2Y2O3+3/2Mg=Y+3/2MgO
YF3+3/2Mg = Y + 3/2MgF2
YCl3+3/2Mg=Y+3/2MgCl2
The results show (fig. 1) that the total flow of these reactions left to right is impossible.

80
70
60
50
G, kJ

40 oxide

30 fluoride
chloride
20
10
0
0 200 400 600 800 1000 1200
()

Fig. 1: Constrain of Gibbs energy on temperature

Meanwhile, the interaction of Y2O3, YF3, YCl3 with Mg with the formation of intermetallics will
allow to carry out metallothermic reactions. In this case, there is a shift of metallothermic reaction
towards formation of intermetallic compound. The system magnesiumyttrium (fig. 2) is
characterized by the formation of three compounds: Mg24Y5, Mg2Y and MgY [4,5].
The optimized parameters for the Mg-Y system published in the scientific work of the authors:
Mohammad Mezbahul-Islam, Ahmad Omar Mostafa and MamounMedraj [4]. All the calculations
show very good agreement with the available experimental data. The enthalpies and entropies of
formation of the intermetallic compounds are listed in Table 1.

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11 Freiberg St. Petersburger Kolloquium junger Wissenschaftler

Fig. 2: Phase diagram Mg-Y

Table 1: Enthalpies of formation of the Mg-Y intermetallic compounds

Compound Enthalpies of formation Entropies of formation Ref.
(kJ/mole.atom) (kJ/mole.atom.K)
Mg24Y5 () -5.8 0 [4]
-7.5 0.4 [6]
-6.1 [7]
-5.84 [8]
Mg2Y () -8.8 -0.66 [4]
-12.0 1.3 [6]
-9.17 [8]
-8.6 [9,10]
MgY () -10.7 -1.26 [4]
-30.3 [7]
-10.64 [8]
-10.2 [9]

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11 Freiberg St. Petersburger Kolloquium junger Wissenschaftler

3 Experimental procedure
Mg-Y master alloy was prepared in the laboratory by the metallotermic reduction synthesis method.
Fig.3 shows a schematic illustration of the experimental equipment. Commercial pure NaCl, CaCl2,
CaF2 concentrate of rare earth metals and commercial pure Mg (99.8% purity) were used as raw
materials. The required amount of these materials was well mixed and compressed to form pellet
10mm in thickness and 11mm in diameter under appropriate pressure. The samples were then placed
in blacklead crucible with magnesium the center of the electric resistance furnace and the reaction
was carried out under the protection of high purity Ar (99.9%). An thermal couple was used for
temperature measurement. Electric resistance furnace heated to a designed temperature (800850C)
and kept at this temperature for 60-90min. Xray diffraction was used to identify the phases of the
specimen. The molten salt was finally decanted, the dross was skimmed off and the melt was stirred
thoroughly to rejuvenate the settled particles before it was cast into metal and mould.

Fig. 3: Schematic view of setup (equipment) for synthesis master alloys: 1 - electric pit-type heating furnace;
2 - leak-free; 3- luting; 4 - glass reactor; 5 - internal thermocouple;6 termocouple furnance; 7- motor-
generator set 8 - pid controller; 9 - control pulpit; 10 - vacuum pump; 11 - CO2 bulb

4 Results and discussion

The YF3 magnesium reduction result is an ingot with an yttrium uniform (table 2).The obtained results
are consistent with the data for thermodynamic research. When using as the reducing agent
magnesium these results indicate that a satisfactory distribution of yttrium in the master alloys.
Structural analysis showed that the resulting master alloy is a coarse structure of the solid solution
with distribution across the whole field of intermetallics.
The influence of temperature and holding time have been researched during recovery of yttrium from
their fluorides to the formation of intermetallic compounds. The data has been obtained indicate that
the process for magnesium reduction of the fluoride is characterized by formation of intermetallic
compounds Mg24Y5 and Mg2Y.

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Table 2: The results of the process for magnesium reduction of yttrium

No. Mg : YF3 in Temperature Dwell Recognize Winning Y, %
experiment mix material (), time, min phase
1 1:0,3 800 90 Mg24Y5 59,4
2 1:0,3 850 90 Mg24Y5 58,7
Mg2Y
3 1:0,3 850 60 Mg24Y5 61,4
4 1:0,3 800 60 Mg24Y5 58,2

5 Conclussion
Thermodynamic analysis of the miniterminal recovery of yttrium and neodymium from their
compounds showed that the occurrence of these reactions from left to right is possible only under
condition of formation of intermetallic compounds.
The proposed method of metallothermic obtaining alloys based on magnesium under conditions of
controlled temperature regimes is promising for further research.
This method can be applied in metallothermic recovery of rare earth metals from low graderaw
materials. In particular: the waste of fosfogipsum production; the waste of alumina production red
mud, where the yttrium content is up 300-400 g/t; the ash and slag wastes with the yttrium content
about 75 mg/kg.
This method of obtaining master alloys is the most versatile and economical in comparison with all
known methods.

References
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Springer, 2006.
[2] Mirza, F. A., and D. L. Chen. "Fatigue of rareearth containing magnesium alloys: a review."
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[3] Roine A. HSC 6.0 Chemistry. Chemical reactions and Equilibrium software with extensive
thermochemical database and Flowsheet simulation/ . Roine// Pori: Outokumpu research
Oy. - 2006. - 448 pp.
[4] Mezbahul-Islam, Mohammad, Ahmad Omar Mostafa, and Mamoun Medraj. "Essential
magnesium alloys binary phase diagrams and their thermochemical data." Journal of
Materials, 2014.
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