DOI 10.

1007/s10717-020-00226-3
Glass and Ceramics, Vol. 77, Nos. 1 – 2, May, 2020 (Russian Original, Nos. 1 – 2, January – February, 2020)

UDC 666.3.016:666.3-134.1

STRUCTURE AND PHASE FORMATION MECHANISM FOR HOLLOW

SPHERES OF ALUMINUM-MAGNESIA SPINEL IN OBTAINING POWDERS
BY CHEMICAL DISPERSION OF ALUMINUM-MAGNESIUM ALLOYS

A. A. Vasin,1, 2 V. P. Tarasovskii,1, 3 A. V. Smirnov,1, 4 A. Yu. Omarov,1, 5

A. V. Reznichenko,1, 6 and T. Yu. Skakova1, 7

Translated from Steklo i Keramika, No. 1, pp. 3 – 9, January, 2020.

The results of an investigation of the processes underlying the formation of hollow aluminum-magnesia
microspheres by chemical dispersion of magnesium-aluminum alloys with heightened content of magnesium
are reported. The mechanism of the formation of microspheres and the factors determining their structural fea-
tures and sizes are elaborated. It is shown that magnesium additives influence the formation of the structure of
hollow microspheres and their number. The fine structure of the powders before and after heat-treatment was
studied.

Key words: chemical dispersion, aluminum-magnesia spinel, raw materials, powders, hollow microspheres,
ceramics, highly porous materials, thermal insulation, refractories.

One of the important problems of ceramic material sci-
ence is the development of a ceramic combining low-density
and high-performance. A great deal of attention is now being
devoted to materials containing aluminum-magnesium
spinel. Aluminum-magnesium spinel counteracts the pene-
tration and action of water, mineral acids, alkaline melts, car-
bon, many metals, vacuum, and metallurgical slags.
In the manufacturing technology for products made from
such material the spinel synthesis stage, to which a great deal
of attention is devoted, is a separate technological operation.
The simplification or elimination of this stage, reduction of
the role of purity and dispersity of the individual raw-mate-
rial components and elimination of the need for their careful
matching, and the optional use of different media during
heat-treatment are very promising and unsolved problems.
The experience gained in the manufacture of ceramic
materials shows that the problem of reducing product mass
while maintaining product performance can be solved by
1
Moscow Polytechnic University (Moscow Polytech), Moscow,
Russia.
2
E-mail: vasin8989@gmail.com.
3 powders and porous ceramic material from chemically dis-
E-mail: tarasvp@mail.ru.
4
E-mail: smirnoff-andrey2009@yandex.ru.
5
E-mail: asif.omarov@yandex.ru.
6 der included the following stages: chemical dispersion of
E-mail: 250871rav@gmail.com.
7
E-mail: tanya.skakova@mail.ru.
using hollow microspheres. By using such hollow micro-
spheres it is possible to control the structure of the pore
space, reduce the density, increase thermal stability, and im-
prove the refractory and heat insulation properties of the ma-
terials. The conventional methods used to obtain sinterable
powders with these characteristics are complicated, expen-
sive, and low-tech.
Today, there exist technologies for obtaining microsphe-
res and microballoons made from Al2O3 and SiO2 but a
method does not exist for obtaining microspheres or micro-
balloons of micron and sub-micron sizes from alumi-
num-magnesium spinel with a large yield of the finished
product. This is what determines the timeliness of the work
performed by the present authors, which is devoted to the de-
velopment of a fundamentally new, technologically simple,
and energy-conserving scheme for producing hollow micro-
spheres of aluminum-magnesium spinel.
The main scientific groundwork for this investigation is a
method which we developed for chemical dispersion of alu-
minum-magnesium alloys, as described in [1 – 8]. In these
works a technological process was developed for obtaining
persed aluminum-magnesium alloys with different magne-
sium content. The technological process of fabricating pow-
chips of the indicated alloys in a water solution of an alkali,

3
0361-7610/20/0102-0003 © 2020 Springer Science+Business Media, LLC
4 A. A. Vasin et al.

lines) 3 of the alloy 1 and at locations where dislocation

lines emerge at the surface of the grains 4 (Fig. 1a ).
Since the rate of such grain-boundary corrosion is
largely determined by the volumetric fraction of the
smallest grains, the alkali should most actively eat away
alloys with the lowest magnesium content because the
amount of the grown intermetallic b-phase is smaller.
a b If the rate of grain-boundary corrosion (Fig. 1b ) is
Fig. 1. Schematic representation of the process of chemical dispersion of the highest along the surface of fine grains (e, f, m, n) in op-
alloy Al–Mg by a water solution of the alkali NaOH: a: 1 ) plate of the dis- posite directions (1, 2, 3, 4 and 6, 5, 4; 11, 10, 9 and 7, 8,
persed material; 2 ) alloy grain; 3 ) intergrain boundaries (solid lines); 9), then small grains and the set of large grains (a, d) as-
4 ) zones of egress of dislocation lines on the surface of grains; dashed line sociated with the low-energy planar boundary will be
(- - - - - -) – spreading and coating of the alloy surface by the alkaline solu- dispersed out of the alloy. The development of grain-
tion; b ) direction of propagation of corrosion along intergrain boundaries boundary corrosion in opposite directions 7, 8, 9 and 11,
(®®®®); e, f, m, n, p, k, z) fine grains; a, b, c, d) large grains; 1, 2, 3, 4 – 6, 10, 9 as well as its unilateral propagation in the direc-
5, 4; 11, 10, 14, 9 – 7, 8, 9) opposite directions of propagation of corrosion
tions 18, 16, 17, 14 and 12, 13, 14 and 15, 16 will result
from the surface into the interior of the alloy; 12, 13, 14; 12, 17, 14; 15, 16,
17; 18, 16) unidirectional propagation of corrosion from the surface into the in precipitation of large grains (c, b) as well as groups of
interior of the alloy. small grains (z, k, p) in the reaction volume.
The formed particles of aluminum-magnesium alloy
(grains) are passivated along the surface of the metal-
washing-off of the precipitate by means of decantation, frac- hydroxide shell, which is a kind of micro-encapsulation of
tionation, and drying and heat-treatment of the powder. the alloy particles and prevents their subsequent destruction.
The results of the investigations show that the obtained
powders contain a finely dispersed phase consisting of sub- STUDY OF THE FINE STRUCTURE OF POWDERS
micron- and micron-size crystals and agglomerates formed BEFORE AND AFTER HEAT-TREATMENT
by the finely dispersed phase, inter-agglomerate pores, and
hollow rounded granules. The formation of hollow rounded It was determined by comparing powders obtained by
particles was recorded in all samples [4 – 8]. As expected, means of chemical dispersion of the alloys AMg6, AMg12,
increasing the mass fraction of magnesium in the initial alloy and AMg20 that the yield of spheroidized particles signifi-
resulted in higher yield of aluminum-magnesium spinel. cantly increases and the size of the particles decrease with
The discovery of spheroidized particles of aluminum- increasing magnesium content. The size range of the sphe-
magnesium spinel with sizes ranging from 1 mm, in the struc- roidized particles for powder made from the alloy AMg20 is
ture of the powder particles after heat-treatment and in the 1 – 20 mm. The powder obtained from this alloy consists pre-
structure of the ceramic material became one of the most dominantly of such particles. The phase composition of the
interesting results of our studies. Rounded granules were powder obtained by chemical dispersion of the alloy AMg20
encountered more frequently with increasing magnesium is represented by the following phases: Al(OH)3 — gibbsite,
content. Al(OH)3 — bayerite, AlO(OH) — g-boehmite,
In the present article we report the results of an investi- Mg2Al(OH)6(CO3)0.5H2O, Al3Mg2. The phase Al3Mg2 was
gation of the processes underlying the formation of hollow found in the powder; its presence is explained by incomplete
aluminum-magnesia spheroidized particles (microspheres). destruction and entry into reaction of the particles of the
The mechanism of the formation of spheres and the factors intermetallic phase because of the passivation of their sur-
determining their structural features and sizes are elaborated. face.
Aside from the large number of spheroidized particles,
MODEL OF THE PROCESS OF CHEMICAL the powder contains submicron- and micron-size crystalline
DISPERSION OF ALUMINUM-MAGNESIUM ALLOY components, independent as well as united into individual
isometric agglomerates. The size of the agglomerates varies
The chemical dispersion of aluminum-magnesium alloys from 5 to 20 mm. A finally dispersed phase in the form of
in NaOH comprises a process of their destruction the pur- submicron and micron crystals consisting of different hy-
pose of which is to comminute the material by means of a re- drated forms is distributed along the surface of the rounded
action resulting in the formation of liquid and gaseous pro- granules. As in the case described in [4], rounded granules
ducts and dispersed particles. As a result of the interaction of possess a layered structure consisting of spherical nuclei,
aluminum-magnesium alloy with a water solution of an al- probably consisting of unreacted alloy and alternating shells
kali, adsorption of the active Na+ ions and OH– groups oc- consisting of different hydrated forms of aluminum. The sur-
curs along the surface of the alloy. The reaction between face relief of the spheroidized particles can be characterized
these reagents is more intense along grain boundaries (solid not only as stepped (as a result of predominant corrosion of
Structure and Phase Formation Mechanism for Hollow Spheres of Aluminum-Magnesia Spinel
12 mm
Fig. 2. Appearance of a spheroidized particle: 1 ) groove of chemi-
cal etching; 2 ) plate-shaped particles; 3 ) stepped relief of the sur-
face; 4 ) ‘needle’ surface relief of spheroidized particle.
the b-phase of the alloy) but also ‘needle-shaped’ (Fig. 2),
which is a result of chemical etching by the alkali along the
high-energy intergrain boundaries. The manifestation of
spheroidization is associated with the minimization of the
surface energy of particles in the course of alkaline corro-
sion. The joining together of such particles as a result of
sticking along the surface MeOH-phase was encountered in
the powder.
The needle structure of their surface is explained by the
formation of needle crystals from a supersaturated sodium
aluminate solution (NaAlO2(solution) ® Al(OH)3(cryst) ). In this
case the centers of crystallization (centers of crystal growth)
could be surface structures of particles with imperfect orien-
Fig. 3. Appearance of the particles of powder) a product of chemical dispersion of the alloy
AMg20 (Al–Mg (20% by weight) after heat-treatment at 1090°C for 1 h.
5
tation (micro-protuberances, micro-indentations, intergrain
boundaries), possessing excess surface energy. In this case
small grooves of chemical etching c corresponding to inden-
tations and crests are formed. As we can see in Fig. 2, the
particles of the finely dispersed phase are represented by iso-
metric particles as individuals as well as joined into agglom-
erates. Plate-shaped particles ranging in size from 0.2 to
3.0 mm are observed.
After heat-treatment at 1090°C (determined by means of
differential thermal analysis, in 1 h) an increase of the frac-
tion of fine-crystalline binder, represented by a mixture of
the crystals a-Al2O3 and Al2MgO4 with nearly isometri-
cally-shaped particles and size from 100 to 300 nm, were re-
corded in the investigated powder by means of x-ray phase
analysis. As a result of heat-treatment the fine crystalline
binder detaches from the surface of rounded particles, which
is a consequence of the different values of their CLTE. Sin-
tering of the finely dispersed phase to the surface of the
rounded granules was observed in rare cases.
After heat-treatment of the powder the spheroidized par-
ticles transform into hollow spheres (Fig. 3). As a result of
previous studies [4, 5] a definite picture of the mechanism of
the formation of the microspheres took shape.
The mechanism of the formation of hollow microspheres
was elaborated on the basis of an investigation of powders
made from the alloy AMg20, which was subjected to
heat-treatment at different temperatures (800 – 1090°C). The
structure and phase components of the spheroidized particles
obtained as a result of chemical dispersion are shown sche-
matically in Fig. 4.
6 A. A. Vasin et al.
5
4
3 2¢
2 5¢
1
Fig. 4. Structure and phase composition of rounded granules ob-
tained as a result of chemical dispersion: 1 ) nucleus, 0.2 – 13.0 mm
in diameter (metallic phase) unreacted aluminum alloy); 2 ) boeh-
mite (layer 0.1 – 3.0 mm); 3 ) bayerite (0.2 – 6.0 mm); 4 ) amorphous
hydrate phase (Al2O3–MgO) × nH2O (10 – 12 mm); 5 ) submicron
particles of bayerite.
In the course of heat-treatment, spinel crystals 3 ¢ are
synthesized from the hydrate phase (Fig. 5), and a-Al2O3
crystals 7 are synthesized from bayerite particles 5. In ad-
dition, the shells from boehmite 2 and fine-crystalline
bayerite 3 join together and transform into a crystalline phase
a-Al2O3 2 ¢.
The heat-treatment temperature of the powder product
(1090°C) is 1.65 – 1.68 times higher than the melting tem-
perature of Al (660°C) and Mg (650°C). At this temperature
aluminum and magnesium in the makeup of the nucleus 1
(see Fig. 5) coexist in the form of heated melt coated by an
oxide film with thickness, according to data obtained by dif-
ferent authors, 10 – 1 – 10 – 4 mm [9 – 11]. It is also known
[12] that as a result of the presence of magnesium in the alloy
the permeability of the oxide film for molecules increases.
It should be noted that crystals of a-Al2O3 and spinel are
arranged in a thin layer 5 ¢ on the inner surface of the shell 2 ¢
as well as in the interior of its intercrystalline pores.
The process of condensation of the crystals of a-Al2O3
and spinel is described as follows:
Al(melt) ® Al2O(vapor) ® AlO(vapor) ® Al2O3(crystals); (1)
Mg(melt) ® Mg(vapor) + Al2O(vapor) + AlO(vapor) ®
Al2MgO4(crystals) . (2)
7
6 3¢
4¢ 1
Fig. 6. Evolutionary transformations occurring in the structure of
microspheres with increasing heat-treatment temperature of the
powder.
The process of whisker formation in the direction of dif-
fusion of molecules of Mg and suboxide vapor is displayed
graphically in Fig. 6.
In the reactions (1) and (2) the role of the oxidizer is
played by the atomic oxygen formed as a result of thermal
dissociation of the molecules of oxygen in air (O2 ® O% +
O%) in the indicated temperature interval. In the sequence of
chemical transformations (1) the degree of oxidation of alu-
minum increases (AlO0.5 ® AlO ® AlO1.5 ) and a crystal
phase corresponding to its maximum degree of oxidation
precipitates.
In the course of the reactions (2) simultaneous interac-
tion of the magnesium vapor molecules can occur with lower
suboxide Al2O vapor molecules and with the molecules of
suboxide vapor with a higher degree of oxidation of alumi-
num AlO. In addition the condensation of spinel crystals will
be observed when the stoichiometric ratio of the atoms is
reached Al : Mg : O (2 : 1 : 4). Thus, the formation of the
crystalline phases a-Al2O3 and Al2MgO4 occurs by means
of a sequence of gas transport reactions in the chains (1) and
(2). Excess magnesium is concentrated in the form of an oxi-
de on the surface. Ultimately, the complete evaporation of
the metallic nucleus 1 (see Fig. 5) followed by condensation
of its vapors on the inner surface of the shell 2 ¢, in the inte-
rior of its intercrystalline pores, and beyond the limits in the
form of crystals result in the formation of a closed cavity.
Fig. 5. Diagram of the structure of hollow
rounded granules, formed during the heat-
treatment process (1090°C, air, 1 h): 1 ) nu-
cleus; 2 ¢ ) crystalline shell from a-Al2O3;
3 ¢ ) Al2MgO4 crystals; 4 ¢ ) molecules of Mg
vapor and Al suboxides; 5 ¢ ) condensed layer
of a-Al2O3 and Al2MgO4; 6 ) a-Al2O3 whis-
kers; – – ®) diffusion direction of molecules
of Mg and Al suboxide vapor; 7 ) MgO crys-
tals.
Structure and Phase Formation Mechanism for Hollow Spheres of Aluminum-Magnesia Spinel
a b
Fig. 7. Study of the internal structure of the cavity of a microsphere: a) spheroidized particle before heat-treatment (cut); b ) hollow micro-
sphere after heat-treatment; c) cut of a hollow microsphere after heat-treatment.
To study after heat-treatment the interior structure of a
spheroidized particle and the cavity of a microsphere using a
FEI VERSA scanning electron microscope, a focused di-
rected ion beam was used to prepare a cut (Fig. 7); an x-ray
spectral analysis attachment was used to determine the com-
position.
Aluminum-magnesium spinel starts to form at 800°C,
and the solid solutions start to form in the temperature range
1000 – 1200°C. The study of the powder showed that in the
process of treatment the shell acquires a structure consisting
of crystals of the solid interstitial solution of a-Al2O3 in the
crystal lattice of spinel. Probably, when the sintering temper-
ature reaches 1090°C the phases MgO and Al2O3, which are
in a free state in the powder, completely transformed into
solid interstitial solutions based on spinel. As a result of
heat-treatment at 1400°C the powder comprises a compact
with a developed system of contacts consisting of hollow
microspheres with a dense crystalline shell made of crystals
of spinel Al2MgO4 and fine crystalline binder, represented
by particles of spinel with non-stoichiometric composition
with a smooth isometric form. The spheroidized particles
(microspheres) are hollow and their shell is high-density.
Recrystallization growth of spinel, comprising a fine-crystal-
line binder, was not recorded at the heat-treatment tempe-
rature.
CONCLUSIONS
The mechanism explaining the influence of magnesium
in aluminum-magnesium alloys on the process of formation
of a powder structure was determined. It consists in the fact
that in the process of chemical dispersion selective
grain-boundary corrosion of the intermetallic phase occurs,
and the amount of this phase increases with increasing con-
tent of magnesium in the initial alloy. The particles formed as
a result of dispersion of the alloy are passivated on the sur-
face of the metal hydroxide shell, which results in their mi-
cro-encapsulation. Electronic microscopy shows a large
number of rounded granules to be present in the powder and
the number of the granules increases predictably (up to 70%
of the volume) with increasing content of magnesium.
7
c
A mechanism was proposed for the structural-phase evo-
lution of the powder in the heat-treatment process, according
to which complete evaporation of the metal kernel of the
capsule occurs and is followed by condensation of its vapors
on the inner surface of the shell, in the interior of its inter-
crystalline pores, and in the form of crystals outside the shell,
which results in the formation of a closed cavity. As a result
of heat-treatment such capsules transform into hollow
microspheres. In the studied microstructure of the new pow-
der material obtained as result of heat-treatment, the powder
comprises a mixture of hollow microspheres with a dense
crystalline shell comprised of crystals of spinel Al2MgO4 and
fine-crystalline binder, represented by particles of spinel with
nonstoichiometric composition and a smooth isometric
shape.
The hollow microspheres comprise a promising base for
creating ceramic materials with porosity > 90% and unique
operational properties. For this reason, an important and
promising direction of further work could be the develop-
ment, based on the method of chemical dispersion, of a tech-
nology for high porosity, ultralight, heat-insulating material
consisting of spinel microspheres bound by a thin interlayer
of a finely dispersed phase of a spinel nature.
This work was supported by the Ministry of Science and
Higher Education of the Russian Federation under Presiden-
tial Grant No. MK-1449.2019.8 for the subject ‘Obtaining,
studying, and applying hollow microspheres of aluminum-
magnesium spinel as an initial powder raw material for the
production of high-performance ceramic’ using equipment
from the Collective Use Center at Moscow Polytech.
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