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T–x–y Diagram of MgO–SiO2–Al2O3 System: Microstructure Design

Article  in  Russian Journal of Inorganic Chemistry · August 2018

DOI: 10.1134/S0036023618080132

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ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2018, Vol. 63, No. 8, pp. 1087–1091. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © V.I. Lutsyk, A.E. Zelenaya, 2018, published in Zhurnal Neorganicheskoi Khimii, 2018, Vol. 63, No. 8, pp. 1050–1055.

PHYSICOCHEMICAL ANALYSIS
OF INORGANIC SYSTEMS

Т–х–y Diagram of MgO–SiO2–Al2O3 System:

Microstructure Design
V. I. Lutsyka, * and A. E. Zelenayaa
aInstitute of Physical Materials Science, Siberian Branch, Russian Academy of Sciences,
Ulan-Ude, Buryat Republic, 670047 Russia
*e-mail: vluts@ipms.bscnet.ru
Received June 1, 2017

Abstract⎯A computer model of the T–x–y diagram of MgO–SiO2–Al2O3 system is used to show the possi-
bility of analysis of its microstructure constitution in terms of competition between primary and eutectic crys-
tals by means of vertical mass balance diagrams calculated for a given centroid over the whole temperature
range. The usefulness of horizontal mass balance diagrams is considered for studying phase relations at a fixed
temperature along the chosen isopleth. Mass balances were used to determine the crystallization path at the
quasi-peritectic liquidus point with the invariant reaction L + Al2O3 = 3Al2O3 ⋅ 2SiO2 + MgO ⋅ Al2O3, whose
composition was taken into account in giving a rationale to corundum armor element technology.

DOI: 10.1134/S0036023618080132

Manufacturing of refractory oxide ceramics meets
some difficulties due to the need to use of high tem-
peratures. The MgO–SiO2–Al2O3 (А–В–С) system
has a wide range of practical applications in technolo-
gies of ceramic and glass-ceramic materials, and it is
used in the study and description of some (forsterite,
periclase, spinel, corundum, and mullite) refractories
[1]. The compounds of this system, such as forsterite
(2MgO ⋅ SiO2), cordierite (2MgO ⋅ 2Al2O3 ⋅ 5SiO2),
and aluminomagnesial spinal (MgO ⋅ Al2O3), have
impressive electrical insulation properties and show
promise for the production of heat-resistant ceramics
[2–5].
Thermodynamic analytical methods when used to
study ceramic systems are directed to solve applied
problems involving calculations of thermodynamic
and thermophysical properties [6, 7]. However, these
methods do not make it possible to restore the com-
plete structure of phase diagrams, and their visualiza-
tion is, as a rule, confined to liquidus surface projec-
tions and equal-value line projections. The assembly
of spatial models from phase fields does make it possi-
ble to obtain a complete phase diagram model and can
serve for a materials scientist as a tool for gaining infor-
mation on the steps of the crystallization process and
the formation of microstructural constituents [8–11].
Alloy microstructure analysis in terms of the com-
petitiveness of crystals. A computer phase diagram
model helps one to elucidate concentration fields with
competitive participation of primary crystals (1) and
eutectic (е) crystals in a quasi-peritectic (Q) or peri-
tectic (Р) invariant reaction. Let us consider the con-
centration field СeCR3QeQC, which adjoins the com-
ponent Al2O3 = C (Fig. 1a). In this field, three phase
reactions occur: primary reaction L1 → C1, monovar-
iant eutectic reaction L → Ce + R3e, and invariant
quasi-peritectic reaction LQ4 + C → R3Q4 + R4Q4. The
quasi-peritectic invariant reaction involves both pri-
mary crystals С1, and secondary eutectic crystals Се. It
should be kept in mind that eutectic crystals Се have
priority of participation in the i invariant reaction due
to their fineness. Depending on the fraction amount of
the eutectic crystals, these crystals will either be com-
pletely consumed in the invariant reaction so that only
primary crystals will remain in excess, or both types of
crystals will remain. For analyzing the microstructure
to be formed, the field СeCR3QeQC is divided by the
line СQe into two fragments. In the fragment СQCQe
eutectic primary crystals are in excess relative to the
invariant reaction, while in the field СQeeCR3, both
primary and eutectic crystals are. On the line СQe the
eutectic crystals will be completely consumed in the
invariant reaction and the amount of primary crystals
will remain unchanged [12–14]. Analytically, this is
confirmed by vertical mass balance diagrams calcu-
lated for a given centroid over the entire range of tem-
peratures; in so doing, one will take into account not
only quantitative ratios for every of the coexisting
phases but also the fractions of their microstructure
constituents (if existing) [15]. Therefore, the calcula-
tion of vertical mass balance diagrams is accompanied
with tables that present phase weight fractions for
every phase field before and after the relevant reaction
is over. One should keep in mind that an individual

1087
1088 LUTSYK, ZELENAYA

qc: 1803
R6
(а) P (b)
Q4 CI L

r
R3 qCR3: 1684.4
Q e s2
G3 CI
eCR3 L R3e
QC
G1
R5 G2 Ce Ce
L Q4
CI R4Q4 R3Q4 R3e hCR3R4: 1578
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

R4 s1 eCR4 C CI R4Q4 R3Q4 R3e

(c)
:0
qc: 1892.4

CI
L (d)
r qc: 1828.2
qCR3: 1811.2 L
CI r
qCR3: 1788.2

L
CI Ce R3e L
CI Ce R3e

R4Q4 R3Q4
CI Ce L R3Q4 R3e Q4
hCR3R4: 1578 CI Ce L R3e Q4
hCR3R4: 1578
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

CI Ce R3Q4 R3e CI R4Q4 R3Q4 R3e

R4Q4 :0

Fig. 1. (a) Phase diagram fragment adjoining Al2O3 = C; and (b–c) vertical mass balances for centroids (b) G1, (c) G2, and (c)
G3 in the field СeCR3QeQC.

rectangle of the invariant reaction in a vertical mass which the phase L disappears and the phase R4
balance diagram shows the conversions that occur at a appears (since the melt is consumed completely, the
constant temperature. R3 and R4 fractions increase and the С fraction
The centroid G1(0.054; 0.208; 0.738) set in the field decreases). For the reaction to occur, as little as Cin =
0.382 is required. Of this amount, the eutectic crystals
CQCQe crosses three phase fields (L + C, L + C + R3,
Ce = 0.062 are first completely consumed: Cin – Ce =
and C + R3 + R4) and the invariant complex at the 0.382 – 0.062 = 0.32. Next, for the reaction to con-
temperature of quasi-peritectic point Q4 (Fig. 1b,
tinue, primary crystals С1 are consumed: C1 – 0.32 =
Table 1) (R1 = 2MgO ⋅ SiO2, R2 = MgO ⋅ SiO2, R3 =
0.389 – 0.32 = 0.069. When the reaction is over, they
3Al2O3 ⋅ 2SiO2, R4 = MgO ⋅ Al2O3, R5 = 4MgO ⋅
amount to C1 = 0.069. Finally, for the centroid G1 the
5Al2O3 ⋅ 2SiO2, and R6 = 2MgO ⋅ 2Al2O3 ⋅5SiO2).
microstructure involves primary crystals C1 = 0.069,
One can see from the calculations and the vertical eutectic crystals R3e = 0.189, and the product of invari-
mass balance diagram that the primary crystallization ant quasi-peritectic reaction R3Q4 = 0.55, R4Q4 = 0.192.
reaction L → C1 occurs in the phase field L + C in the
range 1803–1684.4°С where the fraction of phase C1 For the centroid G2(0.01; 0.14; 0.85) set in the field
increases and the fraction of phase L decreases; as a СQeeCR3, the vertical mass balance diagram (Fig. 1c) is
result, the primary crystals amount to C1 = 0.389. In similar to the one for G1. On the end of the invariant
the three-phase field L + C + R3, the occurrence of reaction, however, the microstructure involves eutec-
the monovariant eutectic reaction L → Ce + R3e and tic crystals Ce along with primary crystals C1. This is
the associated decrease in phase L brings about a gain due to the fact that this reaction needs as little as Cin =
in phase C and phase R3, and by the end of the reac- 0.071 to occur. This amount is fully replenished from
tion they amount to С(C1 = 0.389, Ce = 0.062) = 0.451 the eutectic crystals: Ce – Cin = 0.137 – 0.071 = 0.066.
and R3e = 0.189. At 1578°С, there occurs the invariant Thus, the centroid G2 has the following microstruc-
quasi-peritectic reaction LQ4 + C → R3Q4 + R4Q4, in ture set: primary crystals C1 = 0.402, eutectic crystals

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 63 No. 8 2018

 Т–х–y DIAGRAM OF MgO–SiO2–Al2O3 SYSTEM 1089

Table 1. Mass balances

Phase field T, °C Weight fractions of phases
G1(0.054; 0.208; 0.738) in the field CQCQe (Fig. 1b)
L+C 1803 L = 1, C = 0
(L → C1) 1684.4 L = 0.611, C1 = 0.389
L + C + R3 1684.4 L = 0.611, C1 = 0.389, R3 = 0
(L → Ce + R3e) 1578 L = 0.36, C(C1 = 0.389, Ce = 0.062) = 0.451, R3e = 0.189
L = 0.36, C(C1 = 0.389, Ce = 0.062) = 0.451, R3e = 0.189, R4 = 0
LQ4 + C → R3Q4 + R4Q4 1578 L = 0, C1 = 0.069, R3(R3e = 0.189, R3Q4 = 0.55) = 0.739, R4Q4 = 0.192
{Cin = 0.382; Cin – Ce = 0.382 – 0.062 = 0.32; C1 – 0.32 = 0.389 – 0.32 = 0.069}
C + R3 + R4 0 C1 = 0.069, R3(R3e = 0.189, R3Q4 = 0.55) = 0.739, R4Q4 = 0.192
G2(0.01; 0.14; 0.85) in the field CQeeCR3 (Fig. 1c)
L+C 1892.4 L = 1, C = 0
(L → C1) 1811.2 L = 0.598, C1 = 0.402
L + C + R3 1811.2 L = 0.598, C1 = 0.402, R3 = 0
(L → Ce + R3e) 1578 L = 0.066, C(C1 = 0.402, Ce = 0.137) = 0.539, R3e = 0.395
L = 0.066, C(C1 = 0.402, Ce = 0.137) = 0.539, R3e = 0.395
LQ4 + C → R3Q4 + R4Q4 1578 L = 0, C(C1 = 0.402, Ce = 0.066) = 0.468, R3(R3e = 0.395, R3Q4 = 0.101) = 0.496,
R4Q4 = 0.036
{Cin = 0.071; Ce – Cin = 0.137 – 0.071 = 0.066}
C + R3 + R4 0 C(C1 = 0.402, Ce = 0.066) = 0.468, R3(R3e = 0.395, R3Q4 = 0.101) = 0.496,
R4Q4 = 0.036
G3(0.025; 0.207; 0.768) on the line CQe (Fig. 1d)
L+C 1828.2 L = 1, C = 0
(L → C1) 1788.2 L = 0.818, C1 = 0.182
L + C + R3 1788.2 L = 0.818, C1 = 0.182, R3 = 0
(L → Ce + R3e) 1578 L = 0.166, C(C1 = 0.177, Ce = 0.177) = 0.354, R3e = 0.48
L = 0.166, C(C1 = 0.177, Ce = 0.177) = 0.354, R3e = 0.48
LQ4 + C → R3Q4 + R4Q4 1578 L = 0, C1 = 0.177, R3(R3e = 0.48, R3Q4 = 0.254) = 0.734, R4Q4 = 0.089
{Cin = 0.177; Ce – Cin = 0.177 – 0.177 = 0}
C + R3 + R4 0 C1 = 0.177, R3(R3e = 0.48, R3Q4 = 0.254) = 0.734, R4Q4 = 0.089

Ce = 0.066, R3e = 0.395, and the product of quasi-
peritectic reaction R3Q4 = 0.101, R4Q4 = 0.036.
On line СQe for composition G3(0.025; 0.207;
0.768) (Fig. 1d), the primary and eutectic crystals are
in equal amounts after the eutectic monovariant reac-
tion occurs: С1 = Се = 0.177. The same amount is
required for the invariant reaction to occur. It is for
this reason that eutectic crystals Се are consumed
completely in the course of the reaction, while С1 pri-
mary crystals remain in an unchanged amount. The
microstructure composition for G3 is C1 = 0.177,
R3e = 0.48, R3Q4 = 0.254, and R4Q4 = 0.089.
Calculations of horizontal mass balance diagrams
and crystallization paths. A horizontal mass balance
diagram makes it possible to analyze phase ratios at a
given temperature on a chosen isopleth. Let us con-
sider the isopleth drawn through the composition G1
parallel to R3R4 (Fig. 1а): s1(0; 0.262; 0.738)–
s2(0.262; 0; 0.738) (Fig. 2a). Two temperatures are
selected, Т = 1820 and 1750°С, for which horizontal
mass balance diagrams are calculated: M1N1 (Fig. 2b)
and M2N2 (Fig. 2c). The positions of horizontal sections
M1N1 and M2N2 are also indicated on the isopleth; their
widths are equal to the isopleth width.
The section M1N1 at Т = 1820°С crosses five phase
fields: L, L + R3, L + R4, L + C + R3, and L + C + R4.
The relevant horizontal mass balance diagram (Fig. 2b)
shows the ratio of coexisting phases at this tempera-
ture; the right-hand panel shows an enlarged fragment
for the phase fields L + C and L + C + R3 for the rea-
son that the phase demarcation lines merge. The phase
fields are separated by vertical straight lines; the posi-
tions of these lines are determined by the points of
intersection of the secant lines and the section M1N1.
The diagram for M1N1 is divided by these straight lines
into five fragments, the number equal to the number of
crossed phase fields. The section M2N2 at Т = 1750°С

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 63 No. 8 2018

1090 LUTSYK, ZELENAYA

(а) (d)
L
L qR4: 1882
R4I 1820°C
L+C L + R3 r
qR4C: 1791.4
M1 L + R4 N1(1820°C) 1750°C
M2 N2(1750°C) R4I L
C
L + C + R4 L + C + R3 R4e
L
R4I R4e R3Q4 C Q4
hCR3R4: 1578
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

C+ R3 + R4 R4I R4e R4Q4 R3Q4 C

s1 G4 G 1 s2
1.0

(b) C C L C (e)
0.9

L Q1 Q2
0.8 P
L L Q4
0.7

0.6

0.5 e1 R3
0.4 R3 E1 eCR3
0.3
R4
0.2
G4
0.1 R3
0
R4 eCR4 C
M 1 G4 G1 N1

(c) 1.0
(f)
0.9
L

0.8

L L
0.7

0.6 L
0.5

0.4
L + R1 L + R3
0.3 L + A + R1 G1 s2
R4 R3
0.2 C L+A L + C + R3
L + R4 G L+C
4
0.1
CC L + A + R4 L + C + R4
0
M 2 G4 G1 N2 S1

Fig. 2. (a) Isopleth s1(0, 0.262, 0.738)–s2(0.262, 0, 0.738); (b, c) horizontal mass balances for (b) M1N1 and (c) M2N2; (d) ver-
tical mass balance and (e) crystallization paths for the centroid G4; and (f) the 1750°С isothermal section.

crosses only three phase fields: L + C, L + C + R3, and For comparison, the horizontal mass balance dia-
L + C + R4. Its horizontal mass balance diagram is, grams show the positions of centroids G1(0.054;
accordingly, divided into three parts (Fig. 2c). An iso- 0.208; 0.738) (Fig. 1b) and G4(0.155; 0.107; 0.738)
thermal section is calculated for this temperature (Fig. 2f) (Fig. 2d), and the relevant vertical mass balance dia-

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 63 No. 8 2018

 Т–х–y DIAGRAM OF MgO–SiO2–Al2O3 SYSTEM
grams indicate the horizontal mass balance tempera-
tures T = 1820 and 1750°С.
The crystallization stages shown in the vertical
mass balance diagrams are verified by crystallization
path calculations. For example, the centroid
G4 crosses three phase fields (L + C, L + C + R4, and
C + R3 + R4) and the invariant complex at Q4 (Fig. 2d),
and it is characterized by the following set of phase
reactions: L → R41, L → Ce + R4e, and LQ4 + C →
R3Q4 + R4Q4. Considering the crystallization paths, we
can see that, in passing through the field L + R4, the
melt has its composition changing along the continu-
ation of the straight line R4-G to the liquidus line
eCR4Q4. Then, G4 finds itself in the field L + С + R4,
and the melt composition moves along the liquidus
line fragment eCR4Q4 to the point Q4. On the horizon-
tal complex at Q4, the phase L is completely consumed
as a result of four-phase mass rearrangement. Below
there is the subsolidus field C + R3 + R4.
We used a model phase diagram of the MgO–
SiO2–Al2O3 system to show the possibility of analyz-
ing the microstructural composition in terms of the
competitive participation of primary (coarse-grained)
and secondary eutectic (fine-grained) crystals. We
have calculated vertical and horizontal mass balance
diagrams for determining the ratio of coexisting phases
either over the entire range of temperatures for the
chosen centroid, or on a constant temperature iso-
pleth.
Thus, not only do developed models make it possi-
ble to visualize the geometry of a phase diagram, but
they are a source of information on crystallization and
microstructure formation stages, making it possible to
qualitatively and quantitatively evaluate phase ratios
and phase assemblage ratios for a given composition.
In particular, we have revised the interpretation
[16] of the ternary point of the Т–х–у diagram with
the coordinates (wt %) 14.5 MgO, 44.5 SiO2, 41 Al2O3,
and 1450°С [17], this point being taken into account in
substantiating corundum armor element preparation
technology. This point was reported [18, 19] to have a
melting temperature of 1578°С. The occurrence of
phase reaction LQ4 + Al2O3 → 3Al2O3 ⋅ 2SiO2 + MgO ⋅
Al2O3 is not typical of this point due to the absence of
Al2O3 crystals. While cooled this melt is involved in the
following phase reactions: L → 3Al2O3 ⋅ 2SiO2 + MgO ⋅
Al2O3 (in the range 1578–1482°С; the melt fraction L
is reduced to 88.2 wt %), LP + 3Al2O3 ⋅ 2SiO2 + MgO ⋅
Al2O3 → 4MgO ⋅ 5Al2O3 ⋅ 2SiO2 (1482°С, L is reduced
to 87.1 wt %), L → 3Al2O3 ⋅ 2SiO2 + 4MgO ⋅ 5Al2O3 ⋅
2SiO2 (1482–1460°С, L is reduced 78.8 wt %), and
LQ3 + 3Al2O3 ⋅2SiO2 → 4MgO ⋅ 5Al2O3 ⋅ 2SiO2 +
2MgO ⋅ 2Al2O3 ⋅ 5SiO2 (1460°С; melt disappears com-
pletely). Thus, this melt exists up to 1460°С (the tem-
peratures are given according to [18, 19]).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
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ACKNOWLEDGMENTS
This study was performed in accordance with the
Governmental Task to the Institute of Physical Mate-
rials Science of the Siberian Branch of Russian Acad-
emy of Sciences (project no. 0336-2016-0006) and was
in part supported by the Russian Foundation for Basic
Research through project nos. 15-43-04304 r_Sibir_a,
16-48-030851 r_a, and 17-08-00875 a.
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Translated by O. Fedorova
Vol. 63 No. 8 2018