Refractories and Industrial Ceramics Vol. 51, No.

4, 2010

THERMOMECHANICAL PROPERTIES
OF REFRACTORY MATERIALS OF Al2O3–Si3N4–C COMPOSITIONS
BASED ON ACPB AFTER IMPREGNATION WITH A SOL-GEL
COMPOSITION

L. A. Angolenko,1 G. D. Semchenko,1 E. E. Starolat,1 S. A. Savina,1

S. V. Tishchenko,1 and V. V. Povshuk2

Translated from Novye Ogneupory, No. 7, pp. 29 – 33, July 2010. Original article submitted December 23, 2009.

Comparative characteristics are presented for the physicomechanical properties and oxidation resistance of re-
fractory materials of Al2O3–Si3N4–C composition based on an ACPB for the original materials (fired at
1400°C) and after impregnation with a sol-gel composition and heat treatment at 800°C. A reduction in mate-
rial porosity, increase in strength and reduction in carbon burn-off are due to development of a glassy phase in
the pore space and on graphite flakes due to SiO2 formation with thermal destruction of the organosilicon sub-
stance.
Keywords: silicon nitride, aluminochromium phosphate binder (ACPB), sol-gel composition, physico-
mechanical properties.

Different composites based of a combination of oxide
and oxygen-free compounds, among which of most practical
value are SiC and Si3N4, and also graphite-containing com-
posites, makes it possible to achieve high operating proper-
ties due to strengthening of the useful properties and sup-
pressing undesirable properties, that considerably expands
their field of application [1 – 3].
A promising field for creation of effective refractory ma-
terials for metallurgy is the system Al2O3–Si3N4–C, within
which it is possible to use not only silicon nitride, but also
ferrosilicon nitride FeSi3N4. Ferrosilicon nitride exhibits
high mechanical strength at high temperature, low LTEC,
and absence of shrinkage during repeated firing. As a result
of chemical reaction of silicon, nitrogen, carbon present in
iron at high temperature there is formation of silicon carbide
and silicon nitride bonds, that also governs an improvement
in refractory mix properties [4]. Ferrosilicon nitride is within
the composition of the majority of contemporary imported
refractory mixes.
The mechanism of the modifying action of Si3N4 in ma-
terials of the system Al2O3–C is covered in [5]. Thermody-
namic calculations showed that refractory concretes of the
Al2O3–Si3N4–C system may be strengthened by synthesis in
1
National Technical University, Khar’kov Polytechnic Institute,
Khar’kov, Ukraine.
2
OOO PO Ukrspetsogneupor, Zaporozh’e, Ukraine.
a reducing atmosphere in situ SiAlON with addition of Si3N4
to the concrete and increasing the amount of Si. It has been
established that with an increase in Si3N4 content the strength
of material starts to increase, reaching a maximum with con-
tent of 6% Si3N4, and then it decreases with a further in-
crease in Si3N4 content. With introduction of silicon concrete
strength increases with an increase in Si content. Introduc-
tion of additional SiO2 and Al2O3 nanopowder promotes a
reduction in the temperature for forming b-SiAlON and a re-
duction in the amount of materials with a low melting tem-
perature [6]. Addition of silicon nitride may also be consid-
ered as an antioxidant for different graphite-containing mate-
rials.
Various unmolded refractories are most in demand in the
refractory market, one of the main advantages of which is a
combination of the optimum price and a reduction in con-
sumption in an installation, and also the possibility of realiz-
ing the concept of an “infinite” lining. The principal of creat-
ing an “infinite” lining assumes prior treatment of the surface
of the remaining layer of lining before applying a new refrac-
tory concrete layer. Therefore modification of the surface of
a basic layer may considerably increase the operating life of
a lining, that activates developments in this direction. A
study of the possibility of repeated use of Al2O3–Si3N4–C
composite material based on an aluminochromium phos-
phate binder (ACPB) as a lining material, skull or torcrete

274
1083-4877/10/5104-0274 © 2010 Springer Science+Business Media, Inc.
Thermomechanical Properties of Refractory Materials of Al2O3–Si3N4–C Compositions
Fig. 1. Dependence of water absorption W of rammed mixes of
Al2O3–Si3N4–C composition based on ACPB on the amount of sili-
con nitride (a) and graphite (b ) in the charge.
mix, also makes it possible to resolve the problem of energy
and resource saving.
The area studied was technology of preparing materials
of Al2O3–Si3N4–C composition using an ACPB for creating
unmolded refractories, assuming realization of the principal
of creating an “infinite” lining. The problem studied included
development of compositions of refractory mixes based on
the Al2O3–Si3N4–C composition using an ACPB. Mixes
should have sufficiently high physicomechanical properties
TABLE 1. Dependence of Water Absorption W and Weight Gain DmETS
on the Amount of Silicon Nitride x and Graphite y
Value of parameter Dependence equation
Without Si3N4 W = – 0.0056x3 + 0.0516x2 – 0.126x + 3.02
addition DmETS = – 0.9515x3 + 7.3717x2 – 13.17x + 22.77
1 wt.% Si3N4 W = – 0.0083x3 + 0.0585x2 – 0.0902x + 2.77
DmETS = – 0.2513x3 + 1.533x2 – 0.7217x + 18.4
2.5 wt.% Si3N4 W = 0.0007x3 – 0.0119x2 + 0.0412x + 2.64
DmETS = – 1.2362x3 + 9.3267x2 – 16.21x + 26.87
5 wt.% Si3N4 3 2
W = – 0.0023x + 0.0135x – 0.0112x + 2.57
DmETS = 0.3762x3 – 2.7047x2 + 3.5785x + 26.04
Without graphite W = – 8·10–5y3 + 0.0036y2 – 0.066y + 3.02
DmETS = – 0.0295y3 + 0.6996y2 – 3.634y + 22.77
5 wt.% C W = – 0.0003y3 + 0.0068y2 – 0.0697y + 2.94
DmETS = 0.0159y3 – 0.301y2 + 1.6963y + 16.02
10 wt.% C 3 2
W = – 7·10–5y + 0.0022y – 0.0413y + 2.94
DmETS = – 0.0084y3 + 0.1634y2 – 0.367y + 21.05
15 wt.% C 3 2
W = – 0.0002y + 0.0052y – 0.07y + 2.98
DmETS = – 0.0096y + 0.2108y – 0.9277y + 22.27
3 2
275
Fig. 2. Dependence of weight gain Dm as a result of sol-gel compo-
sition impregnation of rammed mix specimens of Al2O3–Si3N4–C
composition on the amount of silicon nitride (a) and graphite (b ) in
the charge.
with repeated use due to impregnation with an organoelemental
substance. The starting components used were coarse
electrocorundum (56 – 70 wt.%) and fine fraction (24 – 30 wt.%),
finely dispersed silicon nitride (0 – 10 wt.%), graphite
(0 – 15 wt.%), ACPB (10 wt.% above 100%), ethyl silicate
ETS-40. The physicomechanical properties were determined
by the standard procedure [7]. Before low-temperature heat
treatment (1t 800°C for 4 h) material of the Al2O3–Si3N4–C
composition was previously fired at 1450°C, impregnated
with a sol-gel composite based on ethyl silicate
hydrolysate ETS-40 (ETS-40:water:HNO3 = 4:1:0.004)
for 8 h and weight increase was studied after impregna-
tion with the binder with a change in water absorption of
the original material with variation of the amount of sili-
con nitride and graphite.
As may be seen from Figs. 1 and 2 material water ab-
sorption is 5 – 11% and the weight increase in 0.5 – 1.5%.
Their dependence on the amount of silicon nitride is less
clear than on the amount of graphite (Table 1), that is gov-
erned mainly by water absorption W and impregnation ca-
pacity +DmETS: the higher the graphite content, the greater
W and +DmETS.
The dependence of the weight change was studied af-
ter heat treatment at 800°C for 4 h of refractory materials
of the Al2O3–Si3N4–C composition based on ACPB on
the amount of silicon nitride and graphite in the charge for
the original specimens (Fig. 3) and impregnated with a
sol-gel composite (Fig. 4). The average weight loss for
materials containing 5 wt.% graphite is 4% (or 82% of the
original graphite), for 10 wt.% of graphite it is 7.5% (77%
of the original amount of graphite), for 15% graphite it is
11% (75% of the original amount of graphite). Equations
276
Fig. 3. Dependence of Dm of rammed mixes of Al2O3–Si3N4–C com-
position on the amount of Si3N4 (a) and graphite (b ) in the charge.
for the dependence of weight loss [-Dm800] on the amount of
silicon nitride and graphite are provided in Table 2.
As may be seen from Figs. 3 and 4, weight loss depends
little on the amount of silicon nitride, and the least losses are
TABLE 2. Dependence of Weight Loss After Heat Treatment at 800°C
DmETS on the Amount of Silicon Nitride x and Graphite y
Value of parameter Dependence equation
Without Si3N4 Dm800 = 0.0094x3 – 0.0678x2 + 0.1116x + 0.0487
addition Dm800 ETS = 0.0064x3 – 0.0501x2 + 0.0942x + 0.2319
1 wt.% Si3N4 Dm800 = 0.0275x3 – 0.173x2 + 0.1757x + 3.9575
Dm800 ETS = 0.0756x3 – 0.3527x2 – 0.146x + 4.1326
2.5 wt.% Si3N4 Dm800 = – 0.0344x3 + 0.257x2 – 0.5124x + 7.7223
Dm800 ETS = 0.2709x3 – 1.5537x2 + 1.6243x + 6.8047
5 wt.% Si3N4 Dm800 = – 0.0006x3 – 0.1158x2 + 0.7922x + 10.511
Dm800 ETS = 0.3762x3 – 2.7047x2 + 3.5785x + 26.04
Without graphite Dm800 = 0.0019y3 – 0.039y2 + 0.9205y + 0.083
Dm800 ETS = – 0.0101y3 + 0.1946y2 + 0.0366y + 0.2511
5 wt.% C Dm800 = 0.0006y3 – 0.0069y2 + 0.7596y + 0.0504
Dm800 ETS = 0.0006y3 – 0.0061y2 – 0.5133y + 0.2544
10 wt.% C Dm800 = 0.001y3 – 0.0238y2 + 0.8713y + 0.1019
Dm800 ETS = – 0.0037y3 + 0.0552y2 + 0.5012y + 0.2824
15 wt.% C Dm800 = – 0.0011y3 + 0.0138y2 + 0.7407y + 0.0487
Dm800 ETS = – 0.0009y – 0.0118y + 0.8603y + 0.2319
3 2
L. A. Angolenko et al.
Fig. 4. Dependence of Dm of rammed mixes of Al2O3–Si3N4–C
composition after impregnation with sol-gel composition on the
amount of graphite (a) and Si3N4 (b ) in the charge.
typical for material containing 2.5 wt.% Si3N4. The prevail-
ing effect on the mount of weight loss is the graphite content.
Weight loss increases with an increase in graphite content.
On the whole, impregnation of materials of Al2O3–Si3N4–C
composition reduces weight loss by 5 – 10%, and this is
shown in Figs. 5 and 6. Impregnation of specimens makes
it possible to reduce open porosity (Figs. 7 and 8) and loss
of strength (Figs. 9 and 10) after heat treatment of corun-
dum-graphite materials with addition of Si3N4. As may be
seen from Fig. 8a, b, open porosity of corundum-graphite
materials with addition of silicon nitride due to impregna-
tion of a sol-gel composite is less than 4 – 14%, and the
strength (see Fig. 10a, b ) is higher by a factor of 1.5 to
2.0.
Thus, a study of the thermomechanical properties of
original refractory materials of the Al2O3–Si3N4–C com-
position based on an ACPB and after impregnation with a
sol-gel composite made it possible to draw the following
conclusions:
– weight loss with low-temperature heat treatment
(800°C for 4 h) is 4 – 12%, and after impregnation of ma-
terials with ETS hydrolysate it is 3.5 – 10.5%; the reduc-
tion in graphite burn-off may be explained by formation
of a protective glass coating on flaky graphite due to
forming SiO2 with thermal destruction of the organo-
silicon substance;
Thermomechanical Properties of Refractory Materials of Al2O3–Si3N4–C Compositions
Fig. 5. Dependence of weight loss after heat treatment at 800°C for
materials of Al2O3–Si3N4–C composition, containing 5 wt.% graph-
ite, after impregnation with a sol-gel composition (curve) and ETS
gel content in material after impregnation (rectangles) on the
amount of graphite (a) and Si3N4 (b ) in the charge.
Fig. 6. Dependence of weight loss after heat treatment at 800°C for
materials of Al2O3–Si3N4–C composition, containing 5 wt.% graph-
ite, original (n) and after sol-gel composition impregnation (n) on
the amount of Si3N4 (a) and graphite (b )in the charge.
277
Fig. 7. Dependence of open porosity after heat treatment at 800°C
for materials of Al2O3–Si3N4–C composition, containing 5 wt.%
graphite, after impregnation with a sol-gel composition (curve) and
ETS gel content in material after impregnation (rectangles) on the
amount of graphite (a) and Si3N4 (b ) in the charge.
Fig. 8. Dependence of open porosity after heat treatment at 800°C
for materials of Al2O3–Si3N4–C composition, containing 5 wt.%
graphite, original (n) and after sol-gel composition impregnation
(n) on the amount of Si3N4 (a) and graphite (b ) in the charge.
278
Fig. 9. Dependence of loss of strength after heat treatment at 800°C
for materials of Al2O3–Si3N4–C composition, containing 5 wt.%
graphite, after impregnation with a sol-gel composition (curve) and
ETS gel content in material after impregnation (rectangles) on the
amount of graphite (a) and Si3N4 (b ) in the charge.
– open porosity decreases from 30 – 31 to 27 – 29% due
to filling of the pore space with molten glass;
– material loss of strength if reduced on average by a
factor of 1.5 to 2.0 due to the strengthening action of the
glass phase.
REFERENCES
1. G. G. Gnesin, “Oxygen-free ceramic materials based on silicon
carbide and nitride,” Neorgan. Materialy, 29, No. 6, 756 – 763
(1993).
2. N. V. Pitak, T. P. Khmelenko, R. M. Fedoruk, et al., “Silicon car-
bide refractories for blast furnaces,” Ogneupory, No. 10, 29033
(1984).
3. I. D. Kashcheev, V. A. Kamenskaya, and K. G. Zemlyanoi,
“Physicochemical and technological studies of a mix based on
graphite and refractory oxides,” Proc. All-Russian Conf. “Solid
chemistry and new materials, Vol. 1, UrO RAN, Ekaterinburg
(1996).
L. A. Angolenko et al.
Fig. 10. Dependence of loss of strength after heat treatment at
800°C for materials of Al2O3–Si3N4–C composition, containing
5 wt.% graphite, original (n) and after sol-gel composition impreg-
nation (n) on the amount of Si3N4 (a) and graphite (b ) in the charge.
4. Chen Junhong, Sun Jialin, and Deng Xiaolin, “Effect of ferro-
Si3N4 on resistance to oxidation of Al2O3–Si3N4–C refractory
concretes,” (China, University of Science and technology,
Beijing), Naihuo calliao – Refractories, 39, No. 1, 50 – 53
(2005).
5. Lu Chunyan, and Wang Houzhi, “Mechanical properties of
Al2O3–Si3N4–C refractory concretes strengthened by synthesis in
situ SiAlON,” (China, Wuhan University of Science and Tech-
nology), Naihuo calliao – Refractories, 38, No. 3, 160 – 164
(2004).
6. Lu Chunyan, Wang Hauzhi, and Gu Huazhi, “Effect of silica-alu-
mina powder with a colloidal particle size on the properties of re-
inforced SiAlON Al2O3–Si3N4–C refractory concretes,” (China,
Huzhou University), Naihuo calliao - Refractories, 39, No. 3,
188 – 191 (2005).
7. K. K. Strelov and I. D. Kashcheev, Technical Control of Refrac-
tory Production. Textbook for Technical Schools [in Russian],
Metallurgiya, Msow (1986).