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E. Prestes1, A.P. Luz1, D.T. Gomes2, V.C. Pandolfelli1

Sintering Effect of Al and a Boron Source

in High-Alumina Nano-Bonded Refractory
Castables
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The corresponding author, Ana Paula da Luz, is Senior
Researcher at the Materials Engineering Department,
Federal University of São Carlos, Brazil, from which she
earned her Ph.D. in Materials Science and Engineering.
She received B.Sc. and M.Sc. degrees in Chemical and
Materials Engineering, respectively, from the Engineer-
ing School of Lorena (EEL-USP), Brazil. Through July
2015, she has authored or co-authored 53 papers in
peer-reviewed journals and 27 in conference proceedings. She also co-
authored the book “FIRE Compendium Series – Refractory Castable Engi-
neering” with Dr. M.A.L. Braulio and Prof. Dr. V.C. Pandolfelli, which was
recently published by Göller-Verlag, Germany. Her main research interests
include: refractory castables design, processing and characterization, ther-
modynamic simulations, and porous insulating materials.
E-Mail: anapaula.light@gmail.com
Eduardo Prestes is currently a postdoctoral researcher
(UEPG, Brazil) and business partner at ENGEMAT Projects
and Consulting (www.engematpr.com.br). He trained as
a materials engineer (State University of Ponta Grossa –
UEPG, Brazil, 2005), with a Ph.D. Degree in Engineering
and Materials Science from Federal University of São
Carlos – UFSCar, Brazil, 2013. His areas of professional
interest are: refractory castables, asphalt pavement,
nanocellulose-based drug delivery systems and melt processing of polymer
biocomposites.

Victor C. Pandolfelli is Full Professor in the Materials
Engineering Department, Federal University of São Carlos,
Brazil, from which he received B.S. and M.S. degrees in
ceramics. He earned his Ph.D. from Leeds University
(England) and spent a year as a visiting researcher at
École Polytechnique in Montreal (Canada). He has au-
thored or co-authored 2 books, 469 papers in journals
and 233 in proceedings, and holds 8 patents. During his
career, he received 83 international (Japan, Germany and USA) and national
awards for his scientific and technological achievements. Pandolfelli is also
a member of the editorial boards of 12 scientific journals. He is the Latin-
American coordinator of FIRE (Federation for International Refractories
Research and Education) since 2004, an international consortium involving
11 universities and 16 key private sector refractories companies. Pandolfelli
is a full member and serves on the Advisory Board of the World Academy of
Ceramics (WAC), is full member of the Brazilian Academy of Sciences and
of the Brazilian National Academy of Engineering, and is a Fellow of the
American Ceramic Society. He is also Guest Professor of Wuhan University
of Science and Technology (WUST) in China. Since 1993 he has coordinated
Alcoa Laboratory at Federal University of S. Carlos and is responsible for
training and teaching both undergraduate and graduate students. He has
active partnerships with refractory industry companies, raw materials sup-
pliers and end-users.

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Petrochemical refractory end-users face difficulties in finding commercial products with optimized thermo-mechanical proper- castable, colloidal silica,
ties for the low operational temperatures (<900 °C) in fluid catalytic cracking units. Blending colloidal binders with sintering sintering additives,
additives in castable compositions is an interesting alternative that may overcome the limited densification of conventional alumina
cement-bonded systems. This work investigated the effects associated with use of Al and/or boron sources added to high- INTERCERAM 64 (2015) [4-5]
alumina colloidal silica-bonded castables sintered at temperatures up to 1000 °C. In situ measurements of hot elastic modulus
and hot modulus of rupture, and XRD and SEM analyses were performed to explain the reaction mechanisms and phase evolu-
tion associated with Al and boron-based compound performance at high temperatures. The test results indicate that added
boron induced formation of Al4B2O9 and generated liquid phase in the microstructure of the castables. Aluminium powder was
oxidized (giving rise to alumina), which resulted in increased castable stiffness. This latter transformation was only observed
in colloidal silica-containing compositions. The best thermo-mechanical performance in the 600–815 °C range was obtained
for castables containing both Al and boron.

1 Introduction Calcium aluminate cement is the most applied binder in conven-

Improved performance of refractory products in recent years has
been associated with continuous evolution of raw materials, dis-
persing agents, installation techniques and operational practices.
However, there is still a shortage of commercial refractory materials
with suitable properties (e.g. high mechanical strength) designed
for specific applications, such as fluid catalytic cracking units in the
petrochemical industry, at temperatures below 900 °C [1–3].
1 Federal University of São Carlos, Materials Engineering Department,
Rod. Washington Luiz, km 235, São Carlos, SP, 13565-905 (Brazil)
2 Petrobras, CENPES/EB-AB-G-E/EEQ – Rio de Janeiro, RJ (Brazil)
tional refractory compositions used for steel-making processes. At
room temperature, after reaction with water, this additive induces
hydraulic bonding between the fine matrix and coarse aggregates
[4]. Nevertheless, decomposition of cement hydrated phases (i.e.
CAH10, C2AH8, C3AH6 and AH3, where C = CaO, A = Al2O3 and H =
H2O) during drying/heating usually results in an increase of overall
porosity and, consequently, reduction of the mechanical resistance
of refractory materials up to 500 °C [4–6].
Due to their high specific surface area and reactivity, binder suspen-
sions containing nanoparticles (colloidal alumina or colloidal silica)
are an alternative to allow development of castable compositions
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with more suitable thermo-mechanical properties at intermediate
temperatures (<900 °C) [5, 7–9]. In addition, it has been reported
that incorporation of sintering additives (Al, Si, boron-based com-
pounds, etc.) can lead to major improvements in the stiffness and
mechanical strength of different refractory systems in the 500 to
1000 °C range [2, 3, 10]. The enhanced performance of boron-con-
taining compositions has been associated with generation of a tran-
sient liquid (B2O3-rich phase) in their microstructures above 450 °C.
The densification process is sped up by reaction of this liquid with
other materials contained in the refractory mixture, giving rise to
new solid components (i.e. borates) [3, 10]. Boron additives seem
suitable for development of castables for petrochemical applications
as they may induce faster sintering and take advantage of the low
melting temperature of aluminium (~660 °C [10]).
Therefore, this work evaluates the performance of high-alumina
nano-bonded refractory castables containing Al and/or a boron
source. The reaction mechanisms and phase evolution effects due to
the action of these additives were investigated via in situ hot elastic
modulus and hot modulus of rupture measurements, and XRD and
SEM analyses.
2 Materials and techniques
High-alumina vibratable refractory castables were designed accord-
ing to the Alfred particle packing model (q = 0.26) [5]. The base
refractory was composed of tabular alumina (d <6 mm, Almatis,
Germany), reactive aluminas (CL370C and CT3000SG, Almatis,
Germany) and silica fume (MS971D, Elkem, Norway). 1.9 mass-%
Al powder (d <45 μm, Alcoa, Brazil) and/or 1.2 mass-% boron
source (BS, d <45 μm, B2O3 content ~53.84 mass-%) [2] were also
added to the mixture, as described in Table 1. 7 mass-% of a colloidal
silica suspension (binder source) with 40 mass-% solid concentration
(Bindzil 1440, Eka Chemicals, Sweden) was added to the Al2O3-con-
taining compositions to attain castables with roughly 60 % vibrata-
ble flowability. Finally, 0.01 mass-% dead-burnt magnesia was in-
corporated into the dry-mix to induce colloidal silica gelation and,
consequently, setting of the refractory.
The refractories were mixed in a rheometer especially developed for
refractory castable processing [11]. The mixtures were then cast in
metallic moulds to make prismatic samples (150 mm × 25 mm ×
25 mm) that were cured at 50 °C/24 h (without humidity control)
and dried at 110 °C/24 h. The evolution of elastic modulus (E) with
temperature was evaluated for each sample to identify the effects of
Al and BS during sintering. Measurements were performed from 30
through 1000 °C (heating cycles having a heating rate of 2 °C/min)
using the bar resonance technique (ASTM C 1198-91). This method
is based on excitation and detection of the sample’s responding
vibration spectrum using piezoelectric transducers. Wide-frequen-
cy scanning is performed in order to excite and capture the natural
resonance frequencies of the ceramic bars. Elastic modulus is calcu-
lated from the vibration spectrum by applying a Pickett equation
Table 1 • General design of the evaluated castable compositions
Raw material / mass-%
Tabular alumina (d <6 mm)
Reactive aluminas (CL370C and CT3000SG)
Silica fume
Aluminium powder (Al, d <45 μm)
Boron source (BS, d <45 μm)
Colloidal silica (CS, 40 mass-% solids)
Dead-burnt MgO (d <212 μm)
Total water content in the colloidal silica suspension
which correlates the E value, the natural vibration frequencies
and the sample’s dimensions [12]. For the fundamental flexural
frequency of a rectangular bar, Young’s modulus E (in Pa) is giv-
en by:
(1)
where m is mass (g), b is width (mm), L is length (mm), t is thick-
ness (mm), ff is the fundamental resonance frequency of the bar
(Hz), and T1 is a correction factor for the fundamental flexural
mode that accounts for the finite thickness of the bar, Poisson’s ratio
and other factors.
Hot modulus of rupture (HMOR) measurements were made by
3-point bending tests carried out with Netzsch HBTS 422 equip-
ment (Germany) at 600, 815 and 1000 °C using samples pre-fired
for 5 h at the HMOR testing temperature (ASTM C583-8). Due to
their higher reactivity, matrix samples were analysed with XRD to
identify the phase transformations that take place in the matrix
fraction (particle size <100 μm). After thermal treatment at 600,
815 and 1000 °C/5 h, the samples were ground and sieved in a Tyler
#325 mesh screen. The powders were then placed in sample holders
and evaluated on a Bruker D8 Focus device with Cu-K_ radiation
[h = 1,5406 Å] and a nickel filter, using 40 mA, 40 mV and a scan-
ning step of 0.021 °. SEM images and EDS mappings of fired (815
and 1000 °C for 5 h) and polished castable samples were made with
DSM 960 equipment (Zeiss, USA) to identify the phase transforma-
tions that occurred in the refractory microstructure and highlight
the action of the sintering additives.
3 Results and discussion
The evolution of elastic modulus as a function of temperature is an
interesting parameter. It can help to point out the temperature ranges
where the most important microstructural transformations are tak-
ing place in a refractory material. Figure 1 shows E-curves for the ref-
erence CS composition (additive-free mixture) and the castables con-
taining boron source (BS) or aluminium powder (Al). It shows that
densification of the CS samples (due to colloidal silica interaction
with the other materials) took place mainly above 700 °C, leading to a
continuous increase of E-values up to 1000 °C. However, the addition
of sintering additives directly affected the castable’s stiffness, resulting
in markedly different behaviour at high temperature. Faster sintering
of the CS + BS castable was detected in Fig. 1 due to a rapid increase
of E values above 600 °C. The main transformations associated with
the CS + Al material were observed at a higher temperature (>800 °C).
Thus, each additive (BS or Al) promoted densification and improved
stiffness of the refractories in a different temperature range.
Figure 2 presents the hot modulus of rupture (HMOR) of the
evaluated castables. Addition of boron-compound to the castable
(CS + BS) enhanced the samples’ mechanical strength at 600 and
815 °C compared to the reference material (CS).
CS CS + Al CS + BS CS + Al + BS
86 86 86 86
12.1 10.2 10.9 9.0
1.9 1.9 1.9 1.9
– 1.9 – 1.9
– – 1.2 1.2
7.0 7.0 7.0 7.0
0.01 0.01 0.01 0.01
4.2 4.2 4.2 4.2
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1 2
Elastic modulus / GPa
Temperature / °C
Fig. 1 • Elastic modulus evolution during heating (30–1000 °C) of high-alumina
nano-bonded castables with no additive (CS), with 1.2 mass-% boron source
(CS + BS) and with 1.9 mass-% Al (CS + Al). All samples were pre-dried at
110 °C/24 h
3 4
Elastic modulus / GPa
Temperature / °C
Fig. 3 • Comparison of the elastic modulus evolution during heating
(30–1000 °C) for high-alumina nano-bonded castables containing 1.2 mass-%
of boron source (CS + BS), 1.9 mass-% Al (CS + Al) or a blend of the two
additives (CS + Al + BS). All samples were pre-dried at 110 °C/24 h
Nevertheless, due to the low melting temperature (~450 °C [2]) of
this additive and generation of a boron-rich liquid phase in the
refractory structure, a significant drop in HMOR value was seen at
1000 °C. On the other hand, the benefit of Al incorporation in the
alumina-based castable (CS + Al) could be observed at 815 and
1000 °C since Al melting only takes place at approximately 660 °C. It
is well known that fluid catalytic cracking units (FCC) usually oper-
ate in the 600 to 815 °C range. Furthermore, 815 °C is used as the
standard reference value for selection of refractory materials by the
petrochemical industry. Based on the results of Figs. 1 and 2, both
sintering additives (Al and BS) clearly have potential application in
castables for the petrochemical field. Of the two additives, BS seems
to be the most promising candidate.
Table 2 • Hot modulus of rupture measured for the reference
castable (CS) and the composition containing both sintering
additives (Al + BS)
Test temperature / °C
Castable
600 815 1000
CS 12.2 ±2.7 15.0 ±1.2 19.9 ±1.9
CS + Al + BS 18.4 ±1.0 24.4 ±1.5 9.4 ±0.7

Hot modulus of rupture / MPa
Temperature / °C
Fig. 2 • Hot modulus of rupture of high-alumina nano-bonded castables with
no additive (CS), with 1.2 mass-% boron source (CS + BS) and with 1.9 mass-%
Al (CS + Al). The samples were pre-fired at 600, 815 or 1000 °C for 5 hours
Intensity (a.u.)
e / °
Fig. 4 • XRD profile of the CS + Al + BS castable matrix after firing at 600, 815
and 1000 °C for 5 hours. A = Al2O3, B = Al, C = Si, D = SiO2 and E = Al4B2O9
Another interesting alternative is to blend both Al + BS in the casta-
ble composition, as each additive should act at different tempera-
tures and their combined presence might lead to improved mechani-
cal behaviour and densification across a broader temperature range.
Figure 3 shows that a refractory containing both additives (CS + Al +
BS) delivers optimized performance. Sintering reactions start taking
place above 600 °C (accompanied by an increase in E value) and the
sample stiffness steadily increases up to 1000 °C. Table 2 shows
HMOR values for the CS + Al + BS sample at 600, 815 and 1000 °C.
They reinforce a positive role for these sintering compounds at 600
and 815 °C, but although the HMOR value observed for CS + Al +
BS at 1000 °C is better than that of the CS + BS castable in Fig. 2, the
presence of liquid phase in the refractory structure clearly affected
the mechanical strength of the castable containing Al + BS.
To identify the main reaction mechanisms responsible for the re-
sults presented above, samples of the CS + Al + BS refractory matrix
with d <100 μm (containing reactive aluminas, silica fume, colloidal
silica and sintering additives as specified in Table 1) were prepared,
fired at 600, 815 and 1000 °C for 5 hours, and analysed via X-ray
diffraction, producing the results shown in Fig. 4.
After firing at 600 °C, Al2O3, SiO2 and Al were the main phases in the
CS + Al + BS castable matrix. Silicon peaks could be detected for the
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Fig. 5 • SEM images and EDS mapping of Al and Si for the CS + Al + BS castable
after firing at (a) 815 °C and (b) 1000 °C for 5 hours
samples thermally treated at 815 and 1000 °C. Al4B2O9 was the only
crystalline phase derived from BS interaction with the matrix com-
ponents. Its presence could be observed only at high temperature
(1000 °C). The oxi-reduction reaction responsible for Si generation
in the refractory matrix is [13]:
3SiO2 + 4Al A 2Al2O3 + 3Si
This transformation induced the substantial increases in elastic
modulus from 800 up to 1000 °C highlighted in Figs. 1 and 3, and
the significant improvement of hot mechanical strength for the
CS + Al and CS + Al + BS castables at 815 and 1000 °C (Fig. 2 and
Table 2). SEM images and EDS mapping analysis of the Al (still
present in the material fired at 815 °C) and Si elements contained in
the CS + Al + BS castable samples (Fig. 5) showed consumption of
Al and generation of Si, as indicated by Eq. 2, after the refractory
was fired at 1000 °C for 5 hours. Al oxidation led to alumina forma-
tion and new ceramic bonds were most likely generated among the
matrix components of the castable, resulting in a material with im-
proved stiffness.
In order to fully understand the aluminium powder reaction mech-
anism, it is important to identify which silica source (silica fume or
colloidal silica) plays a role in the oxi-reduction transformation of
Eq. 2. Therefore, additional castable compositions containing col-
loidal alumina (CA, 7.0 mass-% of VP Disp. W 640 ZX suspension
containing 40 mass-% solids, Evonik Degussa GmbH, Germany) in-
stead of colloidal silica as binder, with and without Al + BS, were
prepared. Measurements of the hot modulus of rupture at 815 °C
were performed for the colloidal alumina-bonded materials and the
results were compared to those of the CS-based systems (Fig. 6).
As the same amount of silica fume was contained in all castable
compositions (1.9 mass-%), the differences in the HMOR values in
Fig. 6 are mainly related to the binder agent added to the materials.
The better performance of the CS + Al + BS refractory is a conse-
Hot modulus of rupture at 815 °C / MPa
Fig. 6 • Hot modulus of rupture at 815 °C of high-alumina castables containing
colloidal alumina (CA) or colloidal silica (CS) as binder agents
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Fig. 7 • B2O3-Al2O3 phase diagram [14]. The blue dashed line highlights the in-
crease in overall liquid content (6L) at higher temperatures (>1000 °C) when a
(2) composition is located in the B2O3-2Al2O3·B2O3 field
quence of the presence of nano-silica particles that induce higher Al
oxidation.
Given this conclusion, the residual SiO2 phase detected in the XRD
analysis of the CS + Al + BS castable samples fired at 815 and
1000 °C for 5 hours (Fig. 4) should primarily be from silica fume
crystallization. Furthermore, Al4B2O9 generation is due to a reaction
of B2O3(l) and alumina contained in the refractory matrix fraction.
As can be seen in the Al2O3-B2O3 phase diagram of Fig. 7, B2O3(l) (in-
dicated as “melt”) should be found even at temperatures around
800 °C, and under thermodynamic equilibrium conditions in the
presence of alumina, liquid B2O3 can incorporate alumina oxide in-
to its composition. Depending on the firing temperature and alu-
mina content in the system, two different aluminium borates might
precipitate from this liquid phase: 2Al2O3·B2O3 (Al4B2O9) or
9Al2O3·2B2O3·(Al18B4O33).
Between 600 and 1000 °C, a number of sintering effects were associ-
ated with addition of boron source to high-alumina compositions.
From 600 to 815 °C (see Fig. 3 and Table 2) B2O3 melted and gave
rise to a viscous liquid phase which initially filled pores and induced
a faster diffusion rate of the more reactive components in the casta-
ble matrix. This favoured sintering of the structure and led to im-
provement of material stiffness and mechanical strength over that
temperature range.
Although the main phases expected to be found in CS + Al + BS re-
fractory were 9Al2O3·2B2O3 and Al2O3 (according to the matrix com-
position and Fig. 7), the interaction of B2O3(l) and fine alumina at
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1000 °C resulted in 2Al2O3·B2O3 precipitation (see Fig. 4) and also
generation of liquid phase with lower viscosity, indicating that ther-
modynamic equilibrium of the system was not achieved during fir-
ing. The liquid contained in the CS + Al + BS microstructure was
responsible for the drop in hot modulus of rupture at 1000 °C
(Table 2). Moreover, as temperature increases further, it is expected
that 2Al2O3·B2O3 will be decomposed (according to the peritetic
reaction above 1000 °C in Fig. 7), leading to precipitation of
9Al2O3·2B2O3 and additional liquid generation (the 6L indicated in
Fig. 7). Therefore, care must be taken during the design of refractory
compositions containing boron-based additives. When a permanent
liquid is generated, the refractoriness of the castable system can be
adversely affected, preventing its application at high temperatures.
Fortunately, as reported in recent studies [2, 3], depending on the
selected binder system (calcium aluminate cement and/or hydrata-
ble alumina), different reaction products might be formed between
600 and 1200 °C in high-alumina boron-containing castables, in-
ducing consumption of the boron-rich liquid and possibly make the
liquid phase be a transient component of the castable.
4 Conclusions
This work proves that a blend of Al and a boron source can be a suit-
able route for developing high-alumina nano-bonded refractories
with improved thermo-mechanical properties for the petrochemi-
cal industry. The boron-based compound acted mainly between
600–815 °C and benefit from added Al was observed above 800 °C.
A combination of these sintering additives induced better perform-
ance of the evaluated castable across a broader temperature range.
Al oxidation due to reaction with SiO2 was only identified in colloi-
dal silica-containing castables, indicating that the higher reactivity
of this SiO2 source was responsible for transformations that im-
proved hot modulus of rupture values and improved the strength of
high-alumina compositions.
Acknowledgments
The authors are grateful to FIRE, Petrobras, FIPAI and CNPq for
supporting this work.

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Received: 27.07.2015