Ceramics International 43 (2017) 10207–10216

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Ceramics International
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Boron sources as sintering additives for alumina-based refractory castables MARK

a,⁎ a b a
I.D. Giovannelli Maizo , A.P. Luz , C. Pagliosa , V.C. Pandolfelli
a
Federal University of São Carlos, Materials Engineering Department, Rodovia Washington Luis, km 235, São Carlos, SP 13565-90, Brazil
b
Magnesita Refratários S.A., Research and Development Center, Praça Louis Ensch, 240 Contagem, MG, Brazil

A R T I C L E I N F O A BS T RAC T

Keywords: Sintering additives (SA) have great potential to be used in refractories to enhance their thermo-mechanical
Sintering additive properties at intermediate temperatures (600–1200 °C). Boron-based compounds are pointed out as suitable
Boron source options for this purpose as they undergo phase transformations (i.e., decomposition, oxidation, etc.) at relatively
Castable low temperatures, which may lead to boron-rich liquid phase generation and transient liquid phase sintering.
High-alumina
Considering these aspects, the present study aims to evaluate the role of five different SA [boron oxide (B2O3),
boric acid (H3BO3), sodium borosilicate (BS), magnesium borate (BM) and boron carbide (B4C)] when 0.5, 1.0
and 2.0 wt% of these materials were added to alumina-based castable compositions bonded with hydratable
alumina. Flowability, apparent porosity, XRD, hot elastic modulus, thermal shock resistance and mechanical
tests were carried out in order to identify whether (i) transient liquid phase sintering would be favored in these
refractories, and (ii) at which temperature range such compositions might be submitted during service and still
present an improved performance when compared to an additive-free castable (reference). Based on the results,
incorporating boron oxide into the alumina-based castables was not recommended as this hygroscopic material
reduced the flowability of the compositions, preventing a suitable preparation of the samples. The other boron-
containing compounds could be directly added to the high-alumina mixtures without resulting in major changes
in their processing steps. Nevertheless, the paper highlights the importance of selecting a proper SA source and
optimizing its content in the castable composition as these parameters may affect its overall rheology and
thermo-mechanical properties. The formulations containing 0.5 wt% of H3BO3 or B4C, 1 wt% of sodium
borosilicate and 2 wt% of magnesium borate presented enhanced erosion and thermal shock resistances and hot
mechanical strength at 1000 °C and 1200 °C, which makes them potential refractory castables to be used in
petrochemical and aluminum industries.

1. Introduction refractory castables to speed up their densification at lower tempera-

Refractory products have continuously been evolving in order to
fulfill some of the end-users’ requirements, such as environmental
issues and optimization of various industrial production processes.
Consequently, the development of advanced materials (especially
monolithics) has been encouraged [1]. For instance, petrochemical
and aluminum industries (where most equipment operate at maximum
working temperatures around 800 °C and 1250 °C), in general, still use
refractory products originally designed for the steel-making sector.
However, such materials should only present their microstructural
sintering/densification and better thermo-mechanical performance
when subjected to higher temperatures ( > 1300 °C) [2–4]. Hence,
the need for designing novel refractory compositions and/or enhancing
the properties of the available ones to match their operation tempera-
tures, are required.
A likely alternative consists of adding sintering additives (SA) to the
tures (i.e., 600–1000 °C), aiming to reduce energy consumption and/or
the development of products that can be applied at a broader
temperature range (800–1400 °C) [3]. SA powdered materials are easy
to handle and can be directly incorporated into the castables’ dry-mix
[2–7]. Due to their interaction with other raw materials and environ-
mental gases, these additives act generating liquid phases in the
designed microstructure during the first heating treatment of those
refractories, which will later react and result in new refractory phases
(transient liquid) [8]. Braulio et al. [5] evaluated the influence of
various sintering agents (titania, zirconia, magnesium fluoride, mag-
nesium borate and borosilicate) in the properties of Al2O3-MgO-CaO-
SiO2 castables. The authors stated that the selected SA acted as spinel
(MgAl2O4) and calcium hexaluminate (CA6) mineralizer and/or densi-
fier compounds, enhancing the likelihood to generated CA6-platelets
with a high aspect ratio and low amount of liquid in the refractories’
matrix, resulting in outstanding creep resistance, for instance, when

⁎
Corresponding author.
E-mail address: irisgiovam@gmail.com (I.D. Giovannelli Maizo).

http://dx.doi.org/10.1016/j.ceramint.2017.05.047
Received 5 April 2017; Received in revised form 5 May 2017; Accepted 6 May 2017
Available online 10 May 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
I.D. Giovannelli Maizo et al.
Fig. 1. Al2O3-B2O3 phase diagram according to Kim et al. [9].
boron-containing additives were used.
Boron-based materials can be suitable options for improving the
castables’ sintering reactions due to their trend of undergoing phase
transformations (i.e., decomposition, oxidation, etc.) at relatively low
temperatures, which may result in a boron-rich liquid phase. As
highlighted in Fig. 1 [9], B2O3 presents a low melting point
(~470 °C) and the presence of this liquid in an aluminous refractory
composition should: (i) favor faster material transport (diffusion) and
(ii) induce easier interaction with other components of the system.
Furthermore, the interfacial bond strength between platelets and other
grains may also be improved via transient-liquid sintering and
precipitation of borates (i.e., 9Al2O3.2B2O3 and/or 2Al2O3. B2O3,
Fig. 1) [2–4,10].
Unlike the traditional liquid phase sintering, the transient process
relies on the liquid reaction with time leading to novel solid crystalline
compounds at high temperatures. German [11] highlighted that the
following steps should be observed during the transient liquid phase
sintering of an SA-containing composition: (i) swelling by interdiffu-
sion prior to melt formation (Kirkendall porosity), (ii) melt formation,
(iii) spreading of the melt and generation of pores at prior additive
particle sites, (iv) melt penetration along solid-solid contacts, (v)
rearrangement of the solid grains, (vi) solution-re-precipitation of
new phases inducing densification, (vii) diffusional homogenization,
(viii) loss of melt, and (ix) formation of a rigid and strong solid
structure. The progress of these transformations will also depend on
various parameters, including the raw materials’ particle size, additive
content, heating rate and temperature [11].
Various studies [2–6] pointed out that a suitable selection of the
sintering additives (type and amount) is fundamental to effectively
enhance the thermo-mechanical properties of refractories at the
desired working conditions. Additionally, depending on the binding
agents contained in the evaluated composition, the role of the SA may
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Ceramics International 43 (2017) 10207–10216
Fig. 2. Hot modulus of rupture of high-alumina castables bonded with colloidal silica
(CS) or calcium aluminate cement (CAC) and containing 0 or 1 wt% of a boron source as
sintering additive (SA). All samples were pre-fired at 800 °C, 1000 °C, 1200 °C or
1400 °C for 5 h before testing [2].
be greatly affected, resulting in the formation of a permanent liquid
instead of a transient one at high temperatures. Fig. 2 shows, for
instance, the hot modulus of rupture (HMOR) results attained for high-
alumina castables bonded with calcium aluminate cement (CAC) or
colloidal silica (CS) and containing a boron-based additive (1 wt%) [2].
CS-bonded samples (with no SA and pre-fired at the same testing
temperature) presented high HMOR values at 1000 °C due to their
earlier sintering as a consequence of the improved performance of the
nano-binder added to this composition. However, this silica-containing
refractory (CS) showed a continuous decrease of its mechanical
strength above 1000 °C due to the permanent liquid generated in this
castable. CS+SA material, on the other hand, already presented
enhanced mechanical behavior at 800 °C, which was associated with
the interaction of B2O3(l) with alumina and silica, and further pre-
cipitation of crystalline components from the formed liquid. Based on
these results, the authors [2] stated that the CS+SA composition could
be applied to distinct working conditions (from 800 to 1400 °C), such
as those required by the petrochemical and steel-making industries. As
also shown in Fig. 2, the sintering and densification of the CAC
refractory (with no SA) only took place above 1200 °C, resulting in a
HMOR increase due to the formation of CA2 (CaO.2Al2O3) and CA6
phases in the designed microstructure [12]. Nevertheless, unlike CS
+SA composition, the incorporation of the boron-based additive into
the calcium-bonded material (CAC+SA) did not lead to an effective
transient liquid phase sintering. Despite the precipitation of aluminum
borates at intermediate temperatures, a high amount of liquid was still
available in those samples above 1000 °C leading to low HMOR values
[2]. Therefore, the thermo-mechanical performance of high-alumina-
based refractories may be tailored by using suitable binders and
sintering additives.
Adding SA-containing boron to plain alumina castable composi-
tions (considering the use of hydratable Al2O3 sources as the main
binders) is an interesting route for designing advanced refractories for
the petrochemical sector. Based on previous studies of a joint project
between GEMM/UFSCar (Brazil) and ETH (Zurich) [13], incorporating
boric acid into a mixture of fine alumina platelets (aiming to design a
nacre-like bio-inspired microstructure) resulted in a more effective
sintering of the samples and increased the bond strength between the
platelets with the in-situ generation of 9Al2O3.2B2O3, which presents a
low thermal expansion coefficient (5.4×10−6 C−1), elastic modulus of
350 GPa and mullite-type structure [14]. The prepared bio-inspired
alumina samples containing H3BO3 presented a flexural strength of
672 and 280 MPa and a fracture toughness of 11 and 6 MPa m1/2 at
I.D. Giovannelli Maizo et al. Ceramics International 43 (2017) 10207–10216

room temperature and at 1200 °C, respectively [13]. Despite boric acid, cured at 50 °C for 24 h (without humidity control), dried at 110 °C for
other compounds (i.e., sodium borosilicate, magnesium borate, etc. [2– another 24 h and fired at 1000 °C, 1200 °C, 1400 °C, 1450 °C, 1500 °C
7]) also have the potential to be used in mixtures containing not only and 1550 °C with a holding time of 5 h using electric lab furnaces
fine and reactive aluminas, but also coarse aggregates of this oxide. (Lindberg Blue, Thermo Fisher Scientific Inc., USA).
Based on these aspects, the present study aims to evaluate the role Cold flexural strength (3-point bending test, ASTM C133-97) and
of five different boron-containing sintering additives [boron oxide apparent porosity (ASTM C830-00, using kerosene as the main
(B2O3), boric acid (H3BO3), sodium borosilicate (BS), magnesium immersion liquid) measurements were carried out to analyze the dried
borate (BM) and boron carbide (B4C)] when 0.5, 1.0 and 2.0 wt% of samples (110 °C for 24 h).
these materials were added to self-flowing alumina-based castable Additionally, aiming to evaluate the effect of the sintering additives
compositions bonded with hydratable alumina. Cold and hot mechan- during the castable sintering, in situ hot elastic modulus (E) tests were
ical tests were carried out in order to identify whether (i) a transient performed using dried and pre-fired (1400 °C/5 h) samples of the
liquid phase sintering would be favored in these refractories, and (ii) at designed refractories. These measurements were carried out according
which temperature range these compositions might be subjected to to the ASTM C 1198-91 standard using the bar resonance technique
during service and still present an improved performance when (Scanelastic equipment, ATCP, Brazil), which is based on the sample
compared to an additive-free castable (reference). excitation and detection of the correspondent vibration spectrum,
using piezoelectric transducers [17]. Elastic modulus is calculated
2. Materials and techniques based on the resulted vibration spectrum applying Pickett equations,
which correlates the E values, the natural vibration frequencies and the
Alumina refractory castables were designed according to Alfred's sample dimensions [17]. For the fundamental flexural frequency of a
model and considering packing coefficient (q) equal to 0.21 in order to rectangular bar, the Young's modulus is given by:
attain self-flow compositions [15]. All formulations comprised coarse
mf 2f L3
(d ≤6 µm) and fine (d < 45 µm) tabular aluminas, calcined and reactive E = 0.9465 × 3 × T1
b t (1)
fine Al2O3 sources (CL370C and CT3000SG), as well as hydratable
alumina (Alphabond 300) as the main binder. These materials were where E is the Young's modulus (Pa), m the mass (g), b the width
supplied by the Almatis company (Germany and Brazil). (mm), L the length (mm), t the thickness (mm), ff the fundamental
Aiming to speed up the beginning of the sintering process of these resonance frequency of the bar in flexure (Hz), and T1 the correction
compositions and induce the generation of aluminum borates in the factor for the fundamental flexural mode to account for the finite
designed microstructure, five boron-containing compounds were eval- thickness of the bar, Poisson's ratio and others. Tests were conducted
uated as likely sintering additives (SA). As highlighted in Table 1, the in the 30−1400 °C temperature range in air (pO2 =0.21 atm) with
selected materials consisted of: (i) boron oxide (d50 < 10 µm, B2O3 ~ heating and cooling rates of 2 °C/min.
99%, Magnesita Refratários SA, Brazil), (ii) boric acid (d90 < 45 µm, The same method was also used to follow (at room temperature) the
H3BO3 ~ 99%, Synth, Brazil), (iii) sodium borosilicate (BS, d50 < E decay of pre-fired castables (1400 °C/5 h) as a function of thermal
45 µm, containing mainly SiO2 ~ 80.5%, Na2O ~ 8.0%, B2O3 ~ 5.4%, shock cycles (ASTM C1171-91) at 1025 °C (10 cycles, ΔT ~1000 °C,
Magnesita Refratários SA, Brazil), (iv) magnesium borate (BM, d90 < respectively). The measurements were carried out after each 2 thermal
45 µm, B2O3 ~50%, Magnesita Refratários SA, Brazil), and (v) boron cycles (0, 2, 4, 6, 8 and 10) and the E decay were calculated as pointed
carbide (d50 < 10 µm, B4C ~99.0%, Magnesita Refratários SA. Brazil). out in Eq. (2):
A total of 0.5, 1.0 or 2.0 wt% of each additive was added to the designed
composition. Table 1 also points out the resulting B2O3 content ⎛ E − Ex ⎞
Ex decay (%) = ⎜ 0 ⎟ x 100
expected to be generated in the refractory structure at high tempera- ⎝ E0 ⎠ (2)
tures (depending on the selected SA). Further information highlighting
why these experimental procedure was selected will be clear in the where, Ex decay is the elastic modulus drop for cycle X (%). E0 and EX
Results and Discussion section. are the elastic modulus attained after 0 or X cycles (MPa), respectively.
During the castables’ mixing step, the compositions were dry and Thermodynamic simulations were performed to predict the phase
wet-homogenized in a rheometer especially developed for processing transformations involving the interaction of each selected sintering
monolithic refractories [16]. A fixed amount of distilled water (4.8 wt additive with fine aluminas (d µm) contained in the refractory matrix
%) and dispersant (0.2 wt%, Castament FS60, BASF, Germany) were at high temperatures (200–1600 °C). The FactSage® software [version
added to the dry-mixes. After obtaining homogeneous mixtures, their 6.4, Thermofact/CRCTThermofact/CRCT (Montreal) and GTT-
rheological behavior (free-flow) was measured according to ASTM Technologies (Aach(Aach en)] were used for this purpose, considering
C1446-11. The compositions presenting self-flowing feature (free-flow the FactPS and FToxid databases and the Equilib calculation modulus.
≥80% [15]) were molded as bar samples (150 mm x 25 mm x 25 mm), Besides that, the crystalline phases formed in the castables’ matrix
(after firing at 600, 900, 1200 and 1400 °C for 5 h) were also
Table 1 experimentally identified and quantified using the XRD and Rietveld
General information of the evaluated castables. techniques in order to compare these data with the theoretical ones
attained for the equilibrium condition (thermodynamic simulations).
Raw materials Compositions (wt%) The fired samples were ground in a pan mill lined with tungsten
TA TA TA TA+BS TA TA
carbide (AMP1-M, AMEF, Brazil) and evaluated using Bruker equip-
+B2O3 +H3BO3 +BM +B4C ment (model D8 Focus, CuKα radiation [λ=1.54056 Å] and with a
nickel filter, using 450 mA, 40 mV and scanning step =0.02° between
Tabular alumina 84.0 84.0 84.0 84.0 84.0 84.0 2θ =4–80°). Rietveld analyses were carried out using TOPAS 42
(d ≤ 6 mm)
Reactive alumina 14.0 12.0– 12.0–13.5 12.0– 12.0– 12.0–
software (Brucker, Germany).
13.5 13.5 13.5 13.5 Cold erosion resistance of the refractories was evaluated (using
Alphabond 300 2.0 2.0 2.0 2.0 2.0 2.0 samples fired at 1000 °C, 1200 °C and 1400 °C for 5 h) following the
Boron-based – 0.5–2.0 0.5–2.0 0.5–2.0 0.5–2.0 0.5–2.0 ASTM C704 standard (1 kg of 36 grit silicon carbide to erode speci-
additive (0.5– (0.3–1.2) (0.03– (0.2– (1.3–
mens with 100 mm x 100 mm x 25 mm thick, leading to a weight loss
(equivalent 2.0) 0.1) 0.9) 5.2)
B2O3 content) that was converted to a volumetric one).
Hot modulus of rupture (HMOR) measurements were also selected

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I.D. Giovannelli Maizo et al.
Fig. 3. Free-flow values of alumina-based castables containing 2 wt% of hydratable
alumina and different contents (0.0, 0.5, 1.0 or 2.0 wt%) of boron sources (B2O3, H3BO3,
sodium borosilicate [BS], magnesium borate [BM] or B4C) as sintering additives.
to analyze the refractories’ thermo-mechanical performance. This test
was carried out at 600 °C, 815 °C, 1000 °C, 1200 °C and 1400 °C (using
samples pre-fired for 5 h at the same testing temperature) in HBTS 422
equipment (3-point bending device, Netzsch, Germany) and according
to the ASTM C 583-15 standard. Additional tests were also performed
at 1400 °C with specimens pre-fired at 1450 °C, 1500 °C and 1550 °C
for 5 h.
3. Results and discussion
Based on a previous study [15], it was defined that a minimum of
80% of free-flow (FF) level was required to attain a self-flowing
mixture. Fig. 3 shows the measured FF values of each evaluated
composition (with and without boron additive). In general, a significant
decrease of the castable spreading was observed for the SA-containing
refractories, especially for the ones with 2 wt% of such compounds.
Most likely, B2O3 (which is a highly hygroscopic material) interaction
with the distilled water used during the TA-B2O3 compositions mixing
step is responsible for the identified flow decay [6,18], as a fraction of
the liquid was consumed for the hydration of this oxide (Eq. (3))
[19,20]. Consequently, limited water content was available in the
mixture to induce the particles’ spreading during the flowability tests.
B2O3 + 2H2O → 2H3BO3
As pointed out in Fig. 3, a self-flowing mixture was not attained
even when adding only 0.5 wt% of boron oxide to the design castable.
Hence, samples containing 0.5, 1.0 or 2.0 wt% of this SA were not
molded and prepared for additional tests due to the unsuitable and
very low flow of these compositions.
Based on these results, the incorporation of B2O3 into castable
formulations is not recommended, as this additive may negatively
affect their rheology and prevent the proper preparation of samples. As
the refractories containing 2.0 wt% of H3BO3 and B4C did not present
the required free-flow behavior, they were also not considered in the
following tests carried out in this paper. Further investigations are still
required to better understand and describe the effect of these latter
additives in the flow behavior of alumina-based compositions compris-
ing coarse and fine grains and presenting high solid concentration.
After selecting the refractories with suitable self-flowing behavior,
various samples were molded for the cold mechanical strength and
apparent porosity tests after curing (50 °C for 24 h) and drying (110 °C
for another 24 h) steps. Fig. 4 indicates that similar results were
obtained during the cold mechanical strength measurements of the
samples with and without SA (~2–6 MPa), except for the compositions
Ceramics International 43 (2017) 10207–10216
Fig. 4. Cold flexural strength of the designed castables after curing (50 °C/24 h) and
drying (110 °C/24 h). TA = reference, H3BO3 = boric acid, BS = sodium borosilicate, BM
= magnesium borate and B4C = boron carbide.
containing BS or B4C. Sodium borosilicate addition resulted in a
refractory structure with higher porosity when compared to the
reference material [TA =12.5% ± 0.8, TA +(0.5–2.0 wt%) BS =13.2–
14.0% ± 0.9 leading to a lower modulus of rupture values (Fig. 4). On
the other hand, despite the similar apparent porosity levels of TA and
TA + B4C [TA+(0.5–1.0 wt%) B4C =12.6% ± 0.8], boron carbide-
containing refractories still presented higher green mechanical
strength (Fig. 4).
Aiming to identify the starting temperature of the sintering reac-
tions for the compositions and the SA effects on the samples stiffness
behavior, in situ hot elastic modulus analyses were carried out during
the first heating/cooling cycle of the prepared castables. Fig. 5 shows
the E evolution of the dried refractories (110 °C/24 h) from 30 to
1400 °C.
Each graph in Fig. 5 points out the elastic modulus results obtained
for a composition containing one specific SA and different contents of
this compound: 0, 0.5, 1.0 or 2.0 wt% (except for the formulations with
H3BO3 and B4C due to the limited flowability of some mixtures, see
Fig. 3). In general, a significant drop of the samples’ stiffness could be
observed between 110 °C and 700–1000 °C, depending on the added
SA. This behavior can be associated with the decomposition of
hydrated phases [mainly crystalline and/or gel Al(OH)3 and other
(3) amorphous phases] derived from the binding action of hydratable
alumina [21,22]. These transformations were expected to take place
between 110–600 °C, leading to the castables’ elastic modulus drop
due to the increase in the overall porosity level of such materials. After
that, the sintering reactions took place at lower temperatures for the
SA-containing refractories (600–950 °C), resulting in a high increase of
their E values. Conversely, this effect was only observed for TA
(reference = additive-free material) above 1000 °C.
Therefore, these measurements highlighted some advantages of
adding boron sources (induce faster sintering) to alumina-based
refractories. The specific starting temperature at which the reactions
and, consequently, densification of the microstructure take place
depends on the generation of a boron-rich liquid phase into the
compositions. Table 1 shows the expected B2O3 content to be formed
at high temperatures in each evaluated castable containing different
SA. Due to the different natures of the selected boron sources, they
should undergo distinct reactions (i.e., decomposition, oxidation,
melting [18,23,24]) during heating (Eqs. (4)–(7)). Therefore, depend-
ing on the kinetics of these transformations, a suitable content of a
boron-rich liquid phase might be generated in the samples’ structure,
favoring the material's diffusion and precipitation of aluminum borates
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Fig. 5. In situ hot elastic modulus of the evaluated castables containing different sintering additives (0.0, 0.5, 1.0 or 2.0 wt%): (a) boric acid [H3BO3], (b) sodium borosilicate [BS], (c)
magnesium borate [BM] and (d) boron carbide [B4C]. All samples were previously cured at 50 °C/24 h and dried at 110 °C/24 h before testing.

(as will be further discussed). The formation of strong ceramic bonds stable and alumina-rich borate, Eq. (8)) may also play a role in the
among these novel compounds and the original raw materials of the samples´ softening around 900–950 °C (Fig. 5d). After completing this
compositions results in a continuous and increasing stiffening of the reaction (Eq. (8)), the densification of the refractory should progress
refractories up to 1400 °C (Fig. 5). and increase the material's stiffness up to 1400 °C [2,12].
Δ Δ
2H3BO3⟶B2O3(s) + 3H2O Temperature~171°C (4) 2Al2O3. B2O3 + 7Al2O3⟶9Al2O30.2B2O3 (8)

Δ An E increase of the SA-containing compositions could still be

B2O3(s)⟶B2O3(l ) Temperature~470°C
Δ
Mg2B2O5⟶2MgO + B2O3(l ) Temperature~850–1000°C
Δ
B4C + 4O2(g)⟶2B2O3(l ) + CO2(g) Temperature~600°C
Two interesting E changes could be detected in the 700–900 °C and
900–1200 °C temperature range for the TA+0.5 wt% B4C castables
(Fig. 5d). Eq. (7) indicates that this SA should be oxidized around
600 °C, giving rise to liquid boron oxide and CO2(g). As mentioned
before, the former component (B2O3(l)) speeds up the liquid-phase
sintering process of this refractory and induces the precipitation of
2Al2O3.B2O3 in the microstructure at intermediate temperatures (see
Fig. 1), which should result in an E increase. Thus, the elastic modulus
variation observed around 700–900 °C in the profile of TA+0.5 wt%
B4C samples is related to boron carbide oxidation and liquid genera-
tion. At 900 °C, another E drop was observed as a consequence of the
higher content of B2O3(l) available in the refractory structure, favoring
its softening. Moreover, some authors [8,25] stated that the following
transformation involving 2Al2O3.B2O3 + alumina (to generate a more
(5) observed during cooling due to the continuous reactions between
liquid-refractory components and the remaining glassy phase solidifi-
(6) cation [2]. By comparing the TA (additive-free) and TA +1 wt% B4C
(Fig. 5d) materials's behavior, it can be detected that these refractories
showed distinct elastic modulus profiles from 1400 °C down to 30 °C.
(7)
Although TA samples presented a smooth stiffness variation during
cooling, the compositions containing 1 wt% of B4C showed an E
increase from 1400 °C down to 500 °C and a further drop of this
property below 500 °C, which is related to the thermal expansion
mismatch (resulting in flaw formation) of the generated phases and the
original raw materials of the refractory [2]. Considering this negative
effect derived from the action of B4C (when 1 wt% of this additive was
incorporated into the castable), only the composition containing 0.5 wt
% of this SA was evaluated in the following tests.
In order to figure out whether the boron-rich liquid phase (formed
in the designed compositions at high temperatures) would present
transient (mainly consumed during the first heating-cooling cycle) or
permanent (still present in the refractory structure when carrying out
further thermal cycles) behavior, pre-fired samples (1400 °C for 5 h) of
the evaluated castables were re-heated now measuring their elastic

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Table 2 Fig. 6b, despite the good performance of TA-BS refractories at room
Elastic modulus values of the pre-fired (1400 °C for 5 h) castable samples before the in temperature (Table 2), sodium borosilicate induced the generation of a
situ E measurements as a function of temperature.
high liquid content in the evaluated materials even when only 0.5 wt%
Compositions E results (GPa) of this SA was added to the alumina-based mixture. Magnesium borate
(BM)-containing castables (Fig. 6c) also presented a more significant E
TA (additive-free) 113.2 ± 3.7 drop above 800 °C (when compared to the additive-free, TA+H3BO3
TA + 0.5 wt% H3BO3 166.7 ± 1.8
and TA+B4C materials), indicating that, although boron and magne-
TA + 1.0 wt% H3BO3 136.2 ± 2.6
TA + 0.5 wt% BS 170.0 ± 3.1 sium interaction with alumina might have taken place during the first
TA + 1 wt% BS 170.8 ± 2.4 thermal treatment of the samples, most likely these transformations
TA + 2.0 wt% BS 175.5 ± 1.1 did not induce an efficient liquid consumption and precipitation of new
TA + 0.5 wt% BM 170.0 ± 3.4 crystalline phases. Thus, a subsequent heating of these pre-fired
TA + 1 wt% BM 141.8 ± 2.2
refractories still highlights the presence of a glassy phase in the
TA + 2.0 wt% BM 148.8 ± 4.3
TA + 0.5 wt% B4C 146.1 ± 2.1 microstructure and its softening at high temperatures. On the other
hand, the samples containing 0.5 wt% of B4C presented a similar E
profile to the TA (reference, Fig. 6d) castable.
modulus as a function of the temperature. Thermodynamic calculations were carried out using FactSage soft-
Table 2 and Fig. 6 present the actual stiffness (GPa) and the E ware (considering the matrix fraction of the compositions, d < 45 µm)
change (%) attained before and during the in situ hot elastic modulus in order to predict the phases that could be generated in the evaluated
measurements, respectively. After the pre-firing step, the additive-free castables in the 200–1600 °C temperature range. The simulations were
sample was the one with the lowest E value (113.2 GPa), whereas the performed for the compositions containing: 0.5 wt% H3BO3 or B4C and
sodium borosilicate (BS)-containing materials attained values around 0.5 wt% and 2.0 wt% of BS or BM. Fig. 7 shows the phases expected to
170–175 GPa (Table 2). be present in these castables at high temperatures.
In general, the compositions with a lower amount of SA (0.5 wt%) When adding 0.5 wt% of H3BO3 to the alumina castable's matrix,
showed higher elastic modulus results at room temperature (Table 2) aluminum hydroxide (Al2O3.H2O) up to 350 °C and aluminum borate
and also at high temperatures, as a greater softening of the samples (9Al2O3.2B2O3) should be the main phases generated in this system
containing 1.0 or 2.0 wt% of the additives (H3BO3, BS or BM, Fig. 6) (Fig. 7a). Additionally, as reported by some authors [4,6], boron
could be observed. Based on the E percentual change (%) shown in volatilization is also expected to be observed at high temperatures,

Fig. 6. Hot elastic modulus change (%) with temperature of the designed castables containing different sintering additives (0.0–2.0 wt%): (a) boric acid [H3BO3], (b) sodium
borosilicate [BS], (c) magnesium borate [BM] and (d) boron carbide [B4C]. All the evaluated samples were pre-fired at 1400 °C/5 h before testing.

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I.D. Giovannelli Maizo et al.
Fig. 7. Thermodynamic simulation results predicting the phases contained in the castables’ matrix (d < 45 µm) in the temperature range of 200–1600 °C. The following compositions
were evaluated: (a) 0.5 wt% H3BO3, (b) 0.5 wt% B4C, (c) 0.5 wt% BS, (d) 2.0 wt% BS, (e) 0.5 wt% BM or (f) 2.0 wt% BM.
resulting in the decrease of the aluminum borate phase content above
1000 °C, as shown in Fig. 7a. According to the Rietveld analysis carried
out for TA+0.5 wt% H3BO3 matrix samples fired between 1000 and
1400 °C for 5 h, the same trend (decrease of 9Al2O3.2B2O3 content)
was identified in the experimental tests (XRD results not shown here).
Although less intense than for the mixture with boric acid, boron
volatilization was also detected in the thermodynamic simulations of
TA+0.5 wt% B4C composition (Fig. 7b). As shown in Table 1, the
addition of boron carbide to the castable should provide a higher
amount of B2O3(l) to react with alumina after its oxidation at ~600 °C,
resulting in a greater content of 9Al2O3.2B2O3 (Fig. 7b). Due to the
generation of an expressive amount of this borate in the TA+ B4C
castables, it is believed that this phase is responsible for the E drop
detected during the samples’ cooling step (Fig. 5d) for the composition
containing 1 wt% of this SA.
The formation of new solid phases at high temperatures was also
predicted for the refractories containing 0.5 or 2 wt% of BS or BM
(Fig. 8a-b). Based on the calculations, TA-BS mixtures may present
mullite (3Al2O3.2SiO2), whereas 9Al2O3.2B2O3 and magnesium-alumi-
nate spinel (MgAl2O4) is expected to be found in the TA+BM ones.
These three compounds present interesting thermo-mechanical prop-
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Ceramics International 43 (2017) 10207–10216
erties (i.e., high melting point, etc.) [5,6,10] and, most likely, they
should enhance the alumina-based castable performance.
On the other hand, both sintering additives (BS and BM) induced
the generation of the liquid phase in the evaluated castables at
temperatures higher than 1100 °C or at ~1600 °C for the borosilicate
or magnesium borate-containing compositions, respectively. These
results are in tune with the hot elastic modulus measurements carried
out to evaluate the pre-fired samples (Fig. 6b and c), as a greater
softening of the TA+BS and TA+BM samples could be identified above
1000 °C. However, it is also important to highlight that, despite the
liquid formation in these compositions, the actual E values of the SA-
containing compositions were higher (see Table 2) than the reference
material (TA) in the 30–1400 °C temperature range.
XRD measurements and Rietveld calculations were carried out in
order to quantify the crystalline phases (mullite, spinel and borates)
formed in the castable's matrix (d < 45 µm) containing 2 wt% of BS or
BM additives and fired at 600 °C, 900 °C, 1200 °C and 1400 °C for 5 h.
Fig. 8a shows that the TA-BS matrix did not present mullite as pointed
out in the theoretical simulations (Fig. 7d). This result might be
associated with the limited amount of SiO2 available in this composi-
tion, which prevents the generation of this alumino-silicate in the
I.D. Giovannelli Maizo et al. Ceramics International 43 (2017) 10207–10216

Fig. 8. Rietveld quantification of the phases formed in the refractories's matrix (d < 45 µm) after the pre-firing step at 600, 900, 1200 and 1400 °C for 5 h. The castables contained 2 wt
% of: (a) sodium borosilicate [BS] or (b) magnesium borate [BM].

evaluated conditions [26]. Another important aspect is the reduced

amount or lack of aluminum borates in the TA+BS samples fired at
1200 °C and 1400 °C (Fig. 8a), indicating that most likely B2O3
(derived from the SA) should be found as a component of the glassy
(amorphous) phase contained in this system. Although distinct con-
tents of 9Al2O3.2B2O3 and MgAl2O4 were attained by the Rietveld
analysis (Fig. 8b) and thermodynamic calculations (Fig. 7f) for TA
+2 wt% of BM matrix, these phases were still present in the prepared
samples fired at 1200 °C and 1400 °C for 5 h.
Further thermo-mechanical tests were carried out to evaluate the
effect of the SA additives in the castables’ erosion resistance, hot
modulus of rupture (HMOR) and thermal shock resistance. The
following compositions were selected to be analyzed in this step:

(i) TA +0.5 wt% H3BO3 and TA +0.5 wt% B4C due to their suitable
flowability and reduced softening as a function of temperature;
(ii) TA +1 wt% BS [despite the softening of this refractory at high
temperatures (Fig. 6b) due to the liquid phase generation
(Fig. 7d), faster sintering and higher E values (Table 2) could be
Fig. 9. Cold eroded volume of the evaluated castables. All samples were pre-fired at the
attained for this composition when compared to the TA one); and
indicated temperatures for 5 h before the measurements.
(iii) TA +2 wt% BM (as this SA induced the formation of spinel and
aluminum borate in the castable microstructure).
temperatures (Fig. 10a), and also the results for the castables thermally
treated at higher temperatures (1450–1550 °C for 5 h) but evaluated at
Erosion resistance of refractory products carried out at room
1400 °C (Fig. 10b). TA (additive-free) refractory presented lower
temperature is an important test used to select promising materials
HMOR at 1000 °C, but a continuous increase of its mechanical
for petrochemical and aluminum industries, as in these applications
resistance can be detected when raising the firing and testing tem-
the ceramic lining may be subjected to the contact with abrasive
peratures. As shown in Fig. 5, the sintering process of this reference
particles conveyed at high velocity (50 m/s) [2]. Fig. 9 presents the cold
composition should mainly take place above 1000 °C, which explains
eroded volume attained for the AS-containing compositions, as well as
the improved TA samples’ performance in the HMOR measurements
the additive-free (TA) castable after pre-firing the samples at 1000 °C,
carried out at 1200 °C and 1400 °C.
1200 °C and 1400 °C for 5 h.
TA +0.5 wt% B4C and TA +2.0 wt% BM presented the highest hot
The late sintering/densification of the TA composition (as hydra-
mechanical strength at 1000 °C and 1200 °C (Fig. 10a). Such behavior
table alumina requires high temperatures to provide effective material
must be related to the faster sintering and the formation of aluminum
diffusion with the generation of strong ceramic bonds between coarse
borates (2Al2O3. B2O3 and 9Al2O3.2B2O3) and MgAl2O4 phases in these
and fine components of the refractory) resulted in full erosion of the
samples. Nevertheless, after firing the SA-containing compositions at
samples fired at 1000 °C and 1200 °C (Fig. 9). This reference material
higher temperatures (1400–1550 °C) and testing them at 1400 °C
only withstood the wearing caused by the contact with the SiC particles
(Figs. 10a and 10b), the castables presented similar HMOR results
when this castable was previously thermally treated at 1400 °C for 5 h.
(~4.5–8.0 MPa) which can be explained by the partial decomposition
Conversely, by adding SA to the designed mixtures, the earlier sintering
of the alumina-rich borate, resulting in (i) boron volatilization (as
(associated with boron-rich liquid phase generation and precipitation
predicted in the thermodynamic calculations and also identified by the
of new crystalline phases, as mentioned before) led to refractories with
Rietveld calculations carried out for the castable's matrix samples pre-
enhanced erosion resistance. Based on these results, there is a great
fired at 1400 °C for 5 h, Figs. 7 and 8, respectively) and (ii) the liquid
potential for using these SA-containing compositions in equipment for
generation (inducing the softening of these materials as shown in the
the petrochemical and aluminum production processes, as they com-
hot elastic modulus measurements, Fig. 6). Despite these aspects, the
monly operate at working temperatures lower than 1300 °C.
attained mechanical strength values for the boron-containing alumina-
Fig. 10 shows the hot mechanical strength of the samples pre-fired
based castables are suitable and similar to other refractory systems
at 1000 °C, 1200 °C and 1400 °C for 5 h and tested at the same firing

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I.D. Giovannelli Maizo et al.
Fig. 10. Hot modulus of rupture (HMOR) of the designed castables. All samples were pre-fired for 5 h (a) at the same testing temperatures or (b) at 1450, 1500 and 1550 °C for 5 h
before the measurements and evaluated at 1400 °C.
evaluated at 1400 °C [2,3]. Additionally, due to the enhanced perfor-
mance of TA +0.5 wt% B4C and TA +2.0 wt% BM compositions at
1000 °C and 1200 °C (Fig. 10a), these castables might be good options
to be used in petrochemical and aluminum industries.
The damage induced by thermal shock tests was followed by
monitoring the elastic modulus changes of refractory samples (pre-
fired at 1400 °C for 5 h) along 10 cycles under a ΔT of approximately
1000 °C. Fig. 11 indicates the measured E values and their percentual
decay. Although TA +0.5 wt% B4C and TA +2.0 wt% BM samples
showed a higher drop of their stiffness in the 0–10 cycles range
(Fig. 11b), all SA-containing castables still presented higher E values
than the reference material (TA, Fig. 11a). Thus, based on these results,
the designed boron-containing refractories are better options to with-
stand stresses derived from severe temperature changes.
4. Conclusions
This work evaluated the addition of different boron sources (boron
oxide, boric acid, sodium borosilicate, magnesium borate and boron
carbide) in hydratable alumina-bonded castables in order to better
understand their role as sintering additives and develop enhanced
refractory materials for applications that require intermediate working
temperatures (600–1200 °C).
The incorporation of boron oxide into the designed castables is not
Fig. 11. (a) Elastic modulus changes and (b) its decay as a function of the thermal shock cycles (0−10) with ΔT=1000 °C. The samples were pre-fired at 1400 °C/5 h before the
measurements.
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Ceramics International 43 (2017) 10207–10216
recommended as this hygroscopic material reduced the flowability of
the compositions, preventing a suitable preparation of the samples. The
other boron-containing compounds could be directly added to the high-
alumina mixtures without resulting in major changes in their proces-
sing steps. Nevertheless, it is very important to select a proper SA and
optimize its content in the castable composition in order to attain faster
sintering, but with no drawbacks to their thermo-mechanical proper-
ties.
The addition of only 0.5 wt% of H3BO3 or B4C to the evaluated
materials induced the formation of B2O3(l) and the further precipitation
of aluminum borates (2Al2O3.B2O3 and 9Al2O3.2B2O3) in the samples
fired above 600 °C. These transformations sped up the sintering/
densification process, which resulted in refractories with enhanced
hot modulus of rupture, erosion and thermal shock resistances.
However, if an expressive amount of 9Al2O3.2B2O3 is attained in the
evaluated system (i.e. when adding 1 wt% of B4C to the mixture), this
phase may not be well accommodated (thermal expansion mismatch)
in the resulting microstructure and may cause defects that will reduce
the castables’ stiffness. Aluminum borates could not be identified in the
compositions containing 0.5–2.0 wt% of sodium borosilicate, indicat-
ing that this additive effectively acted accelerating the sintering process
(~800 °C) but the remaining glassy phase (derived from the SA)
resulted in a higher softening of the samples (even when evaluating
pre-fired ones) above 1000 °C. On the other hand, 9Al2O3.2B2O3 and
I.D. Giovannelli Maizo et al.
MgAl2O4 were found in the fired refractories containing magnesium
borate. Despite the precipitation of these phases in the castables’
microstructure, all the evaluated compositions did not show full
transient liquid phase sintering, as the samples still presented a greater
softening than the additive-free material (due to the presence of liquid)
when subjected to further heating cycles at high temperatures.
It can be pointed out that boric acid, sodium borosilicate, magne-
sium borate and boron carbide are suitable sintering additives to be
added to hydratable alumina-bonded castables, as they all induced
faster sintering and improved the thermo-mechanical performance of
the evaluated refractories at intermediate temperatures. However,
previous trials must be carried out when selecting the boron source
and its content, as they may affect the overall rheology and hot
mechanical properties of the castable's compositions.
Acknowledgments
The authors are thankful to the Coordenação de Aperfeiçoamento
de Pessoal de Nível Superior (CAPES) and the Federation for
Refractory Research and Education (FIRE) for supporting this work
and to Magnesita Refratários S.A.
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