IMPROVING REFRACTORY CASTABLES BY ADDING A NOVEL

SPHERICAL ALUMINA

Mariana A.L. Braulio*

4Cast-Technical Assistance and Consulting on Refractories, São Carlos, Brazil

Guilherme G. Morbioli, Priscila Guilherme, Victor C. Pandolfelli

Federal University of São Carlos, Materials’ Microstructural Engineering Group

(GEMM/UFSCar), São Carlos, Brazil

Bjorn Myhre, Hong Peng, Arianeh Aamodt

Elkem Silicon Materials, Kristiansand, Norway

* Presenting author (e-mail address: mariana.4cast@gmail.com)

ABSTRACT

The refractory market supplies many types of alumina raw materials, from coarse tabular

or electrofused ones to fine powders (calcined and reactive). Among them, a novel

alternative (AloxX-Spheres 99) has recently been developed, aiming to improve the

castables’ flowability and sinterability at intermediate temperatures, due to its spherical

shape. The objective of this paper is to highlight the benefits attained by AloxX addition

in different processing steps. High-alumina castables bonded with SioxX-Zero or

colloidal silica were evaluated regarding workability, mechanical strength after curing

and drying/firing, water withdrawal, HMOR and thermal shock resistance. The results

indicated that the better packing induced by the addition of AloxX minimized the amount

of water required for shaping and enhanced the physical properties. Furthermore, this

morphology helps to optimize castables’ sinterability, leading to outstanding mechanical

strength values after firing, pointing out its potential to improve the properties of refractory

compositions.

1. INTRODUCTION

Microsilica is well-known by its spherical shape and the consequent advantages

regarding particle packing and castables’ flowability [1]. In this context, a novel alumina

raw material is under development (AloxX-Spheres 99), with a similar morphology

feature. The objective is to improve packing, minimizing the water amount and also

enhancing the castable’s properties.

In parallel to this effort, the continuous search for alternative binders to replace traditional

hydraulic ones (calcium aluminate cement and hydratable alumina) led to the generation

of SioxX-Zero, which is a “dry-version” of a silica-based binder. This material is actually

a microsilica-alumina-based binder for SiO2-gel bonded no-cement castables and has

the advantage of improving the green mechanical strength and the setting / hardening

during curing when compared with colloidal silica-based compositions [2, 3]. Another

benefit is that this raw material is supplied as a dry powder, which eases mixing and

mainly gunning / shotcrete installation.

Considering these aspects, this work addressed the benefits of AloxX as an alumina raw

material alternative and its potential binding effect when coupled with microsilica. The

effect of this product when combined with SioxX-Zero and microsilica was also

evaluated. A colloidal-silica bonded-castable was also prepared in order to be compared

with the SioxX-Zero-containing system. The results highlighted that both products have

suitable performance in different castables’ processing steps, pointing out novel

alternatives for the development of new refractory systems.

2. MATERIALS AND TECHNIQUES

Free-flow castables were formulated considering the Alfred particle packing model (q =

0.21), comprising different contents of AloxX, microsilica (971U) and SioxX-Zero (Elkem

Silicon Materials, Norway), tabular (d ≤ 6 mm) and reactive alumina (CL370 and CT3000,

Almatis, USA). Calcium aluminate cement (Secar71, Kerneos, France) was added (0.5

wt%) in all compositions, except the colloidal-silica one, that was gelled by dead-burnt

MgO (< 45 μm, 98 wt% of MgO, Magnesita Refratários S. A., Brazil). A 50 wt%-solid

colloidal silica suspension was used (Bindizil 50/80, Akzo Nobel, USA). For the castables

containing SioxX-Zero and colloidal silica no dispersant was added, as both products

have already additives. Conversely, for the SioxX-Zero-free composition (15AM), 0.2

wt% of an electrosteric dispersing agent was added (Castament FS20, BASF, Germany).

Table 1 indicates the main differences among the designed castables. AloxX was added

in two different amounts: 5 wt%, which is in tune with industrial reality considering cost

reductions, and 15 wt%, that is the maximum content that was possible to be added

without affecting the particle size distribution. Furthermore, the overall SiO2 content in all

compositions was kept the same (3 wt%).

After defining the water content for a suitable flowability, the materials were cast into 40

x 40 mm cylindrical molds and the mechanical strength was evaluated after curing at

50°C (in wet environment) for 1 day. Mechanical strength tests were also carried out

after firing at intermediate temperatures (5 hours at 350, 600, 800 and 1000°C). The

mechanical evaluation was conducted according to the ASTM C496-90 standard

(Splitting Tensile Strength of Cylindrical Concrete Specimens) in MTS testing equipment

(MTS Systems, Model 810, USA). Apparent porosity of these samples were measured

using ASTM C380-00. Thermogravimetric analyses to evaluate the explosion likelihood

were conducted up to 800°C under a heating rate of 20°C/min, on castables cured for 1

day at 50°C. The thermogravimetric device was developed in the authors’ research group
and the mass loss during drying (W) was calculated [4]. Specimens fired at 600°C were

used to evaluate the castables’ permeability (cylinders with 60 mm diameter and 22 mm

height), according to experimental procedure described by Innocentini et al. [5]. The

permeability constant (k1) was calculated by the Forchheimer’s equation.

Table 1 - Designed castables’ formulations and main studied variables.

Content (wt%)
Raw materials
SM 5ASM 15ASM 15AM 15ACS
Coarse tabular alumina 78 78 76 76 76
Tabular alumina < 45 µm 7 7 2 2 2.45
Tabular alumina < 20 µm 5 0 0 0 0
CL370 4.3 4.3 2.3 2.3 2.3
CT3000 1 1 0 1.2 4.2
AloxX 0 5 15 15 15
SioxX-Zero 3 3 3 0 0
Microsilica 1.2 1.2 1.2 3 0
Colloidal silica 0 0 0 0 6
Secar71 0.5 0.5 0.5 0.5 0
MgO < 45 µm 0 0 0 0 0.05

For the thermal shock analyses (ASTM C1171-91), bars pre-fired at 1000°C for 5h (150

x 25 x 25 mm) were subjected to thermal cycles with a temperature gradient of 975°C

(1000°C to room temperature) and the elastic modulus (E) decay was evaluated. The E

measurements were conducted using the bar resonance technique. Following that, bars

with the same dimensions were molded to evaluate the hot modulus of rupture (HMOR,

3-point bending tests) after firing at 1000, 1200 and 1400°C for 5h. The HMOR tests

were performed at these temperatures in HBTS 422 equipment (Neztsch, Germany).

Besides the compositions listed in Table 1, four other ones were prepared aiming to

highlight AloxX effect and minimize the liquid formation impact: SM MgO (similar to SM,

but with 0.5 wt% MgO instead of 0.5 wt% CAC); 5ASM MgO (similar to 5ASM, with the

same replacement as SM MgO); NANS CAC (based on SM composition, but with no

AloxX and no silica, and with 4.7 wt% of CAC instead of SioxX+microsilica); and 5ANS

CAC (based on 5ASM composition, with 4.7 wt% of cement).

3. RESULTS AND DISCUSSION

Fig. 1 shows the flowability results as a function of time for the different designed

compositions. The water content was set up to provide similar initial free-flow values (90-

100%) and the only castable that did not reach this target was the colloidal silica-bonded

one, due to gelling effects. The water content (in wt%) of each castable was: 5.0 for SM,

4.8 for 5ASM, 4.3 for 15ASM, 4.3 for 15AM and 7.4 for 15ACS. The addition of AloxX

induced a slower decay in the free-flow value with time, pointing out that this raw material

can improve the castables’ workability. Whereas the SM composition presented 1h of

workability, the continuous addition of AloxX increased this time (1h20min for 5 wt% and

more than 2h for 15 wt%). The absence of SioxX and the presence of another dispersant

agent for composition 15 AM led to even better free-flow versus time results.

Nevertheless, when comparing the 15ASM castable with the 15ACS one, it is clear that

SioxX results in higher flowability compared with colloidal silica, which provides time for

suitable shaping of large pieces.

SM 5ASM 15ASM 15AM 15ACS

100
Flowability (%)

80
60
40
20
0
0 20 40 60 80 100 120
Time (min)

Fig. 1 - Flowability versus time curves for different castable formulations.

After defining the water content, green mechanical strength samples were prepared and

evaluated after 1 day curing at 50°C and after curing at 50°C for 1 day followed by drying

at 110°C also for a day. All compositions showed similar values (Fig. 2), except the

15ACS one, once again indicating the benefit of SioxX-Zero binding agent when

compared with colloidal SiO2. The SioxX-Zero-free castable (15AM) also showed
suitable strength, pointing out that the AloxX + microsilica combination can be an

interesting binding route as well. The splitting tensile strength (STS) is the closest one to

the tensile mechanical value, showing in a more realist manner the binding effect of

ceramic compositions.

1day50C 1day110C

2,0

1,6
STS (MPa)

1,2

0,8

0,4

0,0
SM 5ASM 15ASM 15AM 15ACS

Fig. 2 - Green mechanical splitting tensile strength (STS) after curing at 50°C and drying at

110°C, for 1 day, of different castable formulations.

The drying/spalling behavior of samples cured for 1 day at 50°C was analyzed by heating

them up to 800°C, under an aggressive heating rate of 20°C/min. Fig. 3 indicates that

the mixture of Allox + SioxX-Zero + microsilica resulted in the sample’s explosion under

this condition, which is related to the lowest permeability level observed for all the

prepared compositions (Table 2). However, there are three alternatives to keep using

AloxX and SioxX-Zero with no damage: (i) reducing AloxX content (no explosion took

place for the 5ASM composition), (ii) not adding SioxX and using AloxX+microsilica as

the binding system (no spalling for the 15AM castable), (iii) previously drying the samples

at 110°C for 1 day (the same high rate test was conducted and the sample 15ASM did

not spall under this condition). For the 15ACS composition, the water withdrawal was

higher due to the greater amount of water used in this composition.

The mechanical strength at intermediate drying / initial sintering temperatures was

measured and pointed out outstanding values for the 15AM composition (Fig. 4), mainly

at 1000°C (the samples reached the maximum equipment threshold without breaking
up). The AloxX + microsilica combination is thus an interesting binding alternative to

improve mechanical strength at typical temperatures in which calcium aluminate cement

and hydratable alumina are usually under their hydrate decomposition process and, thus,

providing weak bonds to the castables. This is especially appropriate for equipment that

operate in this temperature range, such as aluminum melting furnaces, petrochemical

risers, alumina calciners, and others. Conversely, in the presence of SioxX-Zero, the

increasing addition of AloxX seems to spoil the mechanical property, indicating that

mixing AloxX and SioxX-Zero is not effective. Nevertheless, using just one of them

seems to be suitable as, besides the good results of 15AM castable, the 15ASM

composition was superior than the colloidal silica one (15ACS).

SM 5ASM 15ASM 15AM 15ACS

100,2
99,2
98,2
W (%)

97,2
96,2
95,2
94,2
0 200 400 600 800
Temperature (°C)

Fig. 3 - Weight loss (W) during spalling tests (20°C/min) up to 800°C for different castable

formulations, previously cured for 1 day at 50°C.

Table 2 - Physical properties (permeability - k1 - and apparent porosity - AP) of different

castable formulations, prepared in distinct conditions (dried for 1 day at 110°C or fired at

600°C for 5h).

SM 5ASM 15ASM 15AM 15ACS

k1 - 600°C
3.34 ± 1.25 2.29 ± 0.10 1.51 ± 0.18 3.86 ± 0.67 574.8 ± 95.3
[x10-16 m2]
AP - 110°C
14.18 ± 0.63 12.52 ± 0.39 13.75 ± 0.58 10.52 ± 0.43 17.79 ± 0.69
[%]
AP - 600°C
15.87 ± 0.38 14.71 ± 0.30 15.35 ± 0.74 12.74 ± 1.32 17.93 ± 0.54
[%]
 SM 5ASM 15ASM 15AM 15ACS

16

12

STS (MPa)
8

0
110 350 600 800 1000
Firing temperature (C)

Fig. 4 - Mechanical splitting tensile strength (STS) at intermediate temperatures of different

castable formulations.

Due to the good results attained at 1000°C, thermal shock tests were conducted for

samples pre-fired at this temperature for 5h and using a thermal gradient of 975°C

(1000°C to room temperature). Fig. 5 shows the elastic modulus (E) decay as a function

of the thermal cycles, again highlighting the great performance of the 15AM material. It

did not only present a remarkable initial E value (120 GPa) without any addition of

sintering additive, but also showed the highest elastic modulus (87 GPa) after 8 thermal

shock cycles, decreasing only 26% of its initial value. On the other hand, all other

compositions had initial E values inferior to 83 GPa and higher percentage E decays

after 8 cycles (ranging from 45 to 50%). The AloxX + SioxX-Zero + microsilica containing

compositions (5ASM and 15 ASM) were slightly better than the reference with no AloxX

(SM). However, it seems that an excess of AloxX (15wt%) combined with SioxX-Zero is

not advantageous as the composition containing only 5 wt% of AloxX showed high E

values. For the colloidal silica-bonded system, although the initial E was the lowest one,

it did not present a relevant E loss during thermal cycling, whereas the SioxX-Zero

castables are more sensitive to thermal shock, even though the final E absolute values

are similar.

The best behavior of the 5ASM composition compared with the 15ASM one was also

noticed for the hot modulus of rupture evaluation (Fig. 6). Extremely high HMOR value
was attained at 1000°C for this castable (45 MPa) and also for the 15AM one (48 MPa).

This later was once again the best one of the set of compositions, showing the highest

values for all testing temperature. The mechanical strength decrease observed at

1200°C and 1400°C for all castables might be associated with the presence of SiO2 and

CaO in all compositions, except for the colloidal silica-bonded one (no CAC added).

Furthermore, it is very likely that for Al2O3-SiO2 compositions the sintering dwell time at

1400°C must be longer in order to induce mullite formation.

SM 5ASM 15ASM 15AM 15ACS

Elastic Modulus (GPa)

140
120
100
80
60
40
20
0
0 2 4 6 8
Number of cycles

Fig. 5 - Elastic modulus as a function of the thermal shock cycles for different castable

formulations.

SM 5ASM 15ASM 15AM 15ACS

60
50
HMOR (MPa)

40
30
20
10
0
1000 1200 1400
Testing temperature (C)

Fig. 6 - Hot modulus of rupture at different testing temperatures (1000-1400°C) for different

castable formulations.

In order to minimize this problem and highlight the benefits of adding AloxX to refractory

compositions, different adjustments in the formulations were conducted to analyze the

HMOR (Table 3). When eliminating 0.5 wt% of CAC (SM MgO / 5ASM MgO), the addition

of AloxX was advantageous. However, the HMOR levels at 1200°C and 1400°C were

also low, as the Al2O3-SiO2-MgO system can also generate liquid phase. Conversely, for

the Al2O3-CAC systems (without SiO2 or MgO, NANS CAC / 5ANS CAC), a particular

behavior was detected: AloxX addition was effective for lower temperatures, whereas at

the highest testing temperature (1400°C) the composition without AloxX performed

better. This aspect indicates that the incorporation of AloxX may be evaluated for each

specific system in order to check whether it improves the castable’s performance, as

took place in many steps of this work.

Table 3 - HMOR values for compositions without CAC (with SiO2 and Mg) or with CAC

(without SiO2 or MgO).

Testing temperature (°C)

1000 1200 1400
SM MgO 18.91 ± 2.26 2.99 ± 0.19 1.50 ± 0.11
5ASM MgO 20.14 ± 1.47 4.86 ± 0.93 1.86 ± 0.35
NANS CAC 8.38 ± 1.31 9.38 ± 1.15 16.57 ± 1.73
5ANS CAC 8.58 ± 1.33 10.46 ± 0.94 12.39 ± 0.72

4. CONCLUSIONS

Both AloxX and SioxX-Zero presented interesting results. Whereas AloxX seems to

perform better when coupled only with microsilica (leading to outstanding cold and hot

mechanical strength and thermal shock behavior), SioxX-Zero appears as an interesting

alternative to replace colloidal silica, facilitating the castable’s mixing and installation,

and improving the green mechanical strength. Therefore, both raw materials may be

evaluated with care for new refractory developments, as they can provide better

properties for different processing steps when added separately for distinct purposes.

5. ACKNOWLEDGEMENTS

The authors are grateful to FIRE and Elkem for supporting this work.

Trabajo enmarcado en la red HOREF (312RT0453) de CYTED.

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