MgO SiO2 H2O

bonded MgO based castables

Part 2: Effect of pumping and wet shotcreting on cold and hot

properties and slag resistance
Ningsheng Zhou, Sanhua Zhang, Shuhe Hu, Zhenyong Bi, Luoyang Institute of Refractories Research
Zhiqiang Chen*, Cecilie degrd, Bjrn Myhre, Bjrn Sandberg, Elkem ASA Materials
Presented at UNITECR 03, 8th Biennal Worldwide Conference on Refractories
in Osaka, Japan, October 19-22, 2003.

The fine art of

MgO SiO2 H2O bonded castables

Part 2: Effect of pumping and wet shotcreting on cold and hot
properties and slag resistance
Ningsheng Zhou, Sanhua Zhang, Shuhe Hu, Zhenyong Bi, Luoyang Institute of Refractories Research
Zhiqiang Chen*, Cecilie degrd, Bjrn Myhre, Bjrn Sandberg, Elkem ASA Materials

Abstract
Trial installations of MgO refractory castables in
moulds by pumping and wet sprayed onto wooden
boards were performed using an Allentown Pump RP10. Based on previous work, the self-flowing castable
with microsilica contents of 6 wt% for both selfflowing and vibration castable was chosen out of a
number of test castables. The given two recipes are suitable for pumping due to their flowability and
sufficient working time. The pumped and sprayed samples were compared to the samples prepared in the
laboratory in terms of bulk density, apparent porosity,
cold modulus of rupture, hot modulus of rupture at
1200-1500C and refractoriness under load. Samples
from the lab-prepared, pumped and shotcreted, were
subjected to slag attack by rotary slag test to compare
their slag resistance. Two kinds of steel-making slag
with high and low CaO/SiO2 ratios were used.
Differences have been found and discussed.

1. Introduction
With good resistance to high basicity slag in modern
steel-making processes, MgO clinker is an indispensable raw material for basic refractories, both bricks and
monolithics. High-performance basic monolithic
refractories have attracted strong interest and attention
for state-of-the-art steel-making processes and for
clean steel production, due to many unique advantages.
MgO-based castables have become a hot topic recently. Studies have shown that microsilica added to an
MgO-based castable mix can react with water and
magnesia fines to give strong bonding1, 2, 3). This reaction is believed to be formation of a magnesia-silicatehydrate gel4), which facilitates the setting and binder
strength development. It has also been found that
microsilica in such a system suppresses the slaking
tendency of MgO.
Castables with the MgO-SiO2-H2O bond have been
used in some countries for steel ladles and tundish

weirs or dams. Another key role of microsilica is to

improve flow and setting properties. Otherwise the
mixes would have poor flow characteristics, inhibiting
the use of highly efficient installation techniques such
as pumping and shotcreting. With proper combination
of particle size distribution, microsilica and additives,
MgO-based mixes can be modified to allow for
pumping and wet spraying.
As the castable is heated, microsilica and magnesia
form forsterite. The MgO-SiO2 system mainly relies
upon the forsterite for high temperature bonding4).
Forsterite is a refractory phase with a melting point
about 1890C, and the eutectic in the system of
2MgOSiO2MgO is at 1850C. As alumina is
introduced in the system, a low melting phase is likely
to form, rather than a strong spinel-forsterite bond. It
has been suggested that formation of some in-situ
spinel may counteract the volume shrinkage.
Based on our previously published work as Part 1,
Effect on flow, set and hot properties when substituting
microsilica with alumina in pumpable MgO-based
castables, one recipe was selected from the selfflowing castables, with MS/RA=6/7.2 (wt.), labelled as
EL-3; and one from the vibration castables, with
MS/RA=6/0 (wt.), labeled as EL-5. The El-3 has a freeflow value of 120%, while the EL-5 about 60%. Both
castables have a working time of no less than 2h,
allowing them to be good candidates for trial shooting5).
When a castable is installed by spraying, its properties
will be affected, mainly the increased porosity,
impurity from the accelerator and inhomogeneity,
having influence on the performance and refractoriness
of the lining. Another influence is the lack of
experience in operating the machine, in terms of air
pressure, accelerator type and addition, distance,
moving speed, etc. The aim of this work was to
investigate what effects this new installation method of
wet shotcreting or, in other words, wet spraying, may
have on the hot properties (hot modulus of rupture,
refractoriness under load behavior and slag resistance)
of such MgO-based castables.

2. Procedure
2.1 Samples preparation
In the laboratory, the ingredients were dry-mixed in a
Hobart mixer for 4 min., water was added, and then wet
mixed for an additional 4 min. to make EL-3 and EL-5
samples. Same mixing time and water addition were
used in the case of larger on-site mixer with a batch of
500kg dry mixes one time. 1000kg, in two batches,
mixed-fresh castables, were transported by a crane to
the hopper of the pumping and spraying machine.
The EL-3 and EL-5 castable mixes were pumped and
sprayed by an Allentown Pump RP-10 machine, under
such operation parameters as pumping capacity of 8-10
tons per hour, pumping pressure 14MPa, hose diameter
75mm, hose length 15m, nozzle tip 38mm, air pressure
0.7MPa and air flow 6m3/min. Al2(SO4)3 saturated
solution was used as an instant accelerator to the wet
mixes, with an average calculated addition of 0.12%
solution, based on the dry-mix mass. The distance
between nozzle tip and the sprayed surface was
0.5-1m. The ambient temperature in the workshop was
5-10C. The shoebox-like pumped blocks with a
dimension of 230mm in length, 160mm in width and
140mm in height, and the sprayed blocks, 900 mm in
length, 700 mm in width and approximately 150 mm in
height, were properly cured and then subjected to
400C treatment prior to being cut into different shapes
and sizes for different tests. The pumped specimen was
labelled with P, i.e. PEL-3 and PEL-5, and the sprayed
as S, i.e. SEL-3 and SEL-5.
2.2 Cold modulus of rupture (CMOR)
Samples were then fired at 600C, 1000C, 1200C,
1400C and 1600C for 5h. CMOR was measured on
samples of 40x40x160mm according to ASTM C348.
2.3 Hot modulus of rupture (HMOR)
HMOR measurement was performed on samples of
25x25x150mm in accordance with the standard of
PRE/R18. Samples were pre-fired for 24h at the test
temperatures and allowed to cool before being loaded
into the test furnace. The heating rate was 300C/h for
both pre-firing and testing, and the samples were
allowed to soak at the test temperature for 30 min prior
to loading.
2.4 Refractoriness under load (RUL)
RUL was measured on cylinders of 50mm in diameter
and 50mm in height with a 12mm central bore, as
described in ISO R1893 (1970). Loading was 0.2MPa.
The samples had been pre-fired for 24h at 1500C,
unless otherwise stated. Heating rate was 300C/h for
both pre-firing and testing. The equipment was
designed in accordance with descriptions of ISO
R1893 (1970); the maximum accessible temperature
was 1800C for testing under rising temperature.

2.5 Rotary slag test

Two batches of rotary slag test were conducted, each
using 12 different specimens, with a longitudinal
section of approximately 230mm in length and 60mm
in height, installed to make a drum in the furnace, to be
subjected to the attack of in-plant picked BOF slag
with CaO/SiO2=4.58 and EAF slag with
CaO/SiO2=1.26, respectively. The furnace rotating at 6
rpm was heated to about 1500C and first batch of 1kg
slag was fed; the temperature was raised to 16001650C and another 1kg slag was fed, then soaked at
1650C 50C for 130 min, during which 4kg slag was
fed at a rate of about 1kg per 30-35min. The furnace
was naturally cooled down. The slag-attacked
specimens were sectioned longitudinally. Visual
examination and measurement on local eroded depth
were pursued. Averaged eroded depth (H) was used to
represent slag resistance, calculated by the given
formula: H=Ho-h, where Ho is the averaged original
height, using 3 measurements at a 50mm interval
separating from the central symmetrical line, and
h=hi/11, (i=1~11) is the averaged remaining
unattacked height, using 11 local data at a measuring
step of 10mm symmetrically to the central symmetrical
line.
2.6 Recipes
Chinese-fused magnesia (MgO>98%) was adopted as
the main raw material. Reactive Alumina CTC50 was
supplied from Alcoa and 971U Elkem Microsilica
from Elkem Materials. Table 1 provides the recipes
with q=0.25 for self-flowing castables, while q = 0.28
for vibration castables5). The water addition was kept
at 15.2 vol%.
3. Results and Discussion
3.1 Bulk density (BD) and apparent porosity (AP)
Not surprisingly, samples cast in lab show the highest
BD and lowest AP, see Fig. 1 and Fig. 2. Comparison
of properties of the lab samples to the pumped and the
sprayed will show how much difference is introduced
by the placement method. In Fig. 2 it is seen that the
difference in AP of the 1200-1600C fired castables is
obvious, with the sprayed being the highest, the labprepared the lowest and the pumped inbetween. Too
low of an ambient temperature that the trials were subjected to could be a partial reason leading to reduced
flowability and setting, hence less density and higher
porosity.

Table 1 Composition of the two kinds of castables

Label

EL-3

Castable type

EL-5

Self-flow Vibration

q-value of Andreassen model

0.25

0.28

MS/RA volume ratio

60/40

100/0

3-5 mm

10

10

1-3 mm

27

27

Fused MgO

0-1 mm
-44 micron

Microsilica 971U (MS)

25

27

24.8

30

Reactive Al2O3 CTC50 (RA)

7.2

Dispersant Vanisperse CB

0.25

0.25

Water (15.2 vol.%), wt%

5.16

5.19

Fig. 3 PLC as a function of temperature

3.3 Cold Modulus of Rupture (CMOR)

There is a strength valley for all the samples fired at
1000C, as shown in Fig. 4. This is in accordance with
the finding that forsterite bonding in this system can
only form when temperature goes above 1100C4).
Al2O3 free EL-5, PEL-5 and SEL-5 samples have
higher bending strength than Al2O3, containing EL-3,
PEL-3 and SEL-3 ones from above 1000C, more significant at higher temperature. For both series, the
sprayed samples show lower CMOR than the in-lab
prepared and pumped ones.

Fig. 1 Bulk density of the samples vs temperature

Fig. 2 Apparent porosity of the samples vs temperature

Fig. 4 CMOR as a function temperature

3.2 Permanent Linear Change (PLC)

PLC of the different samples, as shown in Fig. 3,
doesnt show much difference, except for SEL-3.
These castables showed negative PLC at high temperatures due to sintering, but why SEL-3 showed large
expansion from 1000C up and much delayed turndown behavior in PLC (very exceptional when
compared to the others) is beyond understanding for
the time being, probably connected to the accelerator.
This phenomenon is worth further investigation.

3.4 Hot Modulus of Rupture (HMOR)

From Fig. 5 and Fig. 6, it can be seen that HMOR
reaches a maximum at 1300C, and then declines as
temperature increases. HMOR of Al2O3 free series is
higher than Al2O3-containing ones, indicating that
forsterite bonding is favorable to hot strength. Placement method-induced HMOR gap becomes narrower
at higher temperature end; nevertheless the lab samples
demonstrate higher hot strength than the pumped and
the sprayed samples.

Fig. 5 HMOR of EL-3, PEL-3 and SEL-3 vs temperature

Fig. 6 HMOR of EL-5, PEL-5 and SEL-5 vs temperature

3.5 Refractoriness under load (RUL)

RUL behavior of the samples pre-fired at 1500C in
each of the two series is similar, with the sprayed
starting to subside at a slightly lower temperature,
compared with the pumped and the lab-prepared.

Comparing Fig. 8 with Fig. 7 shows some difference in

RUL curves that MgO-SiO2 matrix imparts with higher
RUL than MgO-Al2O3-SiO2 does; at 1500C the EL-5
group shows a 2% expansion, while EL-3 group shows
1.5%. It is well in accordance with HMOR.

Fig. 7 RUL curves for EL-3, PEL-3 and SEL-3 samples

Fig. 8 RUL curves for EL-5, PEL-5 and SEL-5 samples

3.6 Rotary slag test

Chemical composition of the adopted slag is given in
Table 2, with distinguished CaO/SiO2 ratio and ferric
oxide content between the two kinds of steel-making
slag. The photographed sections of the samples after
slag test are shown in Fig. 9 and Fig. 10.
For comparison purpose in each run of the slag test, a
typical CA cement-bonded Al2O3-spinel ladle
castable, marked as AM (using Tabular alumina, whitefused alumina and pre-synthesized MA spinel as raw
materials, MgO content 5% and water addition
5.4 wt%), was also tested as a reference.
Table 2 Chemical composition of the slag
BOF slag

EAF slag

CaO, %

41.69

19.32

SiO2, %

9.10

15.28

Fe2O3, %

31.23

52.66

Al2O3, %

2.14

2.40

MgO, %

10.80

5.81

MnO, %

2.47

4.38

CaO/SiO2 (wt)

4.58

1.26

As basic slag always contains CaO, the MgO-CaOSiO2 system should be considered. Real operating
temperatures in a ladle exposed to basic slag may be up
to 1700C. It is easy to understand that MgO-based
basic refractories have better resistance to basic slag
than Al2O3-based ones, as proved in Fig. 9, that EL-3
and EL-5 show better slag resistance than AMs. Why
the pumped and sprayed samples performed so poorly
in slag resistance, especially PEL-3 and PEL-5 (being
even worse than SEL-3 and SEL-5), remains unclear,
but is believed to be connected to higher porosity,
segregation and the accelerator.
The poor slag penetration resistance to model EAF
slag and ladle slag has been reported by N. Li et al6).
Corrosion of MgO castable by EAF slag was related to
the dissolution of both MgO and M2S into C3MS2 and
CMS, both being low melting phases and easily
corroded and washed away by moving slag. But
periclase can take in Fe2O3. In this work it was found
that MgO castables EL-3 and EL-5 had comparable,
better resistance to EAF (low CaO/SiO2) slag attack
than AM castable, see Fig 10.

Fig.9 Rotary slag test results, BOF slag

The interesting finding from the slag test is that the

pumped and sprayed castables have shown poor resistance to the basic slag. Higher porosity led by
inexperience in adopting adequate additives and
operating the shotcreting may account for the poor
performance.
Surprisingly, the pumped samples show a poorer
esistance to the EAF slag than the sprayed ones, in
particular for PEL-3 with 53.2 mm eroded depth
against 11.2 mm for SEL-3. Same tendency has also
been observed in the case of BOF slag, 33.1mm in
eroded depth for SEL-5, in comparison to 42.8mm for
PEL-5. At the present stage, this can hardly be wellexplained, and deserves further investigation, with
particular attention to the texture in relation to
placement method.

Fig. 11 Slag-refractories interface observed by SEM in EL-5

attacked by BOF slag. C4AF (white light part), MgO
(dark round/granular), C2S (granule in network) and MA
(grey network).

Fig. 10 Rotary slag test results, EAF slag

3.7 Microstructure after slag test

After both BOF and EAF slag tests, the samples prepared by different placement methods had similar
phase composition and distribution, crossing the hot
face to cold face; only the extent was different. Fig. 11
shows the SEM observation of EL-5 attacked by BOF
slag. In the slag-refractories interface, C4AF, MgO,
C2S and MA coexist. Periclase and spinel have
absorbed Fe2O3 to form a solid solution. C2S is a
useful phase to resist slag. Down to the reacted layer,
concentration of CaO and Fe2O3 is lowered; then
C3MS2 and MgO coexist; further on, CMS and M2S
are found; finally, in the unattacked layer, only MgO
and M2S are found dominant.

Fig.12 Slag-refractories interface observed by SEM in EL-5

attacked by EAF slag. MgO (dark), Fe2O3 rich complex spinel
(white ring around MgO and precipitated from MgO), C3MS2 and
CMS (continuous grey part).

Fig. 12 is the SEM micrograph of EL-5 attacked by

EAF slag. In the slag-refractories interface, M, MA,
C3MS2 and CMS. Complex spinel formed around periclase as well as precipitated inside periclase, proved by
as much as 54.8% of Fe2O3 has been detected by
EDAX in the bright ring part, and as a result of that the
Fe2O3 in the slag has reacted with magnesia in the
castable. From hot face down to the reacted layer, the
concentration of CaO and Fe2O3 becomes reduced;
then M and CMS and little MA are found to coexist; M
and M2S are found further down, and the unattacked
layer is composed of M and M2S.

4. Concluding remarks
Through this work, it has been found that for the MgOSiO2-H2O bonded MgO-based castables, placement
method and conditions do have significant influence
on their cold and hot properties as well as slag resistance.
The developed MgO based castables of both selfflowing type and vibration type are pumpable and
sprayable. From an installation point of view they are
successful, while from the point of view of properties
or service performance, further efforts are needed to
reduce porosity, increase strength, enhance refractoriness under load and to improve slag resistance, when
pumping and shotcreting techniques, especially the
latter, are applied.
So far the achieved properties of the MgO-based castables placed by pumping and spraying are not competitive to the in-lab prepared ones under favorable conditions. Optimisation work on additives and ambient
conditions, as well as operating parameters, should be
attached importance.
Some interesting but inexplicable findings, e.g., the
exceptional PLC curve of SEL-3 and pumped samples
showing poorer slag resistance than the sprayed in-slag
resistance, need to be understood and are the basis for
further investigations inspired by this work.

References
1) B. Myhre: Cement-free castables in the system MgO-SiO2:
The effect of bond-phase modifiers on strength, Presented at
the 93rd Annual Meeting of The American Ceramic Society,
Cincinnatti, 1991.
2) B. Sandberg, B. Myhre and J. L. Holm: Castables in the
system MgO-Al2O3-SiO2, Proc. of UNITECR95, Kyoto,
Japan, Nov. 19-22, 1995, Vol. II, p. 173-80.
3) B. Myhre, B. Sandberg and A. M. Hundere: Castables with
MgO-SiO2-Al2O3 as bond phase, Proc. of XXVI ALAFAR
Congress, San Juan, Puerto Rico, Oct. 29-Nov. 1, 1997,
p. I/1-I/10.
4) Nan Li, Yaowu Wei, Hongpeng Wu, B. Myhre and C.
degrd: Properties of MgO castables and effect of reaction
in microsilica-MgO bond system, Proc. of UNITECR 99,
Sep. 6-9, 1999, Berlin, Germany, p.97-102.
5) C. Odegaard, Z. Chen, B. Myhre et al: MgO-SiO2-H2O
bonded MgO castables, Part 1: Effect on flow, set and hot
properties when substituting microsilica with alumina in
pumpable MgO based castables, Proc. of the 4th
International Symposium on Refractories, Dalian, China, Mar.
24-28, 2003, p. 148-156.
6) N. Li, S. Zhang and W. E. Lee: Penetration and corrosion of
magnesia castables by silicate slags. Proc. of UNITECR 01,
Cancun, Mexico, Nov. 4-7, 2001, p.65-79.

Acknowledgment
This work was supported by Henan Gengsheng Refractories Co.,
Ltd., China, allowing use of its shotcreting equipment and rotary
slag test furnace. The authors wish to express their sincere thanks
for the support and convenience provided by Henan Gengsheng
Refractories Co., Ltd.

10

11

The world-wide distribution

network
Elkem Refractories markets Elkem Microsilica
world-wide either directly, through Elkems sales
offices or through local agents.

means reliable supplies. Elkem Microsilica is

produced at various locations in North America and
Europe, and is delivered in a variety of packaging.

Research on refractory applications is carried out at the

main research center in Norway. Our technical staff is
trained to assist producers and users with refractory
technology.

Elkem Microsilica provides users, producers and

installation teams with refractories that give improved
economy. Elkem Refractories stands ready to supply
Elkem Microsilica and related technology for your
current and future needs.

Elkem is the worlds largest producer of high quality

microsilica for refractories. For our customers, this

Elkem Microsilica is registered trademark owned by Elkem.

Brazil:

Microsilica Ltda., Rua dos Botocudos, 335

Diadema - So Paulo, CEP: 09980-170, Brazil
Tel: +55 11 4056-7900, Fax: +55 11 4043-3554
http://www.microsilica.com.br
e-mail: msilica@microsilica.com.br

Japan:

Elkem Materials Japan

Nikko Sanno Bld. no. 401, 5-3, 2-chome Akasaka
Minato-ku - Tokyo 107-0052, Japan
Tel + 81 33584 77 11, Fax + 81 33584 04 37
http://www.elkem.co.jp

China:

Elkem International Trade (Shanghai) Co., Ltd.

Room 2507, Jin Mao Tower, No. 88, Century Boulevard
Shanghai 200121, P.R. China
Tel +86 21 5047 6600, Fax +86 21 5047 0899

Norway:

Elkem Materials, P.O.Box 8126 Vaagsbygd

N-4675 Kristiansand, Norway
Tel +47 38 01 75 00, Fax +47 38 01 49 70
e-mail: microsilica.materials@elkem.no

Denmark:

Elkem Nordic, Bygstubben 13

DK-2950 Vedbk, Denmark
Tel +45 45 66 12 12, Fax +45 45 66 12 06

Russia:

Germany:

Elkem GmbH, Meerbuscher Strae 64 - 78

D-40670 Meerbusch, Germany
Tel +49 2159 675 0, Fax +49 2159 675 111

Elkem Moscow, Krzhyzhanovskogo str. 14, bld 3

P.O. Box 148, 117218 Moscow, Russia
Tel/ fax +7 503 737 7554, Tel +7 095 124 4717
Fax +7 095 331 4411

United Arab
Emirates:

Elkem Materials Middle East

P.O.Box 17821, Dubai, United Arab Emirates
Phone: +971 4 88 17 769, Mobil: +971 50 45 08 611
Fax: +971 4 88 14 736 - e-mail: elkem@emirates.net.ae

USA:

Elkem Materials Inc., P.O. Box 266, Pittsburgh, PA 15230-0266

Airport Office Park, Building 2, 400 Rouser Road
Moon Township, PA 15108-2749, USA
Tel +1 412 299-7242, Fax +1 412 299-7238

Great Britain: Elkem, 305 Glossop Road, Sheffield S10 2HL, England
Tel +44 1142 70 03 34, Fax +44 1142 75 31 03
India:

Elkem India Private Limited

66/67 Mahavir Centre, Plot no. 77, Sector no. 17, Vashi
Navi Mumbai 400703, India
Tel: +91 22 789 6401 /2 /3 /4, Fax: +91 22 789 6409 /10

Italy:

Elkem Italy, Centro Direzionale Colleoni, Palazza Taurus (A3)

Viale Colleoni, 5. I-20041 Agrate Brianza (Milano), Italy
Tel +39 039 60 57 021, Fax +39 039 60 57 019

www.refractories.elkem.com

TVEDT TRYKKERI AS KRISTIANSAND