COMMUNICATIONS

tration between 0.1 and 0.2 mg/l, but at a glue concentration

of about 0.8 mg/l. Further advantages of PEG compared with
glue are the clearly slower chemical decomposition rate, the
possibility of setting a definite cathodic potential by variation
of the molecular weight and the constant chemical composition. However, our systematic investigations have shown that
there will be no improvement in the deposition type of the
cathode deposits when PEG is only added compared with the
classical inhibitor system of glue and thiourea until now. It is
known in copper electrorefining and electroplating that a
high quality of cathodic deposition can usually only be
achieved through a combination of inhibitors and activators.
The major target of our further investigations is to find additives that show a depolarizing effect in combination with
PEG. In addition to that criterion these additives should be
sulfurfree to reduce the level of sulfur in the cathodes in comparison to the traditional used thiourea.
Received: March 24, 2004

[1]
[2]

[3]
[4]
[5]
[6]

[7]
[8]
[9]

M. Stelter, H. Bombach, Erzmetall 2001, 54, 432.

M. Stelter, H. Bombach, in Copper 2003 Cobre 2003,
Volume 5, The Canadian Institute of Mining, Metallurgy an Petroleum, Monteral, Canada, 2003, p. 555
567.
D. Schab, H. Bombach, K. Hein, Erzmetall 1997, 50, 614.
H. Bombach, K. Hein, D. Schab, Erzmetall 1995, 40, 703.
H. Bombach, K. Hein, R. Vermeersch, BHM 1999, 144,
18.
B. Langer, P. Stantke, EPD Congress (Ed.: G. W. Warren), The Minerals, Metals & Materials Society, 1995,
p. 559569.
M. Goffman, WO-Patent 84/03307.
N. Nesterov, H. Bombach, M. Stelter, in Proc. EMC Congress 2001, Vol. 1, Friedrichshafen, p. 121130.
M. Stelter, H. Bombach, N. Nesterov, JOM 2002, 54 (4),
32.

______________________

Material and Process

Development of Advanced
Refractories for Innovative Metal
Processing**
By C. G. Aneziris,* F. Homola and D. Borzov
As the new generation of secondary metallurgy and advanced continuous casting technologies have been developed
in the last decade, refractory materials have met the greatest
challenge in order to secure the high metal quality under economical and ecological aspects. During service refractories
must not only tolerate high temperature but also withstand
stresses (thermal and/or mechanical) as well as resist combined attacks by liquids such as molten metals, slags and
fluxes. Especially in near net shape casting technologies enhanced corrosion and erosion performance is required followed by thin wall thickness design of functional components
such as submerged entry nozzles or casting channels.[1,2] In
addition the processing of these advanced refractories has to
fulfil all the requirements for a large geometry component
manufacturing whereby the task of low shrinkage during firing dominates.
In recent years the Institute of Ceramic, Glass and Construction Materials of the Technische Universitt Bergakademie Freiberg has been involved in research studies of process
and material development of MgO carbon bonded materials
(MgO-C) as high-performance refractory ceramics because of
their superior properties according to corrosion and thermal
shock resistance as well as the unique benefits out of a low
shrinkage pyrolisis firing process. MgO-C refractories are established construction materials of converters, electric-arc
furnaces, transfer and treatment ladles.[3] The carbon increases the corrosion resistance of magnesia carbon bricks
caused by all types of liquids (molten slag and metals) and
improves their thermomechanical properties, particularly
their thermal shock resistance. In addition carbon offers excellent electrical properties in order to use these advanced refractories also as smart, functional refractories and especially
as smart refractory casting components.

[*] Prof. C. G. Aneziris, Dr. F. Homola, Dr. D. Borzov

TU Bergakademie Freiberg
Institute of Ceramic, Glass and Construction Materials
D-09599 Freiberg, Germany
E-mail: aneziris@ikgb.tu-freiberg.de

[**] The authors would like to thank Bakelite AG and Rtgers AG

for the supplying of the binder system. The financial support
from the Deutsche Forschungsgemeinschaft (DFG) is also
gratefully acknowledged.

562

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/adem.200400417

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

Aneziris et al./Materials and Process Development of Advanced Refractories

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

COMMUNICATIONS

In terms of this work a phenolic resin binder has been

combined with a new Carbo-resin called CARBORES in order
to improve the anisotropic carbon structure for advanced mechanical, chemical and thermomechanical properties with 14
wt.% residual carbon. In a further step an electrical potential
has been applied to the MgO-C refractory in contact with slag
at elevated temperatures in order to improve the corrosion
and oxidation performance for an application as a casting
nozzle or casting channel.
In Europe either coal-tar pitches or hardening synthetic
resins are used as binders for these high-grade refractories. In
Asia and America resin bonded magnesia carbon products,
mostly with an addition of antioxidants, are preferred.[4] A
big disadvantage of the coal-tar pitches is the content of carcinogenic aromatics, especially the benzo[a]pyrene. Alternatives to the benzo[a]pyrene-rich coal-tar pitch are hardenable
artificial resins, especially phenolic resins. The resins have
the advantage that they can be mixed with the refractory
granular materials without warming. The coke residue is
similar to pitch, approximately 5060 %. A problem is the isotropic phase of the coke residue resulting from resins leading
to more oxidation and thermo mechanical sensitiveness. On
the other hand there is a new Carbo-resin product (CARBOnaceous RESin), which is a high melting coal-tar resin.
Although it is produced out of coal it contains extremely
low carcinogenic aromatics, especially the benzo[a]pyrene
(< 300 ppm).[5] It is a coal-tar resin which forms a high temperature binder with a high coke residue reaching values up
to 85 % according to ISO 6998. At a temperature higher 200 C
the Carbo-resin softens and contributes after coking in contrast to resins with a highly oriented graphite-like carbon
structure (improvement of the carbon anisotropic structure).
One target of the present work is to compare an environmental friendly phenolic binder with additions of the new Carboresin.
By applying an electric potential at refractories the wetting
behaviour against metal/slag-melts can be modified for improved service life. Especially the high erosion, corrosion and
anti-clogging requirements can be fulfilled.[6] Riaz and Mills
describe the effect of an electric potential of 1 V on the wettability and thereby on the corrosion resistance of refractories
in contact with slags.[7] In their experimental arrangement,
one electrode is placed on a Pt substrate (it substitutes electrically conductive refractories) and another electrode in the
slag. It is proposed that due to this arrangement the entered
electrons influence the surface tension at the interface slag/
platin. After Wanibe the infiltration of slag into capillaries
and pores of the refractory decreases with decreasing surface
tension and with increasing viscosity.[8]
In the present work the mechanisms of an electrically assisted high temperature wettability of resin-bonded carbonmagnesia (C-MgO) refractories in contact with casting slag
will be illustrated, whereby for the first time both electrodes
will be connected to the C-MgO refractory specimen,
Figure 1. The modification of wettability by applying an elec-

Fig. 1. Arrangement with both electrodes at the refractory.

tric field is forced due to coulomb interferences and/or due

to the formation of reaction layers/passivation layers and/or
due to changing of the aggressiveness of the slag by local partial electrolysis.
The corrosion mechanisms of carbon-bonded MgO refractories play thereby a decisive role. These mechanisms include
especially carbon's non-wettability against silicate slags (so
that liquid penetration is limited) and in addition reduction
by C of MgO to form Mg vapour which reoxidises and deposits as layer of secondary MgO at the slag/refractory-interface
which prevents further oxidation of C.[911]
Experimental
Part I: Improving the anisotropic carbon structure: For the production of MgO-C bricks two binder compositions based on a
liquid resol (solution in ethylene glycol), a powdered resin
(with 9 % Hexa) and the new Carbo-resin were prepared in
accordance with the principal scheme in Table 1. Fused magnesia and sintered magnesia grains 05 mm were added in
optimal packing tightness. Their properties are listed in
Table 2. Further both compositions contained 12 % natural
graphite (94 % Carbon; specific surface area 1 m2/g). The
batches for pressing were homogenized at room temperature

Table 1. Compositions.

composition Nr.

1.

2.

Resol

2,5 wt.%

2,5 wt.%

Powdered resin

1,0 wt.%

Carbo-resin

1,0 wt.%

Table 2. Properties of the MgO raw materials used.

MgO

Bulk density, g/cm3

MgO

Fe2O3

C/S-ratio

Fused magnesia

3,52

97,8

0,5

Sintered magnesia

3,43

98,0

0,12

http://www.aem-journal.de

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

563

COMMUNICATIONS

Aneziris et al./Materials and Process Development of Advanced Refractories

in a pilot-plant-scale Eirich mixer and then moulded in an industrial press at 150 MPa (format of the bricks 4P12/13 kg).
Following industrial hardening at a final temperature of
180 0C, the specimens (cylinders, sticks, cubes for fracture mechanical characterisation) were cut out for further tests. Some
of the cut specimens were coked at 1000 0C in the special retort filled with carbon grit.
Part II: Electrically assisted high temperature wettability: In
a novel hot stage microscope with a sample area of
60 60 40 mm the wetting angle of a resinbonded MgO-C
refractory based on composition 2 (cylindrical samples
50 mm in diameter and 25 mm in height, 14 % carbon residue
and 10,2 % open porosity after coking) against an aggressive
casting slag powder of the type Scorialit C 189/V3 supplied
by Metallurgica with a basicity of 0,83 (26,3 % SiO2, 19,6 %
CaO, 8,66 % Na2O, 2,26 % Fe2O3 and 26,6 % C as main parts)
was registered due to the sessile drop method. According to
data sheet the softening point of the casting powder is approx. 950 C, the melting point 1020 C and the flowing point
approx. 1040 C. The infiltration depth was used as measure
for the corrosion attack. An uniaxial pressed cylinder of the
casting slag powder (10 mm in diameter and 15 mm in
height) was placed on the MgO-C refractory.
The furnace of the microscope has a maximum operating
temperature of 1650 C and is coupled with a PC-system for
purpose of data interpretation. Due to oxygen measurements
by the aid of a k-sensor the possibility to apply electric potentials in defined atmospheres at high temperatures is given.
In order to investigate the influence of electric current on
corrosion resistance the following tests have been carried out:
Test 1, without an electric current,

Fig. 2. Composition 2 (500 0C), mesophase crystals.

Test 2, with an electric current of 5 A,

Fig. 3. Composition 2 (after coking), anisotropic structure.

Test 3, with an electric current of 0,5 A and

Test 4, with an electric current of 0,05 A.

inserted into predrilled holes (20 mm from the corrosion surface, 25 mm distance between the electrodes). Corundum
tubes serve as oxidation protection of the tungsten rods and
the contact zone MgO-C/corundum-tube is additionally
sealed by high alumina cement castable. All tests were carried
out at 1500 C by holding the max. temperature for 30 min.
The heating rate was 10 K/min. All tests were repeated 3
times.

As an atmosphere serves standardised air with a 100 l/h

flow. The direct current is supplied by a constant current
holder (Statron) and herein after referred to as current. Several preliminary tests with different electrode materials and arrangements had been carried out in order to define an oxygen
resistant coupling at elevated temperatures. The contact
occurred by means of tungsten rods which had been parallel

Table 3. Properties of bricks.

composition

after hardening

after coking

Bulk density,
g/cm3

CCS,
Bulk density,
N/mm2 g/cm3

1: Resol +
powdered Resin

3,00

76

2: Resol +
Carbo-resin

3,00

60

expansion, %

CCS,
OP,
N/mm2 %

HBS,
MPa

0,28

27

10,7

0,20

31

10,2

2,92

0,29

2,94

0,26

a in pressing direction; b vertical to pressing direction

564

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

http://www.aem-journal.de

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

Aneziris et al./Materials and Process Development of Advanced Refractories

ture of composition 1 and 2 after coking was determined, see
Figures 5 and 6. Both compositions reached approximately
the same strength value but noticeable differences occurred
by calculating the characteristic fracture length Lch according
to
Lch = GF E / rF2
with GF the specific fracture energy, E the Young's modulus
and rF the strength. The specific fracture energy was calculated by
GF = 1/A F dd
with A the fracture surface area, F the load (force) and d the
displacement
The Lch for composition 1 was equal to 29 mm and for
composition 2 55 mm. Materials which show relatively low
degradation of their mechanical properties under imposed
strain are usually called flexible by refractory specialists, so
composition 2 presented a higher flexibility.
Part II: Electrically assisted high temperature wettability: According to the wetting angle approximately the same effects
were observed at all specimens, independently if current was
applied or not. Up to 1100 C all samples were not wetted by
the silicate slag casting powder because of not yet burnt out
or not yet oxidised carbon (by MgO), wetting angle larger
than 120. Above 1140 C, clearly over the flowing point of
the casting slag powder, the melt wetted all test specimens
with a slightly lower spreading of the slag in case of the electrically assisted specimens.

Fig. 5. Force/displacement behaviour, composition 1.

Fig. 4. Composition 1 (after coking), isotropic structure.

Table 4. Pore-size distribution.

composition 1

composition 2

d10[nm]

75

55

d50[lm]

3,7

0,7

principal ingredient [lm]

0,2...0,6
50...80

0,1...0,4
0,7...2,5
Fig. 6. Force/displacement behaviour, composition 2.

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

http://www.aem-journal.de

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

565

COMMUNICATIONS

Results
Part I: Improving the anisotropic carbon structure: The properties after hardening and after coking of the two compositions
are listed in Table 3. According to the Cold Crushing Strength
(CCS), the Open Porosity OP) and the three point Hot Bending Strength (HBS) determined at 1400 C no noticeable differences were observed between composition 1 and 2.
For the investigation of the oxidation behaviour cylindrical
specimens were exposed to a temperature of 1200 C (holding
time 3 h). The oxygen partial pressure in the kiln corresponded to the ambient air. No difference in the oxidation behaviour of the two compositions was measured when the
possible measurement accuracy was taken into account. Both
compositions exhibited a mass loss of 6 0,3 %. Also the cut
faces had now visible difference.
The microstructure of the compositions was studied by
means of SEM analysis. In Figure 2 mesophase crystals of
composition 2 at a temperature of 500 C were identified.
These structures were also identified after coking at 1000 C,
Figure 3. In contrast, no crystalline zones were detected in
composition 1, Figure 4. In Table 4 the recorded values of the
pore volume structure are listed. The pores in the batches
tended to lie in two size ranges (principal fractions). These
two ranges differed widely. Most of the pores of composition
2 (containing Carbo-resin) were lying in relatively small diameter ranges.
In a special notch tensile strength device for refractories
with a special specimen geometry as described in the literature[12] the load/displacement relationship at room tempera-

COMMUNICATIONS

Aneziris et al./Materials and Process Development of Advanced Refractories

Fig. 7. Test 1, without current.

Fig. 9. Test 3, with a current of 0,5 A.

Fig. 8. Test 2, with a current of 5 A.

Fig. 10. Test 4, with a current of 0,05 A.

The infiltration depth of the melt into the refractory as well

as the decarbonisation depth of the specimens were taken under consideration for the evaluation. Thereby the formation
of the MgO protective layer affected positive both, the corrosion resistance as well as the oxidation resistance.
Figures 7 to 10 present cross sections of the four tests listed
above, whereby the upper side is infiltrated by slag. The
added quadrate corresponds to 10 10 mm. The differences
between the tests without and with current are clearly visible.
By the application of electric current a lower corrosion/infiltration depth is obtained. Surprisingly the best results in
terms of infiltration were achieved with 0.05 A, see Table 5.
The decarbonisation (particularly on the sides, brown areas)
was considerably lower in case of specimens that were supplied by electric current. In case of tests 2 to 4 an MgO-protective layer with higher density was identified, whereby in case
of 5 A the highest oxidation resistance was registered (high
density MgO-layer), see Figures 11 and 12.
Figures 13 and 14 present the top-views of the surface of
the MgO-C specimens on the corrosion frontal side with the
outspreaded slag. It is obvious that in case of electric current

Table 5. Infiltration depths and thicknesses of the MgO-layers, average values of three
tests for each case.

566

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

slag infiltration
approx. [mm]

MgO-layer formed
approx. [mm]

1. without current

1,2 1,7

0,5 1,2

2. current of 5 A

0,8 1,1

0,31,3

3. current of 0,5 A

0,7 1,1

0,2 0,6

4. current of 0,05 A

0,5 1,0

0,3 1,0

a slag microstructure with a higher density occurred. Either

the current contributed to the change of slag chemistry or the
dense protective layer of the secondary MgO below the slag
reduced the infiltration. The second claim was confirmed by
EDX-analysis. By applying currents the oxide chemical composition of the slag remained approximately the same as before testing, in case of no current the oxide amounts of SiO2
and CaO were both strongly reduced.

http://www.aem-journal.de

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

Aneziris et al./Materials and Process Development of Advanced Refractories

COMMUNICATIONS

Fig. 11. SEM-micrograph, test 1 without current, surface area of the porous MgOlayer (500x).
Fig. 14. SEM-Micrograph, test 3 with 0,05 A, top-view of the surface, slag surface
with higher density (1000x).

Fig. 12. SEM-micrograph, test 2 with 5 A, area of the MgO-layer with higher density
(500x).

Fig. 13. SEM-micrograph, test 1 without current, top-view of the surface, porous slag
surface (1000x).

Discussion: According to Part I due to the new binder combination with additions of CARBORES the tasks of lowering
emissions during processing of MgO-C refractories as well as

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7

Fig. 15. Left slag infiltration between two grains without current, right slag infiltration between two grains at a specimen supplied with current.

improving the mechanical performance by formation of higher flexible structures (especially for large component manufacturing) were achieved.
In part II by the application of an electric potential a higher
oxidation resistance and a higher corrosion resistance (lower
infiltration depth) were obtained. In all specimens an MgO
protective layer was formed, whereby in case of an electric
potential a significantly higher density of the MgO layer was
generated. Independently from the electric potential, the
MgO-layer contributed to the oxidation resistance (by reduction of the oxygen diffusion) and to the corrosion resistance
(by reduction of the open porosity) at the zero-current specimens as well as at the specimens supplied with current.
The MgO-layer with a higher density (specimens supplied
with current) led to an increased oxidation and corrosion
resistance. Additionally and independently from the formation of a MgO-layer (e.g. at another refractory system), the
application of a voltage activated the attractive coulomb
forces between the polarised grain boundary/grain wall and
a polarised melt after the principle model in Figure 15. By
means of the attraction the infiltration towards specimen interior was reduced.

http://www.aem-journal.de

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

567

COMMUNICATIONS

It was surprisingly observed that the high electric current

(test 2) led to a higher oxidation resistance (formation of a
MgO-layer with a higher density); however a lower corrosion
resistance was achieved (i.e. a higher infiltration depth) in
comparison to a specimen supplied with a lower current
(test 4). The MgO presents at 1500 C a higher electric conductivity than the MgO at room temperature (electric isolator).
But its electric conductivity at elevated temperatures is significantly lower than the carbon conductivity. The formation of
the MgO-layer with a higher density contributed as an electric isolator and reduced the electric conductivity of the Carbon/MgO-microstructure. This phenomenon led to the reduction of the attractive coulomb forces and thereby a higher
slag infiltration was registered.
The arrangement of Riaz and Mills was also investigated
in terms of this study. In case of their arrangement the electrode in the slag contributed only at a specific local point. By
moving the slag electrode the slag followed the electrode
movement. Further the corrosion resistance of this electrode
against the aggressive slag system had to be taken under consideration.
In case where two or more electrodes (arrangement of
Fig. 1) are applied in the refractory a surface area is polarised
and the whole surface area is protected against slag infiltration.
The application of electric potentials improves the corrosion and oxidation resistance of MgO-C refractories and in
combination with new mechanically enhanced carbon structures the horizon for advanced applications in near net shape
innovative metal casting technologies up to 1600 C as smart
refractory nozzles or channels or slide gates is opened.
Received: March 24, 2004

[1] K. Asano, A. Ishi, Taikabutsu Overseas 1991, 71, 50.

[2] C. G. Aneziris, Habilitation, RWTH Aachen, 2000.
[3] J. Suren, A. Gardziella, R. Solozabal, UNITECR
CONGRESS '91 Reprints 1991, pp. 260264.
[4] G. Buchebner, R. Neuboeck, S. Grasseger, Biennial
World-wide Congress UNITECR '01 Vol.1, 2001, pp. 324
335.
[5] W. Boenigk, Feuerfest-Seminar, Bad Neuenahr 1994.
[6] C. G. Aneziris, F. Homola, D. Melzer, Conference on
Refractories 2003, Prag, pp. 2635.
[7] S. Riaz, K. C. Mills, cfi/Ber. DKG 2002, 79(3), E 47.
[8] Y. Wanibe, H. Tsuchida, T. Fujisawa, H. Sakao, Trans.
ISIJ 1983, 23, 331.
[9] A. Watanabe, Y. Takeuchi, Taikabutsu Overseas 1981, 1,
40.
[10] T. Horio, H. Fukuoka, K. Asano, Taikabutsu Overseas
1986, 6, 11.
[11] T. Suruga, Taikabutsu Overseas 1998, 18(4), 5.
[12] H. Harmuth, E. K. Tschegg, Fatigue & Fracture of Eng.
Mater. & Struct. 1997, 20, 1585.

568

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Studies on a Novel Route

to C/SiC**
By Eberhard Mller, Rosemarie Dittrich,
and Kirsten Moritz
Silicon carbide is a suitable matrix for carbon-fiber-reinforced composites due to its stability at high temperatures.
Hitherto several especially highly sophisticated - techniques
have been used for preparing C/SiC,[1] for example: chemical
gas phase infiltration (CVI), liquid polymer infiltration (LPI)
or (reactive) liquid silicon impregnation (LSI) of CFRC (carbon fiber reinforced carbon). Most of them are time consuming and very expensive. Therefore a new route using electrophoretical infiltration for preparing C/SiC was investigated.
The electrophoretic infiltration of fiber rovings or fabrics
seems to be a promising method for producing fiber-reinforced composites. The infiltration of conducting as well as of
non-conducting fiber mats by this method has been described
in the literature. Various fiber/matrix combinations have
been already investigated, such as stainless steel fibers/silica
matrix,[2] SiC fibers/mullite matrix,[3,4] alumina fibers/alumina matrix[4] and NextelTM 720 fibers (mullite/corundum)/
mullite composition matrix.[5] For infiltrating non-conducting
fibers the fabrics are positioned in front of the deposition electrode. In the case of an electrophoretic infiltration of carbon fiber mats with SiC powders the fiber preform can be directly
used as deposition electrode due to its electrical conductivity.
Experimental
Starting materials: The particle sizes of powders applied for
the electrophoretic infiltration should be sufficiently small to
enable the particles to pass the extremely narrow interspaces
between the single filaments of a fiber roving and to fill the
woven fibre mat as completely as possible. Each roving consists of a more or less dense packaging of several thousand fibers with diameters of about seven micrometers. Two fabrics
were used: SIGRATEX (SGL Carbon Group) KDL 8048 with
3000 filaments and KDL 8023 with 1000 filaments per roving.
The particle sizes also influence sintering activity and microstructure of the sintered matrix material. Ideally, nanoscaled powders should be applied. However, only a few relatively expensive nano-sized SiC powders are commercially

[*] Prof. E. Mller, R. Dittrich, Dr. K. Moritz

TU Bergakademie Freiberg
Institut fr Keramische Werkstoffe
Gustav-Zeuner-Str. 3, 09596 Freiberg, Germany
E-mail: mueller@ikw.tu-freiberg.de

[**] Financial support of this project by the Deutsche Forschungsgemeinschaft is gratefully acknowledged. This project is part
of a compound project performed commonly with the Universities of Saarbrcken, Bayreuth and Ilmenau.

DOI: 10.1002/adem.200400404

ADVANCED ENGINEERING MATERIALS 2004, 6, No. 7