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Wear of Silicon Nitride Bonded Sic Bricks in Aluminium Electrolysis Cells
Wear of Silicon Nitride Bonded Sic Bricks in Aluminium Electrolysis Cells
Keywords: Aluminium Electrolysis, Refractory materials, Wear mechanism, Silicon nitride bonded silicon carbide, Sidewall blocks
Abstract 3
Samples from a sidewall of an aluminium electrolysis cell were Sample locations
submitted for study of the wear mechanism of the Si3N4 bonded
SiC-brick. Samples were studied using a combination of chemical 2
analysis, microscopy, SEM-EDS and powder-XRD. Unused
bricks from two suppliers were used as reference materials.
1
The unused bricks are very similar. Differences are found in the
grain size of the SiC and in the binder (E-Si3N4 content varies
between bricks in also internally in individual samples). All bricks
have a coarse matrix and higher porosity in the core.
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Figure 4. Formation of SiC and Si3N4 on a big Si-metal grain.
Figure 2. Sample location 1; Hydration products in the matrix Sample location 1
(reflected light microscopy)
The SEM – Element distribution map with composite images for
In general the matrix-material is sub-microscopic in grain size. different combinations of elements is given in figure 5. Sodium
Figure 3 shows that SiC is more stable than the matrix of Si3N4. and oxygen could only be found in the matrix between SiC and
The epoxy in the top left-hand corner represents the outside of the Si3N4. Fluoride is absent in the mapping. Other areas in the
brick. The SiC-grains that stick out are oxidized and the matrix sample were also examined for fluoride but without success.
has disappeared.
Na
Artifacts Na SiC
Figure 3. Direct melt attack on Si3N4 bonded bricks, sample SiO2
location 1 Na Na
Na
In the matrix some brightly shining Si-metal could be seen, which Na Si3N4
had partly reacted to SiC and Si3N4 (Figure 4.) In the matrix, red
shining grains were found, which were iron oxide (hematite). Na Na
Several bright white isotropic grains of FeSi metal were found in a. b.
the matrix.
O O
SiC
O
O O
Si3N4
O
O O
c. d.
Figure 5. Sample location 1, Elemental distribution.
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The picture on top in figure 5 shows a back scatter image with
three round Si-Fe metal crystals in a SiC grain. On the right hand
side of the image silicon nitride and smaller SiC grains make up sodium silicate SiC
the matrix. Based on element mappings four composite images are
shown (figure 5a-d.) The aluminium mapping (not shown) gives a
signal below background level which means that no Al-containing
phase is present in the mapped area.
SiO2
The element mapping shows that sodium and oxygen are
concentrated in the matrix as a replacement of the Si3N4 (Figure
5a and 5c.) Some artifacts from sample preparation are observed
and they do not indicate the presence of F. In figure 5a the dark
blue gives a clear indication of the Na-distribution, in figure 5c,
the light green shows the oxygen to correlate with Na. Figure 5b Figure 7. SEM micrograph showing reaction order of attacked
shows Si3N4 as purple and the green areas the oxidized matrix. In SiC. Location 2.
figure 5d Si3N4 is marked with yellow and pink represents SiC. 1. Oxidation SiC – SiO2
Iron, nickel and zircon were found as impurities in the Si metal. 2. Reaction of Na2O or NaOH with SiO2
XRD analysis was performed and the detected phase content are Figure 7 also shows pure SiO2 in contact to SiC and sodium
given in table 1. silicate, which serves as evidence for a primary oxidation of SiC
and a secondary reaction with sodium oxide. The only fluorides
Phase content (XRD) sample location 1. found were NaF and CaF2. Closer to the shell iron was found
Į-SiC, Na2SiO3, Si2N2O, ȕ-Si3N4, Į-Si3N4 together with calcium as a brighter separate phase with a
Table 1. Phase content of used brick from location 1. consistent stoichiometry corresponding to the chemical
composition of FeCa2Na10O28.
Autopsy sample location 2 SiC
The material looks porous and partly reacted. One side of the
sample was impregnated with epoxy before cutting. sodium silicate
The sample shows rimmed remnants of SiC grains in a sodium (Na : Si = 1 : 10)
silicate matrix with some Si3N4 and some NaF and SiO2, see
figures 6 and 7. Single point analysis was carried out to determine
the chemical composition at positions of interest. Sodium silicates sodium silicate
(Na : Si = 1 : 3)
were found with different sodium content, depending on the
location in the matrix. The SiO2 content of the sodium silicates
was much higher in the reaction zone around the SiC than it was
in the matrix where the sodium silicate glasses were found, see Rest Si3N4
figure 8.
NaF FeCa2Na10(Si10O28)
pore
NaF
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The XRD sampling represents a profile through the wall and sampling allowed moisture of normal atmosphere to react with
results are given in table 2. The “Towards joint” sample mainly primary reaction products in the sidewall of the e-cell.
consists of products from reaction of cryolite with Si-compounds.
The “Center” sample is highly porous (compared to the unaltered Na2O + H2O Æ 2 NaOH (1)
brick) and contains oxidation products and matrix phases with
partial oxidation (SiAlON). The “Towards shell” sample is the NaF + H2O Æ NaOH + HF (2)
least altered and shows only the initial stages of attack. In this
sample both reaction with cryolite and oxidation play a role, 2 NaOH + SiO2 Æ Na2SiO3 + H2O (3)
because the Al-oxide bearing phase Nepheline was detected.
Cryolite presence must be due to penetration through joints. The NaOH + CO2 + H2O Æ Na2CO3 · H2O (4)
steel shell shows some rusting behind the SiC bricks and this
confirms the presence of oxygen. NaOH + CO2 Æ NaHCO3 (5)
Secondary reactions took place after the pot was switched off and
cooled down. The period of storage between switch off and Figure 11. HF-gas attack on Si3N4 matrix. Location 3.
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between these parts. The black areas, representing porosity, are
Figure 12 below shows the cell with the assumed attack more frequent inside than outside. The dark crystals in the matrix
mechanism. With SiC bricks oxidation is a significant problem are ȕ-Si3N4 and the bright ones Į-Si3N4. The ȕ-Si3N4 crystals in
involving an exchange mechanism of oxygen possibly with part A have irregular shapes and needle shaped crystals of ȕ-Si3N4
fluorides that destroy the sidewall as time passes especially at and were observed in part B, especially in Material 2 (observed with
SEM). Part B of Material 2 shows larger areas of connected ȕ-
above the bath level. Figure 12 shows the role of the critical Si3N4 in the matrix than in Material 1.
agents O2, H2O, Na2O, and HF).
O2 Material 1, outside (part A) Material 1, inside (part B)
High SiF4
porosity and
SiO2 H2O
HF
Bath level
Porosity,
nepheline,
albite and Cryolite compounds
Material 2,outside (part A) Material 2, inside (part B)
SiO2
Na
SiC
ȕ-Si3N4
Na2SiO3 porosity
Na2O
Į-Si3N4
O2
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confirmed by SEM-analysis. The only significant difference and between the shell and the bricks. Good covering practice is
between the four sample compositions is found in the N-content also important. Improved materials without Si3N4 may also be an
of the outer part (A) of Material 2, which is about 30-50% higher option.
than all other N-values.
Oxidation resistance
The differences between the core and the shell of Material 1 and 2.5
Material 2 lies in the coarser matrix and higher porosity of the
2
Si3N4
aluminium, NaAlF4, CO and CO2. 50
SiC
40
30
20
Instead we find sodium hydroxide and assume that sodium metal 10
or sodium oxide combined with moisture is the cause of the 0
A B C D E F
chemical attack. HF gas is also assumed to cause chemical attack. Product
In [3] it is shown that a significant amount of HF is generated in a
modern aluminium electrolysis cell. Figure 15. Oxidation resistance, chemical resistance and chemical
Only at the bath level (location 2) Na-Al-silicates were found. composition (partly) of nitride bonded SiC products [2.]
A more realistic test on Si3N4 bonded SiC sidewall bricks to study Acknowledgements
the chemical attack in an electrolysis cell system should involve The authors wish to thank Sieger van der Laan, Jan Trouw, Jurgen
Na-metal together with oxygen, moisture and NaF in a Bakker, Siegfried Benninghoff and the people at Aluminium
temperature range between 300 and 1000°C. This will imitate the Delfzijl BV for their invaluable help.
attack mechanisms we observe and would allow a better
distinction between good and poor products. Determining the Literature
amount of ȕ-Si3N4 or the ratio to Į-Si3N4 is also an important [1] Skybakmoen et al., “Chemical Resistance of Sidelining
quality criterion. We intend to implement this in our evaluation of Materials”, Light Metals 1999, p215-222.
sidewall products and we hope to be able to report on this in the [2] Selected supplier information and data sheets.
future. [3] Patterson, Hyland, Moxnes, Welch, “Reducing HF emissions
from Al electrolysis cells,” Proceedings of Seventh Australasian
Today product quality of sidewall bricks is mainly evaluated by Aluminium Smelting Technology Conference and Workshops
three parameters: chemical composition, chemical resistance as (11-16 November 2001) ISBN 073341851.
determined by the polarised test and oxidation resistance. For a
number of SiC products from various suppliers these parameters
are compared in figure 15. It is obvious that only in the oxidation
test a significant difference is observed.
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