Ceramics International 43 (2017) 19881996

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Detailed studies on microstructural evolution during the high temperature

corrosion of SiC-containing andalusite refractories in the cement kiln
crossmark
preheater

Dominika Madej , Jacek Szczerba
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-
059 Krakow, Poland

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

Keywords: The corrosion chemistry of SiC-modied andalusite refractories has been studied using a post-mortem approach
Refractories that considers both K+ and Ca2+ ions as the main corrosive agents existing in the cyclone preheater applied in
Andalusite the cement production line. The transient progress of corrosion reactions was investigated as the function of
Silicon carbide distance from the face exposed to the corrosive media (hot face) to the relatively little altered middle zone of
Corrosion model
Al2SiO5-SiC brick. Chemical alteration of the Al2SiO5 and SiC grains was examined and discussed on the basis of
Heating microscopy thermal analysis
phase equilibria in binary (CaO-SiO2, K2O-SiO2) and ternary (K2O-Al2O3-SiO2, CaO-Al2O3-SiO2) systems. Ca
and K-Si-oxide phases along with Ca-aluminosilicate gehlenite Ca2Al2SiO7 and K-aluminosilicates kalsilite
KAlSiO4 and leucite KAlSi2O6 were formed as a consequence of the reactions between both SiO2 and Al2SiO5
with CaO and K2O. The heating microscopy thermal analysis was used to evaluate the behavior of SiC-/ZrSiO4-
andalusite refractory bricks in contact with a partly decarbonized material.

1. Introduction
The non-basic rigid-shaped refractory bricks or monolithics includ-
ing reclay and high-alumina products are successfully used as
refractory lining of equipment items of the cement manufacturing
plant, i.e. multi-stage cyclone preheater, rotary kiln and coolers.
Fireclay products contain below/equal 45% Al2O3 and high-alumina
bricks contain above 45% Al2O3 [1]. As a result of the applied raw
material such as high-alumina aluminosilicate, i.e. andalusite, there is a
resulting classication of SiC-containing andalusite refractories, inves-
tigated in this paper as high-alumina products. Alkali-rich fuels and
raw materials generate critical conditions within the cement produc-
tion line and they can especially lead to an imbalanced alkali sulphur
ratio (ASR). The alkali metal ions seem to have the ability to diuse
into the brick microstructure, causing structural spalling that occurs
when an oxide (Al2O3, SiO2) based brick reacts with alkali, and form
phases with lower density which results in volume expansion, and then
cracks formation. These phenomena are dened as alkali bursting
and have been extensively studied in the literature [29]. Stjernberg et.
al. [9] reported that the disintegration of mullite in the bricks via the
reaction with alkali metals (that results in the formation of K- and Na-
aluminoslicate minerals) is associated with a volume expansions of
between 20% and 25%, which can cause spallation by alkali bursting of
the refractory lining. Other aggressive substances which may corrode
the refractory lining are SO2 from fuel and raw feedstock and chlorine,
contained mainly in the raw feedstock [48].
Considering the above new ways of modication of aluminosilicate
refractories are proposed and presented in the literature [1013]. The
improvements are related especially to the microstructural design in
multi-phase systems. Some of refractories can be enriched with oxide-
or non-oxide compounds and additives. Bo et. al. [10] reported that the
introduction of Si powder markedly improves the densication via
quartz phase generation from the oxidation process of silicon lling in
part of pores, and then reduces potassium (K2O) penetration into
bauxite-SiC composite refractories. Baspinar and Kara [11] reported
that the improvement may be related to the optimization of the
corrosion bahavior of mullite refractories against an attack by vapours
containing sodium (Na2O) by ZrSiO4 addition to the binder matrix.
Prigent et. al. [12] concluded that the use of mullitised andalusite raw
material in the aluminosilicate refractory bodies limits the liquid phase
formation during gas corrosion caused by sodium. Our previous
investigations of the wear mechanism by means of post-mortem
studies of Al2SiO5-ZrSiO4 refractory brick removed from cyclone
preheater found that both K+ and Ca2+ ions cause chemical corrosion

Corresponding author.
E-mail address: dmadej@agh.edu.pl (D. Madej).

http://dx.doi.org/10.1016/j.ceramint.2016.10.166
Received 18 August 2016; Received in revised form 15 October 2016; Accepted 24 October 2016
Available online 27 October 2016
0272-8842/ 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
D. Madej, J. Szczerba
[13].
This paper is a continuation of our previous work [13] regarding the
high temperature corrosion of SiC-containing andalusite refractories in
the cement kiln preheater. The fundamental purpose of this paper is to
investigate the mechanism of high temperature corrosion as observed
by post-mortem investigations of the SiC-modied andalusite refrac-
tory brick. The exact mechanism in this corrosion process have been
illustrated using single grain models, i.e. the components of refractory
brick both Al2SiO5 and SiC that the phases have been continuously
altered by K+ and Ca2+ corrosive ions. Phase equilibria in the binary
(CaO-SiO2, K2O-SiO2) and ternary (K2O-Al2O3-SiO2, CaO-Al2O3-SiO2)
systems at 1100 C were used to explain the chemical and phase
alterations studied in the Al2SiO5-K2O(CaO) and SiC/SiO2-K2O(CaO)
grain micro-regions. The purpose of this work was also to select the
material (ZrSiO4-andalusite refractory brick or SiC-andalusite refrac-
tory brick) for applications in oxidizing atmospheres at temperatures of
about 1100 C.
2. Experimental procedure
2.1. Preparation of SiC-containing andalusite brick
The SiC-containing andalusite brick was prepared using andalusite
(granularity < 2.0 mm, chemical composition (wt%): Al2O3 57.28, SiO2
40.97, Fe2O3 1.03, TiO2 0.22, MgO 0.16, CaO 0.21, K2O 0.35, Na2O
0.09), burned bauxite (granularity < 0.1 mm, chemical composition
(wt%): Al2O3 89.31, SiO2 6.33, Fe2O3 1.14, TiO2 2.93, MgO 0.07, CaO
0.02, K2O 0.01, Na2O 0.02) and a low-grade refractory clay (chemical
composition (wt%): Al2O3 37.00, SiO2 58.00, Fe2O3 2.40, TiO2 0.5,
MgO 0.3, CaO 0.2, K2O + Na2O 1.6) as raw materials and silicon
carbide as a modifying component (granularity < 2.0 mm, its chemical
composition (wt%): SiC 99.56, free Si 0.18, free C 0.02, SiO2 0.24). The
composition of Al2SiO5-SiC brick was as follows (wt%): andalusite 60.0,
silicon carbide 30.0, burned bauxite 5.0 and refractory clay 5.0.
Phosphoric acid 85% (5 wt%) was added during batch homogenization.
The rectangular specimens 23011440 mm were formed by cold
pressing under a pressure of 120 MPa, and nally heat-treated at
1200 C.
2.2. Industrial-scale corrosion test of SiC-containing andalusite brick
In this study, post mortem examinations of SiC-containing anda-
lusite brick have been performed after 8 months of industrial operating
conditions up to 1100 C. For this end, a hole slightly larger than 5 cm
was drilled through the refractory brick and then it was placed on a
chrome-steel supporting tube inside the fourth level cyclone. The tested
brick was at the same time exposed to a corrosive media containing
gases (oxides: CO2, CO, SO2, H2O, K2O, Na2O, NOx; ions: Cl-, K+, Na+,
OH-, H+; heavy-metal vapours i.e. heavy metals with a high relative
volatility: Se, Bi, Pb, Tl, Cd and Hg; heavy metals with moderate
volatility: Rb and Cs), liquids and solid particles of cement raw meal.
The chemical composition of the partly decarbonized material sampled
from the stage-IV cyclone of cement kiln preheater in wt% is as follows:
SiO2 17.04, Al2O3 4.82, Fe2O3 1.64, CaO 54.50, MgO 1.40, Na2O 0.23,
K2O 4.68, SO3 2.86, Cl- content 2.40, loss on ignition (L.O.I.) 12.89.
The phase composition of the analyzed material was as follows: CaO,
KCl, CaCO3, SiO2 quartz, Ca3Al2O6, Ca(OH)2, Ca2SiO4 [13]. Corrosion
of SiC-containing andalusite brick was proceeded when refractory brick
was located in stage-IV cyclone where this solid particles have been
suspended in the gaseous phase.
2.3. Sample preparation and analysis technique
Both as-delivered and corroded SiC-containing andalusite refrac-
tories were analyzed. Some basic physical properties of the uncorroded
sample were determined. Apparent porosity (A.P.) and bulk density
1989
Ceramics International 43 (2017) 19881996
(B.D.) were determined according to PN-EN 9931:1998 P [14].
Three-point bending strength tests were performed as cold and hot
modulus of ruptures (CMOR, HMOR), according to PN-EN 993
6:1998 P [15] and PN-EN 9937:2001 P [16], respectively. The cold
crushing strength was performed according to PN-EN 9935:2001 P
[17]. The thermal expansion of the material was determined by a
dilatometer (NETZSCH DIL 402C) in the temperature range 20
1200 C.
The corroded brick was split into ve separate layers with a
thickness of 8 mm. The corroded brick was cut along the thick of brick
(Z direction). Approximately 100 g of as-delivered refractory brick and
each of the newly separated samples were ground to particles below
63 m. To determine the phase composition of the initial and corroded
samples X-ray powder diractometry method was applied. The X-ray
diraction (XRD) patterns were recorded with an automated
PANalytical XPert diractometer with Cu K radiation (=1.5418 ).
The patterns were recorded from 10 to 90 2 in steps of 0.008. For
mineral identication, the obtained diractograms of samples were
compared with the database provided by the International Centre for
Diraction Data-ICDD PDF2 database. Chemical composition analysis
of both uncorroded and corroded andalusite-based materials was
performed as 1) loss on ignition, total carbon, free carbon and silicon
carbide, total and free silica and total and free silicon according to PN-
EN ISO 210682:2010 P [18] 2) nitrogen, oxygen and metallic and
oxidic constituents according to PN-EN ISO 210683:2010 P [19] 3)
the total SO3 and Cl contents in spent Al2SiO5-SiC brick were
measured by the wet analytical method. The microstructural changes
of the as-delivered and tested samples were characterized by scanning
electron microscopy NOVA NANO SEM 200 of FEI, equipped with a
EDS system of EDAX. For this purpose, resin embedded samples were
polished, coated with carbon to be conductive and then examined.
Moreover, the preheated powdered cement raw material, sampled from
the cement kiln preheater (stage-IV cyclone), was examined according
to the procedure presented in Ref [13].
2.4. Laboratory-scale investigations of the SiC / ZrSiO4-containing
andalusite refractories and partly decarbonized material mixtures
using heating the microscopy thermal analysis
The heating microscopy thermal analysis (HMTA) was used to
analyze dimensional changes as a function of temperature during heat
treatment processes of the SiC or ZrSiO4-containing andalusite refrac-
tories and partly decarbonized material mixtures. For this purpose, a
homogenized mixture of the powdered samples of SiC / ZrSiO4-
modied bricks (50 wt%) and the partly decarbonized raw material
(50 wt%) sampled from the 4. preheater stage of cement rotary kiln
were used to form cubes of 3-mm height, in a manual press. The
changing of the samples shape was conducted by Carl Zeiss MH01
microscope at a heating rate of 10 C/min. The data of the sample
height were collected at intervals of 10 C during the experiment, and
shrinkage curves were obtained. The relative height change of the
sample (h) was calculated according to formula 1.
h(T) h 0
h (T) = 100[%]
h0 (1)
h0 initial height of the sample
h(T) height of the sample at elevated temperature T.
The beginning of sintering process temperature (Ts) as the rst
point less than 98% of the initial height of the sample was determined
from the shrinkage curve.
D. Madej, J. Szczerba Ceramics International 43 (2017) 19881996

Table 1
Chemical composition of uncorroded and corroded SiC-containing andalusite refractories as charged in the experiments (by XRF and wet chemical methods).

Analysis Unreacted brick Zone of corroded refractory brick

Ia IIa III IIb Ib

wt%

Loss on ignition at 750 C (L.O.I.) 0.21 1.08 0.29 0.28 0.21 0.30
SiC content 31.9 28.3 29.6 35.3 35.5 32.0
SiO2 content 19.7 19.7 21.2 15.3 14.6 15.8
Free carbon content 0.20 0.30 0.23 0.22 0.19 0.24

Oxides content determined by XRF Al2O3 40.9 35.1 37.7 37.4 37.4 34.5
Fe2O3 0.93 0.86 0.93 0.92 0.94 0.81
CaO 0.17 2.78 0.85 0.64 0.92 4.87
K2O 0.30 6.07 3.59 3.31 3.27 4.11
P2O5 2.87 2.23 2.64 2.58 2.47 2.31
TiO2 0.34 0.30 0.31 0.31 0.30 0.27
ZrO2 0.52 0.03 0.20 0.28 0.46 0.36
others 1.87 3.19 2.23 3.32 3.51 4.04
Cl- content 0.009 0.799 0.047 0.027 0.106 0.209
SO3 content 0.09 0.06 0.23 0.14 0.23 0.39

3. Results

3.1. Unreacted brick

3.1.1. Chemical analysis and X-ray diraction

The chemical composition of the as-delivered SiC-containing anda-
lusite refractories is shown in Table 1 (unreacted brick) together with
the results of penetrated zones of corroded brick. The phase composi-
tion of the uncorroded brick determined by X-ray diraction shows the
presence of the Al2SiO5 and SiC as major components of refractory
brick and Al2O3, two SiO2 polymorphs: quartz and cristobalite, mullite
solid solution; AlPO4 as minor components were detected. The
appearance of the mullite phase may be attributed to the process of
partial mullitization of both refractory clay and andalusite during the
heat treatment procedure at 1200 C [20,21].

3.1.2. Microstructural study and physical properties

The overview image of the microstructure the SiC-modied anda-
lusite refractories contains silicon carbide that is dicult to distinguish
from the aluminosilicate matrix as well as andalusite (Al2SiO5) grains
that are similarly scaled as dark shades of gray in SEM image (Fig. 1).
Thus, EDS analysis was used to obtain some compositional information
on a specic grain. All the major mineral phases were distinguished
and quantied as typical EDS spectra exposed in Fig. 1a. The detection
of Si and C in point 1; Si, Al and O at point 2; and Si, Al, O and P at
point 3 has enabled us to identify SiC, Al2SiO5 and grains of andalusite
(Al2SiO5) with a small admixture of phosphorus, respectively (Fig. 1).
Based on the contents of the identied elements at point 3 (Fig. 1a) Fig. 1. Overview image of the microstructure of the as-delivered SiC-containing
andalusite refractories. Points 13 EDS analysis: 1 SiC, 2 coarse grain of andalusite
evaluated by SEM/EDS, the grain could be also identied as an
(Al2SiO5), 3 grain of andalusite (Al2SiO5) with an admixture of phosphorus. (a) The
andalusite matrix with inclusion of AlPO4 that was formed during the EDS spectrum corresponding to the region marked as point 3 in Fig. 1.
reaction of phosphoric acid with aluminum oxide. A network of mono-
aluminum phosphate was formed after heat-treatment process within
Table 2
the SiC-modied refractory brick results in a product with a combina- The physical properties of SiC-containing andalusite brick.
tion of chemical and ceramic bonds. The initial sample contains clearly
identiable pores (black spots) in a ne-grained matrix and andalusite Properties Value
grains with an initial network of cracks. Additionally, some physical
Bulk density, g/cm3 2.58
properties of the uncorroded SiC-containing andalusite brick sample Apparent porosity, % 14.6
were presented in Table 2. Cold crushing strength (CCS), MPa 107.8
Cold modulus of rupture at 25 C (CMOR), MPa 17.8
Hot modulus of rupture at 1200 C (HMOR), MPa 5.1
3.2. Post-mortem examination Linear thermal expansion coecient (201200 C), K1 6.95106

The corrosion behavior of SiC-modied andalusite refractories in

contact with corrosive media containing gases, liquids and solid
particles of cement raw meal was evaluated. The refractory brick after

1990
D. Madej, J. Szczerba Ceramics International 43 (2017) 19881996

Fig. 2. Tested SiC-containing andalusite brick after industrial-scale corrosion test in

cement kiln preheater.

the corrosion test was withdrawn from the cyclone preheater after 8
months of exposure to the extremely alkaline environment at the
temperature up to about 1100 C. This approach was adopted to
compare corroded (Fig. 2) and un-corroded bricks, especially to
determine the changes in chemical and phase compositions and
microstructure of these samples. Representative samples for the post
mortem examinations were prepared and investigated according to the
appropriate procedures described in Section 2.3.

3.2.1. Chemical analysis

The results of X-ray uorescence analysis (Table 1) show that
although both potassium and calcium penetrate into the brick,
potassium could be considered as a more eective agent that reacts
chemically with the primary mineral phases present in red high-
alumina brick. The macroscopic observation of the corroded brick
(Fig. 2) conrms chemical reaction phenomena due to the attack of
corrosive agents. The penetration of both alkaline vapours and alkaline
condensates caused corrosion failure due to volume expansion and
cracks formation, generally known as alkali bursting. The highest
concentration of both potassium and calcium was determined in two
reaction (outer) zones, Ia and Ib (along the Z direction). As the
exposure time proceeded, the concentration gradients were formed
from the refractory / cement kiln, the preheater environment interface
decreased, and in the middle zone III, located at half brick thickness,
some penetration and minor reactions occurred. Two intermediate
zones, IIa and IIb, were also formed, exactly as described in Ref [13]..
Thus, it can be conjectured that K+, Ca2+ and Cl ions are entrapped
into the SiC-containing andalusite brick as new mineral phases formed
as a results of attack by corrosive media on the primary mineral phases.
3.2.2. X-ray diraction
The chemical phase of corroded SiC-containing andalusite brick
may have changed with a changing chemical composition during
exposure to the K, Ca-rich environment. Based on XRD experimental
diraction data and according to a comparison of the XRD spectra
(Fig. 3), generated by samples before and after being corroded in the
cement kiln preheater, it can be stated that K-aluminosilicates and Ca-
aluminosilicates were formed as a result of a reaction between
andalusite particles and potassium or calcium, respectively. The
mineralogical composition of corroded refractory brick consists of
kalsilite (KAlSiO4), leucite (KAlSi2O6) and gehlenite (Ca2Si2SiO7) as a
three-phase corrosion product formed across the thickness of an
adequate zone. Secondary K-aluminoslicate phases, i.e. kalsilite
KAlSiO4 and leucite KAlSi2O6, are distributed throughout the whole
mass of the refractory brick. It is worth noting that in Ia sample, the
peak intensities related to the kalsilite phase is higher than other
samples which may be ascribed to the highest amount of K2O in the
chemical composition of the corroded Ia zone (Table 1). X-ray
diraction patterns contain the strongest lines of kalsilite and leucite
that correspond to the interplanar spacing values of 3.10800
Fig. 3. X-ray diraction patterns of the uncorroded and corroded SiC-containing
andalusite refractory brick.
(Reference code: 00-0481028) and 3.35750 (Reference code: 01-
076-2298), respectively [22]. Likewise, the appearance of the strongest
diraction peak of gehlenite, corresponding to the interplanar spacing
value of 2.85136 (Reference code: 98-002-4588) [22], was found in
the corroded Ib zone with the highest CaO content. It should be noted
that the presence of mullite is observed in both uncorroded and
corroded materials. This may be due to the fact that the mullitization
process of high-alumina refractory raw materials, i.e. andalusite and
refractory clay. The aluminum phosphate, whose peak seems to overlap
with the strongest line of cristobalite was detected in uncorroded brick.
The formation of AlPO4 phase was attributed to the reaction of
phosphoric acid with aluminum oxide. Additionally, potassium chlor-
ide was only detected in the edge zones Ia and Ib. In all XRD patterns,
related to the samples (Fig. 3), the peaks of andalusite and silicon
carbide phases are easily detectable.
3.2.3. Microstructural study
The results of the microstructural investigation performed after
testing a SiC-modied andalusite refractory brick in the cement kiln
preheater are shown in Figs. 48. The brick microstructure was
inltrated by corrosive agents, generating two reaction zones Ia and
Ib, two intermediate zones IIa and IIb, and middle zone III with K and
Ca concentration gradients across brick layers (Table 1). Below the hot
face region (interface), an inltrated and corroded brick microstructure
was observed (Fig. 4a). In the inltrated brick microstructure, the
corrosion of both andalusite, Al2SiO5 and silicon carbide, SiC compo-
nents took place. From one point of view, the main reaction products
between Al2SiO5 and K2O or CaO were mainly K-aluminosilicate and
Ca-aluminosilicate, respectively. At some micro-areas/points of the

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D. Madej, J. Szczerba Ceramics International 43 (2017) 19881996

Fig. 6. (a). SEM image of the fractured surface of the corroded SiC-modied andalusite
Fig. 4. (a). Overview image of the microstructure of the corroded SiC-modied
brick (hot face). (Point 1) EDS analysis: 1 K-Si-oxide phase, (b) The EDS spectrum
andalusite refractory brick (reaction zone). (Points 17) EDS analysis: 1 KCl, 2
results corresponding to the specic region marked as point 1 in Fig. 6(a).
Ca2Al2SiO7, 3 SiC, 4 Ca3(PO4)2, 5 Al2SiO5, 6 KAlSiO4 with Ca3(PO4)2 inclusions,
7 K2O-Al2O3-SiO2 phase similar in chemical composition to KAlSi2O6. (b) The EDS
spectrum results corresponding to the specic region marked as point 2 in Fig. 4(a).

Fig. 5. A detailed SEM image of the micro-area of SiC grain visualizes in Fig. 4a (Point
3). EDS analysis: 1, 2, 4 Ca-Si-oxide phases, 3 SiC.

partly corrosion aected andalusite matrix, the weight percentages of

elements were determined by the quantitative EDS microanalysis in
SEM (Table 3), and then they were compared to the concentration of
elements in a stoichiometric compound, specied also in weight
percentage. Thus, the phase compositions was estimated indirectly.
In this way, the secondary phases in the reaction zone were identied.
K-aluminosilicates of kalsilite, KAlSiO4 (Table 3, point 6) and leucite,
KAlSi2O6 (Table 3, point 7) types and the Ca-aluminosilicate of Fig. 7. (a). SEM image of the polished cross section of the corroded SiC-modied
andalusite brick (intermediate zone). (Points 15) EDS analysis: 1 Al2SiO5, 2
gehlenite, Ca2Al2SiO7 (Table 3, point 2 and Fig. 4b) type form an outer
KAlSi2O6 with KCa(PO3)3 inclusions, 3 SiO2, 4 SiC, 5 KAlSi2O6 with AlPO4
reaction ring around the unreacted andalusite, Al2SiO5 grain core inclusions. (b) The EDS spectrum corresponding to the point marked as 5 in Fig. 7(a).
(Table 3, point 5). Likewise, due to diusion processes, the chemical
composition of the SiC grains was also transformed, having become 2 and 4(Fig. 5 and Table 4) were Ca-Si oxide phases, and they have
mainly enriched with K-oxide or Ca-oxide at the rims (Fig. 5). This type not been clearly identied as binary phases in the phase diagram of the
of reaction would be expected whenever oxidation of SiC particles with CaO-SiO2 system [23]. K-Si-oxide phase was detected on the oxidized
the formation of SiO2 occurred. The intermediate phases of points 1,

1992
D. Madej, J. Szczerba Ceramics International 43 (2017) 19881996

Table 5
EDS point elemental analysis corresponding to the specific regions marked as points 1
3 and 5 in Fig. 7a.

Point Element (wt%)

O Al Si P K Ca

1 51.2 32.2 16.6

2 41.5 16.2 14.3 9.2 14.2 4.6
3 52.0 48.0
5 42.1 20.1 15.3 8.0 14.5

also that the SiC particle (point 4) oxidation occurred, forming silica-
rich rims (point 3). Along with the deposited KCl (point 1) and K2(S,
Cr)O4 (point 2), crystals within open pores of brick (Fig. 8) were found.

Fig. 8. SEM image of the polished cross section of the corroded SiC-modied andalusite 3.3. Heating microscopy of the SiC/ZrSiO4-containing andalusite
brick (intermediate zone) with deposited KCl (Point 1) and K2(S,Cr)O4 (Point 2) crystals refractories and partly decarbonized material mixtures
within open pores of brick.

With the objective to obtain design data for further applications of

Table 3 both SiC- or ZrSiO4-containing andalusite material as the at brick
EDS point elemental analysis corresponding to the specific regions marked as points 12
lining in the devices in ceramic industry with high-temperature and
and 47 in Fig. 4a.
strong alkaline environments, the present paper deals with the micro-
Point Element (wt%) structure and phase composition characterization of the SiC-andalusite
refractory brick, corroded under the cement kiln preheater condition as
O Mg Al Si P Cl K Ca Ti Fe
an appendix for our last research paper [13]. A coupling of a phase
1 47.8 52.2 transition with macroscopic dimensional changes presents various
2 40.0 0.4 18.0 9.4 1.1 0.8 0.8 29.5 interesting features whose importance is becoming increasingly evi-
4 44.2 18.7 0.7 36.4 dent. Expansion and/or shrinking curves during heat treatment
5 49.8 34.2 16.0
processes of the SiC- or ZrSiO4-containing andalusite refractories and
6 41.0 15.7 14.1 2.9 0.4 21.2 4.7
7 43.2 14.7 18.6 0.9 0.4 14.4 5.4 0.6 1.8
partly decarbonized material mixtures were obtained by the heating
microscopy thermal analysis (HMTA) and are presented in Fig. 9. The
sintering temperature of the SiC and ZrSiO4-containing andalusite
Table 4 refractories and partly decarbonized material mixtures as a dimen-
EDS point elemental analysis corresponding to the specific regions marked as points 1, sional variation corresponding to the 2% with respect to the rst
2 and 4 in Fig. 5. image acquired, which is taken to be 100%, were determined. The
Point Element (wt%)
following results were obtained for these samples Ts=1235 C (SiC-
containing andalusite brick and partly decarbonized material) and
O Al Si Cl K Ca Ts=1245 C (ZrSiO4-containing andalusite brick and partly decarbo-
nized material). It is clearly seen that the data are very close together.
1 38.2 44.3 17.5
2 41.4 0.8 31.8 26.0
Nevertheless, the shape of the shrinkage curves diers signicantly
4 33.6 1.0 8.8 2.1 2.7 51.8 from each other. When heated, SiC-containing andalusite brick and
partly decarbonized material mixture expands more than the ZrSiO4-
containing andalusite brick and partly decarbonized material mixture
surface of crystal grain of SiC (Fig. 6a-b, point 1) and they have not up to 1100 C. The following expansion results were obtained for these
been clearly identied as binary phases in the phase diagram of the
K2O-SiO2 system [24]. This is also clearly illustrated in the left SEM
image (lower magnication) of the Graphical abstract. Nevertheless, it
might be supposed that further chemical reactions would occur
through the formation of both Ca-silicate phases and K-silicate phases.
Besides, calcium phosphate, Ca3(PO4)2 (Fig. 4a and Table 3, point 4)
has been produced by the reaction between aluminum phosphate
(AlPO4), being a bonding phase within refractory brick, and calcium
ions, according to reaction 2:

3CaO + 2AlPO4 Ca3(PO4)2 + Al2O3 (2)

Two elements i.e. K and Cl, were also identied using SEM/EDS
microanalysis, thus indicating the presence of a deposited potassium
chloride, KCl (Fig. 4a and Table 3, point 1).
Based on the results shown in Fig. 7a and provided in Table 5 it can
be concluded that the partly-reacted portion of the brick, which is
located deeper, diers from both the hot face region and the reaction
zone of a brick. The main corrosion product appears to be the K-poor
phase, i.e. KAlSi2O6 (Fig. 7a-b and Table 5, points 2 and 5) with
inclusions of P-containing compounds. The SEM analysis conrmed Fig. 9. Shrinkage curves of SiC and ZrSiO4-containing andalusite refractories and partly
decarbonized material mixtures.

1993
D. Madej, J. Szczerba
Fig. 10. Heating microscope images obtained at dierent temperatures. A1 SiC-modied andalusite brick and partly decarbonized material mixture, A2 ZrSiO4-modied andalusite
brick and partly decarbonized material mixture.
samples, i.e. about 12% and about 6%, respectively. It is worth
mentioning that the eects produced by heating SiC-Al2SiO5 brick
with the corrosive agent arise from the mineralogical changes produced
by increasing temperatures and the formation of the high viscosity of
the slica-rich glassy phase developed due to the interfacial reactions of
oxidized SiC particles with K-bearing partly decarbonized material.
Dierently, the liquid phase, having lower viscosity, was formed via
heat treatment processes of the ZrSiO4-Al2SiO5 brick and partly
decarbonized material mixture and hence the samples were signi-
cantly deformed at 1280 C (Fig. 10).
4. Discussion
The phenomena that occur during refractory corrosion in the
cement kiln preheater and a model that explains the chemical and
micro-structural changes in a thin-wall refractory lining without
temperature gradient conditions were investigated in detail in our
previous paper [13]. This decision should therefore follow the same
approach considering the K+ and Ca2+ ions as the main corrosive
agents that easily penetrate through the pore channels of the material.
The transformation of the andalusite compound (Al2SiO5 Al2O3
SiO2) into the new K- and Ca- bearing phases could be adequately
explained by the isothermal section of the phase diagrams of the
ternary systems K2O-Al2O-SiO2 and CaO-Al2O3-SiO2 at 1100 C pre-
sented in Ref [13]. The andalusite grain will be gradually altered into
orthoclase KAlSi3O8, leucite KAlSi2O6 and the most K-rich phase, i.e.
kalsilite KAlSiO4, forming the andalusite grain-rimming reaction zone.
Andalusite grain transformation under the inuence of Ca2+ ions into
Ca-aluminosilicates could be explained using a similar approach
involving the shrinking core model (SCM). Thus, the formation of the
Ca-aluminosulicate phases, i.e. anorthite CaAl2Si2O8 (CAS2), and
gehlenite CaAl2Si2O7 (C2AS), is expected. The elaborated data con-
cerning the phases in equilibrium across the lines from point K2O and
CaO to the point represented by the composition of andalusite (Al2O3
62.93 wt%, SiO2 37.07 wt%) in the phase equilibria in the K2O-Al2O-
SiO2 and CaO-Al2O3-SiO2 at 1100 C are also discussed in Ref [13].
1994
Ceramics International 43 (2017) 19881996
Regarding a modifying agent of these refractories, i.e. silicon
carbide, it was found that the Ca- and K-Si-oxide phases occurred in
the SiC grain-rimming reaction zone. The chemical reaction between
SiC and both CaO and K2O were preceded by oxidation of silicon
carbide particles, leading to the formation of a silica layer. Based on the
K2O-SiO2 phase system [24], the melting point of alkali silicates is in
the range 7501100 C. These alkali silicates formed during the
corrosion process can melt and form a sticky coating on the surface
of SiC particles which then reacts with the components of an alumino-
silicate matrix. Likewise, based on the CaO-SiO2 system [23], the
melting point of calcium silicates exceeds the temperature of the
sample during a corrosion experiment. Hence, the solid-state reactions
could be expected to occur in the SiC/SiO2-CaO grain area. Based on
theoretical considerations on the reaction mechanism in the systems
K2O-SiO2, K2O-Al2O3-SiO2, CaO-SiO2 and CaO-Al2O3-SiO2 and the
presented results we expect that the corrosion reactions at the single-
grain level would proceed from stage I to III, which is graphically
presented in Fig. 11.
HMTA was used to evaluate dimensional changes of the SiC /
ZrSiO4-containing andalusite refractories and partly decarbonized
material mixtures during their heat treatment process. The method
developed in this work allows an unambiguous assessment of the
behavior of both materials in contact with aggressive medium that
cause corrosion processes to be achieved, from microprocessed images
and a HMTA dimensional change curve. These trials provided some
surprising results, and raised questions about the replacement of
ZrSiO4 with SiC. An exposure of the SiC-modied to strong alkaline
environments up to temperature of about 1100 C results in signicant
expansion. Hence, the most appropriate material for the future use in
oxidizing atmospheres at the temperature of about 1100 C is the
ZrSiO4-containing andalusite refractory brick. Nevertheless, due to the
formation of high viscosity of the silica-rich glassy phase that helps to
maintain the shape of the sample, the most appropriate material to be
used at the temperatures above 1100 C seems to be the SiC-containing
andalusite refractory brick.
D. Madej, J. Szczerba Ceramics International 43 (2017) 19881996

Fig. 11. Proposed schematic presentation of the micro-scale model for formation mechanism of secondary phases in SiC-modied andalusite refractories; KAS2 KAlSiO4, KAS4
KAlSi2O6, KAS6 KAlSi3O8, CAS2 CaAl2Si2O8, C2AS Ca2Al2SiO7, C12A7 Ca12Al14O33, C2S Ca2SiO4, AS Al2SiO5. Stages I-III.

5. Conclusions phenomena generated new K-aluminosilicate, Ca-aluminosilicate, Ca-

This study provides an example of detailed post-mortem examina-
tions of corroded SiC-modied andalusite refractories. For this pur-
pose, an industrial-scale corrosion test at the fourth stage cyclone
preheater in the Polish cement plant was performed. The sample was
aected by solid particles of a partly decarbonized raw meal suspended
in the gaseous phase during 8 months of industrial operating condi-
tions up to the temperature of about 1100 C. The inltration of
reactants, especially K+ and Ca2+, into the refractory substrate and then
the in situ corrosion reactions of Al2SiO5 and SiC phases occurred.
Before, the SiC particles were oxidized, forming silica-rich rims. These
silicate and K-silicate phases. Based on the SEM results and theoretical
considerations presented in this paper we expect that the phase
changes within the microareas of K2O-SiO2/SiC(grain) and K2O-
Al2SiO5(grain) could proceed along the liquid phase formation. Along
with these eects, microstructural changes within the microareas of
CaO-SiO2/SiC(grain) and CaO-Al2SiO5(grain) were found to proceed in
a solid state. The products formed were mainly investigated by
microstructural techniques (SEM with energy-dispersive X-ray analy-
sis) and X-ray diraction. The identied secondary phases in SiC-
modied refractory ceramics were Ca and K-Si-oxide phases along with
Ca-aluminosilicate gehlenite Ca2Al2SiO7 and K-aluminosilicates

1995
D. Madej, J. Szczerba
kalsilite KAlSiO4 and leucite KAlSi2O6. The network of mono-alumi-
num phosphate (AlPO4) within the ceramic matrix of the brick was also
transformed into KCa(PO3)3 and Ca3(PO4)2, due to the attack by K+
and Ca2+ ions. Secondary KCl and K2(S, Cr)O4 crystals were found in
the open pores in the SiC-Al2SiO5 brick.
Since the attack of alkalis on the aluminosilicate refractories is an
increasingly observed wear phenomenon called alkali bursting in the
areas of the cement plant (multi-stage cyclone preheater, rotary kiln,
coolers), SiC-modied non-basic refractory ceramic composites need to
be highlighted and the only eective way of increasing corrosion
resistance of refractory lining appears to be an improved densication
of the brick structure. The heating microscope was ideal for studying
the direct observation of SiC-modied andalusite material in contact
with the partially decarbonized raw material during a heating cycle and
it allowed a comparison with the results of damage measurement of
ZrSiO4-modied andalusite material to be carried out.
Acknowledgements
The research was performed at Faculty of Materials Science and
Ceramics of AGH within the connes of the project no 11.11.160.617.
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