International Materials Reviews

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Use of phase diagrams in studies of refractories

corrosion

S. Zhang & W.E. Lee

To cite this article: S. Zhang & W.E. Lee (2000) Use of phase diagrams in studies of refractories
corrosion, International Materials Reviews, 45:2, 41-58, DOI: 10.1179/095066000101528304

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Use of phase diagrams in studies of
refractories corrosion
S. Zhang and W. E. Lee
Typical applications of phase diagrams to specific
problems of refractories corrosion are highlighted.
Saturation solubilities of refractories components
in molten slags can be estimated using existing
phase diagrams. These can then be used to predict
the corrosion behaviour, and qualitatively compare
the corrosion resistance, of a refractory in different
slags or different refractories in the same slag.
If the slag is not saturated with refractories
components, using relevant phase diagrams, the
conditions under which solid reaction product
phases form at refractories/slag interfaces can be
predicted, which assists understanding of direct
and indirect dissolution. By checking the
compatibility between impurities or additives and
refractories components at high temperatures,
their influence on corrosion resistance can be
predicted, aiding their selection. Phase diagrams
also reveal that atmosphere affects refractories
corrosion resistance by altering the valence of
some components (in particular, iron oxide) in the
refractories and/or slags. The compatibility
between refractories and slags indicates the
corrosion resistance of different refractories,
assisting refractories selection for specific
applications. Finally, phase diagrams can be used
to assist design of refractories composition.
Repeated experimental corrosion test results show
good agreement with phase diagram predictions.
Therefore, use of the information which is
available in existing phase diagrams can reduce
the need for expensive and time consuming
experiments to evaluate high temperature
corrosion of refractories (and other ceramics).
IMR/351
© 2000 IoM Communications Ltd and ASM International.
The authors are in the Department of Engineering
Materials, The University of Sheffield, Mappin Street,
Sheffield S1 3JD, UK.
Introduction
Refractories are non-metallic materials used to line
many industrial furnaces for high temperature pro-
duction of other materials such as metals, glass,
cement, and petrochemicals. Decreased service life of
refractories is caused by damage arising from, for
example, deformation at high temperature, thermal
shock, mechanical abrasion, and chemical corrosion.
Among these factors, chemical attack by the slag is
often the most critical.
To determine chemical corrosion mechanisms and
to compare corrosion resistance of different refractor-
ies, several test methods have evolved.1,2 However,
many of these tests are expensive and time consuming,
and in some cases, they are conducted just to
re-establish information already known and generally
ISSN 0950–6608
available in existing phase equilibrium diagrams.
Although the importance of phase diagrams to studies
of refractories corrosion has been highlighted,3–7 and
a few cases such as attack of Al O –SiO refractories
2 3 2
by alkali oxides well studied,4,6,7 their use is far from
ubiquitous.
This paper seeks to emphasise applications of phase
diagrams to specific refractories corrosion problems
using typical examples. Previously reported experi-
mental results which were not well explained have
been re-analysed and earlier discrepancies clarified
using the relevant phase diagrams.
Significance of saturation solubility of
refractories oxide phases in liquid slag
Dissolution of solid oxides in liquid slag is governed
by: (a) chemical reaction (or solution) at the
refractories/slag interface or ( b) transport (or
diffusion) of reacting species.8 In the latter case,
dissolution rate can be expressed in terms of the
Nernst equation
J=D(C −C )/d . . . . . . . . . . (1)
s m
where D is the diffusion coefficient (m2 s−1), C and
m
C are, respectively, concentration and saturation
s
solubility of refractory in the slag (g m−3), and d is
the effective boundary layer thickness (m).
Increasing D or decreasing d (i.e. increasing
D/d) increases dissolution rate J. Besides this, it is
clear from equation (1) that the value of C −C
s m
strongly influences dissolution rate. If the slag is
saturated with refractory oxide, then J=0. Naturally,
to minimise the dissolution rate, it is necessary to
minimise C −C . For example, with increasing MgO
s m
content in the slag, the corrosion of the periclase
phase in magnesite–dolomite or in magnesite–chrome
refractories will decrease. If C =0, then the value of
m
C −C reaches a maximum and thus, so does the
s m
dissolution rate.
Fortunately, the saturation solubility of the refrac-
tories oxide in liquid slag can be estimated using
existing phase diagrams. By then checking the differ-
ence between the concentrations and saturation solu-
bilities of the main refractories components in the
molten slag, their relative resistance to slag attack
can be compared, and thus the influence of refractories
composition on corrosion resistance can be predicted.
Consider the influence of MgO concentration
and saturation solubility in silicate slag on the dissolu-
tion of solid MgO. Matsui et al.9 examined the
dissolution rate of sintered and fused MgO grain into
silicate slags at 1600°C by measuring the weight
changes of MgO grain before and after heating in the
slags given in Table 1. Using the phase diagram
(showing MgO solubility data)10 shown in Fig. 1, the
saturation solubility of MgO in each slag can be
International Materials Reviews 2000 Vol. 45 No. 2 41
42 Zhang and Lee Use of phase diagrams in studies of refractories corrosion

%
wt-

2 Weight loss of fused (F-1) and sintered (S-1)

MgO grain corroded for different times at 1600?C
by slags A-0, A-5, and A-10 given in Table 1
1 CaO–MgO–Fe O –SiO phase diagram at 1600?C (after Ref. 9)
2 3 2
with MgO saturation solubilities in liquid phase:
Per. periclase, Sp. spinel (after Ref. 10)
a basicity (CaO/SiO weight ratio (C/S)) of 1·0, then
2
the saturation solubilities of MgO, Cr O , and Al O
estimated. The saturation solubilities of MgO in the 2 3 2 3
in the slag at the test temperature are calculated to
slags at 1600°C thus obtained and the C −C values be ~24·3 wt-% (point L on Fig. 3a), ~7·1 wt-%
s m 1
are listed in Table 1, showing the C −C values (point L on Fig. 3b), and ~63·2 wt-% (point L on
s m 2 3
corresponding to slags A-15, B-10, and C-10 are Fig. 3c), respectively. Clearly, Cr O has the lowest
negative (-ve). These slags are thus oversaturated with 2 3
solubility in the slag whereas Al O has the highest,
respect to MgO at 1600°C, so they cannot dissolve 2 3
so that in a CaO–SiO based slag (with C/S ratio
MgO at this temperature. On the other hand, the 2
around 1·0), increasing the Cr O content in MK will
C −C values for slags A-0, A-5, and A-10 are 2 3
s m be expected to increase the corrosion resistance of
positive with A-10<A-5<A-0. Since the D/d values the refractories, but increasing the Al O content in
of these three slags are only slightly different9 accord- 2 3
MK would decrease slag corrosion resistance. Finger,
ing to equation (1), the dissolution rate of solid MgO induction furnace, and rotary slag test results12–15
in them will increase in the following order, agree with the above predictions based on the calcu-
A-0>A-5>A-10. Consistent with these predictions, lation of saturation solubilities. Figure 4, for example,
Matsui et al.9 found that slags A-15, B-10, and C-10 shows the rotary slag test results of Ichikawa et al.12
did not dissolve MgO at 1600°C, while the order of and Hiragushi et al.13 In Fig. 4, the corrosion
MgO dissolution rate in slags A-0, A-5, and A-10 was resistance of refractories is indicated by the relative
as predicted based on the calculation of saturation corrosion (or wear) index. Higher corrosion (or wear)
solubilities (Fig. 2). index means greater corrosion. With higher Al O
Refractories are composed of many components 2 3
content in the brick, the corrosion is greater (Fig. 4a),
and by checking the saturation solubility of each in and with higher Cr O content in the brick, the
molten slag, the influence of refractories composition 2 3
corrosion is lower (Fig. 4b).
on corrosion resistance can be predicted. A good Another relevant example is the influence of carbon
example is the influence of relative contents of Cr O , (C) content and periclase crystal size in MgO grain
2 3
Al O , and MgO in magnesia–chrome refractories on the corrosion resistance of MgO–C refractories
2 3
(MK) on their corrosion resistance. Figure 3 shows used in basic oxygen furnaces (BOFs). Figure 5 shows
CaO–MgO–SiO , CaO–Cr O –SiO , and CaO– the phase relations in the CaO–MgO–Al O –SiO
2 2 3 2 2 3 2
Al O –SiO ternary phase diagrams.11 Assuming a system at liquidus temperatures in planes of constant
2 3 2
test temperature of 1700°C and CaO–SiO slag with Al O spaced at 5 wt-% intervals.16 From the iso-
2 2 3
therms shown in Fig. 5, the saturation solubilities of
Table 1 Chemical composition and saturation MgO in CaO–Al O –SiO (CAS) slags with various
solubility C of MgO in various slags 2 3 2
s basicities can be calculated. Figure 6, as an example,
(wt-%) (data from Ref. 9) shows the saturation solubility of MgO in the CAS
Slag slags with 10 wt-% Al O but different basicities at
2 3
A-0 A-5 A-10 A-15 B-10 C-10 1700°C. With increasing slag basicity from 1·0 to 3·0,
the saturation solubility of MgO in the slag decreases
CaO 43·0 40·1 39·2 36·9 43·4 47·4
SiO 21·5 19·3 20·8 19·9 15·2 11·7
from ~29 to ~12·5 wt-%. The BOF slag in the ‘early’
2 stage is acid (C/S around 1·0), but changes to basic
Fe O 35·0 32·7 32·0 29·9 30·5 31·3
2 3
MgO 0 4·8 8·3 12·4 8·8 8·8 in the ‘late’ stage (C/S above 3·0).17 In the early stage,
C ~9·0 ~8·5 ~10·0 ~10·0 <8·0 <8·0 the solubility of MgO in the slag is high (Fig. 6) and
s
C –C ~9·0 ~3·6 ~1·7 -ve -ve -ve
s m the dissolution of MgO from the MgO–C refractories
International Materials Reviews 2000 Vol. 45 No. 2
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 43

(a) (b)

wt-% wt-%
(c)

wt-%

3 Phase diagrams of a CaO–MgO–SiO , b CaO–Cr O –SiO , and c CaO–Al O –SiO systems (Ref. 11)
2 2 3 2 2 3 2

into the slag is a dominant factor affecting their
corrosion resistance. So in this case, increasing the
content of C (which is an inert component to silicate
slag) or using MgO with larger crystal size (e.g. fused
MgO) will be expected to improve the corrosion
resistance of the MgO–C refractories. However, in
the late stage, the saturation solubility of MgO in the
slag becomes low (Fig. 6), so dissolution of MgO in
the slag is not a serious problem. In this case, C
oxidation becomes the dominant factor affecting the
corrosion resistance so that increasing the C content
or using MgO with larger crystal size will not greatly
improve the corrosion resistance of the MgO–C
refractories. In some cases using too much C decreases
the corrosion resistance because of the oxidation of
C and the weak nature of the resulting bond. These
conclusions are supported by rotary slag test results
(Figs. 7 and 8). Figure 7 shows that in a more acid
slag (slag A, C/S=1·5), increasing the graphite con-
tent in the brick improves the corrosion resistance
( lower corrosion index), but in a basic slag (slag B,
C/S=3·3), increasing the graphite content from 5 to
20 wt-% does not obviously improve corrosion resist-
ance, and increasing its content to above 20 wt-%
lowers corrosion resistance. Figure 8 shows that, in
an acid slag (C/S=1·2), increasing C content (from
5 to 15 wt-%) and use of MgO with larger crystal
size (B), increases the corrosion resistance, but in a
basic slag (C/S=2·5) these changes have little effect.
Direct and indirect dissolution:
prediction of formation of reaction
products at refractories/slag
interfaces
Dissolution of refractory oxide into silicate slag gener-
ally can be homogeneous (congruent or direct) or
heterogeneous (incongruent or indirect). The former
occurs between refractory oxides and molten slag
International Materials Reviews 2000 Vol. 45 No. 2
44 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
(a)
(b)
4 Wear index (rotary slag test) of MgO–Cr O brick
2 3
as function of a Al O content12 or b Cr O
2 3 2 3
content,13 showing that increasing brick Al O
2 3
content increases corrosion, but increasing
Cr O content decreases corrosion: slag
2 3
composition (A) C/S=1·0, Al O =10 wt-% and
2 3
(B) C/S=1·0, Al O =30 wt-%
2 3
when ions from the refractory oxides dissolve directly
into the melt, while the latter occurs when one or
more solid reaction products form at the refractory
oxide/slag interface separating the oxide from the
slag.2,20–26 Because of the formation of a solid
interface product layer (or layers) in the latter case,
the dissolution rate will be decreased. Obviously, to
understand the corrosion mechanism clearly and
evaluate the corrosion resistance, it is necessary to
know the conditions under which solid reaction prod-
ucts form at the refractories/slag interface at high
temperature. The following two examples, dissolution
of Al O and MgO in CAS (or CMAS) slag, illustrate
2 3
how to use phase diagrams to predict formation of
reaction product layers at high temperatures.
Corrosion of Al O by CAS or CMAS slag
2 3
Consider the dissolution of Al O in four CAS slags
2 3
with the same Al O content (25 wt-%) but different
2 3
C/S ratios (0·5, 1·0, 1·5, and 2·0). These four slags are
indicated on the CaO–Al O –SiO phase diagram
2 3 2 CMAS slag favours the formation of solid MA spinel
(Fig. 3c) by points a, b, c, and d, respectively. Draw
a straight line between each of these points and the
Al O apex (A). Because the line aA does not hit
2 3
the boundary curve (EF) between the CA primary
6
field and Al O primary field, and the temperature of
2 3
International Materials Reviews 2000 Vol. 45 No. 2
invariant point E corresponding to DCAS –A–CA is
2 6
~1500°C, with a test temperature above 1500°C, CA
6
layer formation is not expected in this slag. In other
words, if CA is observed in the microstructure, it has
6
formed on cooling not at the test temperature. The
lines bA, cA, and dA intersect with the boundary
curve EF, but the temperatures corresponding to the
intersection point are different (~1720, 1780, and
1810°C, respectively). Assuming a test temperature
of 1600°C and a composition of 90 wt-% solid
Al O +10 wt-% slag, then the amounts of precipi-
2 3
tated CA corresponding to the slags b, c, and d are
6
calculated to be ~15·6, 27·8, and 39·7 wt-%, respect-
ively. These results indicate that increasing the
basicity of the CAS slag will favour the formation of
solid CA at high temperature, i.e. favour the indirect
6
dissolution of Al O in the slag.
2 3
For the case of CMAS slag, whether solid CA
6
forms or solid MA spinel forms at high temperatures
depends on the relative CaO and MgO contents in
the slag, which can be estimated using the CaO–
MgO–Al O (Fig. 9)27 and CaO–MgO–Al O –SiO
2 3 2 3 2
phase diagrams (with 5–15 wt-% MgO) (Fig. 10).28
Although the CaO–MgO–Al O phase diagram is too
2 3
simple to predict the detailed corrosion process of
Al O in the CMAS slag, it provides some useful
2 3
information regarding the formation of solid CA or
6
MA at high temperature. Draw a straight line between
the Al O apex (A) and invariant point (X) corres-
2 3
ponding to DA–CA –MA in Fig. 9. The CaO/MgO
6
ratio corresponding to this line is ~4·4. Therefore, if
the CaO/MgO ratio in the CMAS slag is above ~4·4,
then, the joint line between the point A and slag
composition point will hit the boundary curve (XY)
between the Al O primary field and the CA primary
2 3 6
field. Consequently, a CA layer is expected to form
6
adjacent the solid Al O . If the CaO/MgO ratio in
2 3
the CMAS slag is below ~4·4, then the joint line
will hit the boundary curve (XZ) between the Al O
2 3
primary field and the MA primary field, so that in
this case an MA layer is expected adjacent the solid
Al O .
2 3
If more components are included in the system, the
critical CaO/MgO value will be a little different from
the value (4·4) estimated above. For example, if SiO
2
is included in the system, based on the CaO/SiO –
2
Al O –MgO phase diagrams given by Kitai,29 the
2 3
critical CaO/MgO value is calculated to be ~4·5
when the C/S ratio of the slag is between 1·0 and 3·0.
The above CaO/MgO ratio (~4·5) can be used to
predict experimental results approximately. Sandhage
and Yurek21 found a CA layer formed adjacent to
6
solid Al O in a slag with CaO/MgO=7·0, but an
2 3
MA layer formed adjacent solid Al O in slags with
2 3
CaO/MgO<~4·5. The present authors examined
the dissolution of Al O in a Fe O and MnO contain-
2 3 x
ing CMAS slag with CaO/MgO=6·0, so a CA layer
6
formed adjacent the solid Al O .30
2 3
The fact that increasing MgO concentration in
at high temperature is also reflected in the phase
diagrams shown in Fig. 10 which shows that the area
of MA liquidus surface increases with increasing MgO
content in the system.
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 45

(a)

(b) (c)

(d) (e)

(f) (g)

a 5 wt-%Al O ; b 10 wt-%Al O ; c 15 wt-%Al O ; d 20 wt-%Al O ; e 25 wt-%Al O ; f 30 wt-%Al O ; g 35 wt-%Al O

2 3 2 3 2 3 2 3 2 3 2 3 2 3
5 Phase relations at liquidus temperature in different Al O content planes (5–35 wt-%) of CaO–MgO–
2 3
Al O –SiO system (Ref. 16)
2 3 2
International Materials Reviews 2000 Vol. 45 No. 2
46 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
6 Saturation solubility of MgO in CAS slag as
function of slag basicity at 1700?C (calculated
from Fig. 5), showing saturation solubility of
MgO in acid slag is much higher than in basic
slag
Now consider the influence of slag basicity and
MgO content in the slag on the dissolution of Al O .
2 3
Figure 11 shows the saturation solubilities of Al O
2 3
at 1600°C in CM(A)S slags with 10 wt-% MgO but
different basicities (calculated by using the 1600°C
isotherms shown in Fig. 10b). As shown in Fig. 11,
with increasing slag basicity, the saturation solubility
of Al O in the slag increases. Based on this considera-
2 3
tion, increasing the basicity of the CMAS slag will
be expected to increase the dissolution of Al O .
2 3
However, as stated above, increasing the slag basicity
favours CA layer formation at high temperature and
6
makes Al O dissolution become indirect, which will
2 3
decrease the dissolution rate. Therefore, the overall
dissolution rate of Al O is determined by the balance
2 3
between these two contradictory factors. Miller
and Shott31 examined the influence of CMAS slag
(with 10 wt-% MgO) basicity on corrosion resistance
of Al O -based refractories. Their results (Fig. 12)
2 3
showed that CMAS slag corrosiveness increases with
increasing basicity, and for fused cast alumina, the
slag with a basicity (C/S) of 2·14 is ×10 more
corrosive than that with a ratio of 0·76. These results
suggest that for Al O dissolution, the influence of
2 3
increasing saturation solubility is greater than that of
CA layer formation, and explains why Al O based
6 2 3
castables are not successful in the slag lines of steel-
making ladles, where because of the high basicity
slag (in some cases, the lime content in the slag is
>70 wt-%),32,33 basic refractories such as MgO–C
(Ref. 34), and MgO–Al O (Ref. 35) bricks are gener-
2 3
ally used.
Figure 13 shows the variation of saturation solu-
bility of Al O at 1600°C in CMAS slag (C/S=1·0)
2 3
with MgO content in the slag (calculated from
Fig. 10). It can be seen that with increasing slag MgO
content, the saturation solubility of Al O in the slag
2 3
decreases. Since increasing the MgO content in the
slag also favours MA spinel layer formation at high
temperature (indirect dissolution), it can be deduced
International Materials Reviews 2000 Vol. 45 No. 2
7 Influence of graphite content on corrosion of
MgO–C bricks in acid (A, C/S=1·5) and basic
(B, C/S=3·3) slags at 1650?C (rotary slag test),18
showing that in acid slag (A) increasing graphite
content in brick decreases corrosion, but in
basic slag (B) increasing graphite content from
5 to ~20 wt-% has little effect on corrosion
resistance and further increasing graphite
content from 20 to 30 wt-% lowers corrosion
resistance
that increasing the slag MgO content will greatly
decrease the dissolution of Al O in the slag. Finger
2 3
test results given by Sandhage and Yurek22 (Fig. 14)
verify this conclusion.
Corrosion of MgO by CAS (or CMAS) slag
Dissolution of MgO into CAS (or CMAS) slag can
also be direct or indirect, dependent on whether an
MA spinel layer forms at the MgO/slag interface at
high temperatures. This can be predicted using the
phase diagrams shown in Fig. 5.
As shown in Fig. 5a and b, there is no liquidus
surface of MA in the phase diagrams with 5 and
10 wt-% Al O , indicating that to form an MA layer
2 3
at high temperatures, the Al O content in the CMAS
2 3
slag should be above 10 wt-%. In other words, if the
Al O content in CMAS slag is below 10 wt-%, no
2 3
MA reaction layer forms at high temperatures. There
is a small area of MA liquidus surface shown in the
diagram with 15 wt-% Al O (Fig. 5c). The area only
2 3
covers small temperature (~1300 to ~1580°C) and
slag basicity (C/S from ~0·55 to ~1·2) ranges, indi-
cating that solid MA spinel may form only when
temperature and slag basicity are within these ranges.
When the Al O content in the slag increases to above
2 3
15 wt-%, the area of MA surface becomes more
extensive and covers a wider temperature range. In
this case, as shown in Fig. 5d–g, the formation of MA
solid phase is mainly controlled by the slag basicity.
For example, at 1600°C, as shown in Fig. 5d and g,
the slag basicity (C/S) at 20 wt-% Al O should be
2 3
less than 1·1, and at 35 wt-% Al O less than 2·1.
2 3
Based on the above analyses, increasing Al O
2 3
content in the slag and decreasing the slag basicity
generally will favour the formation of solid MA at
high temperature. If the slag Al O content is lower
2 3
than a critical value and/or the slag basicity is higher
than a critical value, then the solid MA layer at
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 47

8 Influence of graphite content and MgO grain quality on corrosion of MgO–C brick in acid (C/S=1·2)
and basic (C/S=2·5) slags,19 showing that in acid slag, increasing graphite content or use of MgO
with larger crystal size improves corrosion resistance, but in basic slag it does not; A MgO with
smaller crystal size, B MgO with larger crystal size

wt-%

9 CaO–MgO–Al O phase diagram (Ref. 27)

2 3
International Materials Reviews 2000 Vol. 45 No. 2
48 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
(a)
(b)
a 5 wt-%MgO; b 10 wt-%MgO; c 15 wt-%MgO
10 Phase relations at liquidus temperature in different MgO content planes (5–15 wt-%) of CaO–MgO–
Al O –SiO system (Ref. 28)
2 3 2
high temperature will not be expected to form, i.e.
direct dissolution of MgO in the slag will occur.
Furthermore, because the saturation solubility of
MgO in the slag increases with increasing slag Al O
2 3
content (Fig. 15),36 so will dissolution of MgO in the
slag. However, if slag Al O content is higher than
2 3
the critical value and the basicity of the slag is lower
than the critical value, then a solid MA layer at high
temperature will be expected to form, so again indirect
dissolution of MgO occurs. In this case, the dissolu-
tion rate of MgO in the slag will be determined by
the balance between the effect of formation of an MA
layer and that of changing saturation solubility caused
by increased Al O content in the slag. As shown in
2 3
Fig. 15, in a low basicity slag, when the content of
Al O increases above a critical value (for example
2 3
for the slag with C/S=1·0, it is 30 wt-%), further
increasing Al O content will greatly decrease the
2 3
saturation solubility of MgO in the slag. In this case,
the dissolution rate of MgO will greatly decrease due
International Materials Reviews 2000 Vol. 45 No. 2
(c)
to the indirect dissolution and the lower saturation
solubility of MgO in the slag. On the other hand, in
a high basicity slag (e.g. C/S=3·0, Fig. 15), on increas-
ing the slag Al O content from 10 to 35 wt-%,
2 3
because no MA layers are expected to form
(Fig. 5b–g), direct dissolution will occur. Nevertheless,
because the solubility of MgO only changes slightly
when the slag Al O content increases from 10 to
2 3
~25 wt-% (Fig. 15), the Al O content in the slag
2 3
should have little influence on the dissolution of
MgO. However, when the slag Al O content
2 3
increases above ~25 wt-%, the MgO solubility gre-
atly increases with the slag Al O content. Since the
2 3
resulting dissolution of MgO is direct, it will increase
with the slag Al O content.
2 3
The above predictions are verified by the rotary
slag test results given by Herzog37 (Fig. 16). In the
slag with basicity (C/S) of 2·3, direct dissolution of
MgO should occur, because the slag basicity (2·3)
is higher than the upper limit (2·1) for formation
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 49

11 Effect of slag basicity on saturation solubility

of Al O in CM(A)S slag (MgO content= 13 Saturation solubility of Al O in CM(A)S slag
2 3 2 3
10 wt-%) at 1600?C (calculated from Fig. 10b) at 1600?C as function of slag MgO content
(calculated from Fig. 10)

14 Corrosion rate of sapphire in CMAS slag at

1550?C as function of slag MgO content (finger
test) (after Ref. 22)

12 Effect of slag basicity on corrosion of Al O

2 3
based bricks, showing that increasing slag
basicity markedly increases corrosion (in
24 h¬1·06 mm h−1) (after Ref. 31)

of solid MA at the test temperature (1600°C).

Consequently, increasing the slag Al O content from
2 3
20 to 35 wt-% increases the MgO refractories cor-
rosion rate (Herzog did not discuss this in his paper).
On the other hand, in the low basicity slags (e.g.
C/S=1·0), when the content of Al O in the slag is
2 3
above, for example, 35 wt-%, indirect dissolution of
Al O should occur and the saturation solubility of
2 3
MgO becomes low (Fig. 15), so the MgO dissolution 15 Saturation solubility of MgO in CMAS slag at
rate decreases with increasing slag Al O content 1700?C as function of slag Al O content (after
2 3 2 3
from 35 to 40 wt-% (Fig. 16). Ref. 36)
International Materials Reviews 2000 Vol. 45 No. 2
50 Zhang and Lee Use of phase diagrams in studies of refractories corrosion

TEMPERATURE, °C
wt-%

17 MgO–B O phase diagram (Ref. 11)

2 3
B2O3

16 Corrosion rate of MgO brick in slags with

different basicities as function of slag Al O
2 3
content (rotary slag test).37 In basic slag (C/S=
2·3), corrosion increases with increasing slag
Al O content due to direct dissolution and
2 3
increased saturation solubility of MgO, but in
acid slag (C/S=1·0), it decreases with
increasing slag Al O content because of
2 3
indirect dissolution

Influence of refractories purity on

corrosion resistance
Existing phase diagrams provide useful information
MgO C2S
on the compatibility between the main refractory
components and impurities at high temperature and 18 Composition triangle of MgO–C S–B O
thus can be used to predict the influence of impurities 2 2 3
section of CaO–MgO–B O –SiO system (Ref. 3)
on corrosion resistance. Consider the influence of 2 3 2
B O impurity in MgO refractories. Figure 17 shows
2 3 Influence of refractories additives on
the MgO–B O phase diagram.11 Even a small
2 3 their corrosion resistance
amount of B O markedly decreases the temperature
2 3
of liquid formation in MgO from the melting point To improve specific properties, minor levels of addi-
of pure MgO (~2800°C) to 1358°C. Dicalcium sili- tives may be made to refractories such as the use of
cate, C S, is commonly formed as a secondary phase antioxidants (e.g. Al (Refs. 39–42)) in carbon contain-
2
at MgO grain boundaries. Examination of the MgO– ing refractories to improve oxidation resistance and
C S–B O phase diagram3 at 1550°C (Fig. 18) reveals high temperature mechanical strength. Aluminium
2 2 3
that the liquid phase coexisting with periclase+C S metal is also known to influence corrosion resistance.
2
contains some 80 wt-% C S and 10 wt-% B O , i.e. Whether addition of Al to MgO–C refractories is
2 2 3
in the presence of periclase, B O will flux some 8 beneficial or harmful is the subject of some contro-
2 3
times its weight of C S at this temperature. Therefore, versy.43,44 Although disagreement has been attributed
2
the presence of even tiny amounts of B O in MgO to factors such as graphite purity45 or MgO grain
2 3
may disintegrate the MgO grain by fluxing the C S quality,46 the influence of slag composition needs
2
grain boundary phase. Figure 19 shows the results of consideration.
Watanabe et al.38 in which wear increases markedly Two main factors in corrosion of MgO–C refractor-
by increasing B O to only ~0·07 wt-%. ies are dissolution of MgO in the slag and oxidation
2 3
International Materials Reviews 2000 Vol. 45 No. 2
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 51
19 Influence of B O content in MgO grain on
2 3
corrosion rate of MgO–C bricks, showing
that slight increase of B O content in MgO
2 3
grain markedly decreases corrosion
resistance (Ref. 38)
of C by oxidising atmosphere or Fe O and MnO
x 2
from the slag.47,48 Addition of Al metal powder to
MgO–C refractories has a positive effect on corrosion
resistance by encouraging formation of a dense MgO
layer and inhibiting C oxidation, but it also has a
negative effect by increasing the saturation solubility
of MgO in the slag (Fig. 15). As shown in Fig. 15, in
an acid slag, the saturation solubility of MgO in the
slag is high, so MgO dissolution in the slag is the
dominant factor affecting the corrosion resistance. In
this case, even if a dense MgO layer forms, it will
quickly dissolve in the slag. Furthermore, Al O
2 3
formed from oxidation of Al will increase the satu-
ration solubility of MgO in the slag (Fig. 15), counter-
acting the positive effect of Al addition, so that it
may not have an overall positive effect on the cor-
20 Corrosion of MgO–C bricks with and without Al addition in acid slag A (C/S=1·0) and more basic
slag B (C/S=2·0):51 Al addition slightly improves corrosion resistance in more basic slag, but does
not in acid slag
rosion resistance. On the other hand, in a basic slag,
because the saturation solubility of MgO in the slag
is low and is not sensitive to the change of Al O
2 3
content in the slag (Fig. 15), the problem of C oxi-
dation becomes more serious than the dissolution of
MgO in the slag. Consequently, because Al addition
encourages MgO dense layer formation (which can
remain at the refractories/slag interface for a long
time) and effectively inhibits C oxidation, it has a
positive effect on corrosion resistance. Ikesue et al.49
tested the effectiveness of Al addition to MgO–C
bricks in a basic slag (C/S=3·0). They found that
the Al addition improves the corrosion resistance. On
the other hand, Baker and Brezny50 found that Al
addition to MgO–C bricks resulted in severe cor-
rosion in an acid slag (C/S=1·0). Asano51 used a
rotary slag test to examine the effect of Al in two
slags with basicity of 1·0 (slag A) and 2·0 (slag B). His
results (Fig. 20) show that Al addition to MgO–C
refractories improves their corrosion resistance
slightly in the more basic, but not in the acid, slag.
Silicon (or SiC) and B C are also used as additives
4
to carbon containing refractories.52,53 The CaO–SiO
2
and CaO–B O phase diagrams (Fig. 21)11 show a
2 3
problem when using such additives in ZrO –C refrac-
tories. In these refractories, oxides (SiO and B O )
2 2 3
formed from oxidation of Si (or SiC) and B C are
4
not in equilibrium with the stabilising agents (e.g.
CaO) in the ZrO grain at high temperature, so they
2
will react with each other to form CaO–SiO and
2
CaO–B O compounds. The formation of these com-
2 3
pounds will cause ZrO destabilisation so the ZrO
2 2
grain disintegrates, adversely affecting the corrosion
resistance.54
Influence of atmosphere on
refractories corrosion resistance
The oxygen partial pressure in a refractory lined
enclosure may vary in service, leading to a change of
International Materials Reviews 2000 Vol. 45 No. 2
52 Zhang and Lee Use of phase diagrams in studies of refractories corrosion

TEMPERATURE, °C

(a)

(b)

21 Phase diagrams for a CaO–SiO and b CaO–B O systems, compositions in wt-% (Ref. 11)
2 2 3
valence of some components (in particular, iron oxide)
in the refractories and/or slag. This can significantly
affect the refractories corrosion resistance.
Consider the influence of atmosphere on corrosion
resistance of Al O –SiO refractories containing, or
2 3 2
in contact with, iron oxide. Figure 22 shows solidus
surfaces in the Al O –SiO –FeO and Al O –SiO –
2 3 2 2 3 2
Fe O systems.27 Under strongly reducing conditions
2 3
International Materials Reviews 2000 Vol. 45 No. 2
(Fig. 22a), a liquid will develop at as low as 1210°C
when a fireclay brick consisting initially of mullite
and tridymite (or cristobalite) absorbs a small amount
of iron oxide. If, however, the brick is higher in Al O
2 3
and originally consists of mullite and corundum, a
liquid will not form until a temperature of 1380°C is
reached, even after a considerable amount of iron
oxide has been absorbed by the brick. In air, Fig. 22b,
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 53
(a)
22 Projections of solidus surface in iron oxide–Al O –SiO system in a reducing and b oxidising
2 3 2
atmospheres (Ref. 27)
(a)
a in reducing atmosphere; b in oxidising atmosphere
23 1500?C isothermal sections through CaO–MgO–iron oxide system; MW magnesiowustite, MF
magnesioferrite, L liquid (Ref. 27)
the lowest temperatures of liquid formation for bricks
of the same compositions as above are considerably
higher. On addition of iron oxide a fireclay brick
develops a liquid phase only after a temperature of
1380°C or higher is reached, while a high alumina
brick with absorbed iron oxide withstands temper-
atures at least as high as 1460°C before liquid starts
forming.27
An important difference between the two diagrams
(Fig. 22a and b) is related to the manner in which
iron can be accommodated in the crystal structures
of the phases present. Two of the crystalline phases
present in alumina–silica refractories, mullite and
corundum, can accommodate iron ions in their
lattices, but only in the ferric state (Fe3+). Under
reducing conditions, where the iron in the oxide
phases is present almost exclusively as Fe2+, incorpor-
ation of Fe in the crystalline phases cannot take place.
Hence, even small amounts of iron oxide absorbed
(b)
(b)
cause a liquid to develop at temperatures above 1210
and 1380°C, depending on the Al O /SiO ratio of
2 3 2
the original brick (Fig. 22a). In air, on the other hand,
a substantial proportion of the iron is present as
Fe3+. Hence moderate amounts of iron oxides can be
absorbed by alumina–silica refractories in air without
formation of a liquid phase even at temperatures
above those of the three-phase triangles labelled 1380
and 1460°C in Fig. 22b. Composition triangles in
which liquid is one of the phases present therefore
extend all the way over to the Al O –SiO side of
2 3 2
Fig. 22a, whereas the analogous areas in Fig. 22b
terminate before reaching the Al O –SiO side.27
2 3 2
The above analyses indicate that Al O –SiO
2 3 2
refractories have better corrosion resistance in oxidis-
ing than in reducing atmosphere. Based on this con-
clusion, it can be deduced that C in Al O (–SiO )–C
2 3 2
refractories may have different effects on the corrosion
resistance of Al O (–SiO ) grain phases, depending
2 3 2
International Materials Reviews 2000 Vol. 45 No. 2
54 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
TEMPERATURE, °C
(a)
(c)
24 Phase diagrams of a MgO–FeO (Ref. 11), b MgO–Fe O (Ref. 11), c CaO–FeO (Ref. 28), and d CaO–Fe O
2 3
(Ref. 28) systems
on the local reducing conditions. If C only reduces
Fe O in the refractories or slag to FeO, then
2 3
Al O (–SiO ) grains resistance to slag attack will
2 3 2
be decreased. However, if C further reduces FeO to
metallic Fe, the liquid formation temperature and
the slag viscosity are expected to increase so improv-
ing the resistance of the Al O (–SiO ) grains to slag
2 3 2
attack.
Now consider the influence of atmosphere on the
corrosion resistance of MgO–CaO refractories con-
taining, or in contact with, iron oxide. The MgO–
CaO–FeO and MgO–CaO–Fe O phase diagrams at
2 3
1500°C (Fig. 23)27 reveal a large difference in the
extent of the area where no liquid phase is present at
the two different oxygen pressures. Under strongly
International Materials Reviews 2000 Vol. 45 No. 2
TEMPERATURE, °C
(b)
(d)
2 3
reducing conditions (Fig. 23a), a CaO–MgO mixture
of composition A can take up about 22% iron oxide
without a liquid phase developing at 1500°C. In air
(Fig. 23b), however, only 3% iron oxide can be taken
up before a liquid phase develops at the same temper-
ature. Hence, maintaining strongly reducing con-
ditions within a dolomite refractory body exposed to
iron oxide attack is desirable.27 The carbon in
MgO–CaO–C or tar bonded MgO–CaO bricks for
oxygen steelmaking vessels is believed to serve this
purpose. In addition, however, carbon probably plays
other important roles in the chemistry involved during
use of such bricks. For example, the carbon reduces
some iron oxide in the refractories and/or in the slag
to metallic iron, which enhances the liquid formation
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 55
(a) (b)
a 0 wt-%C; b 10 wt-%C; c 20 wt-%C
25 Influence of brick CaO content, slag basicity (C/S), and slag iron oxide content (T. Fe) on corrosion
rate of MgO(–C) and MgO–CaO(–C) refractories (Ref. 57). In low basicity and low iron oxide slag
(C/S=1·2 and T. Fe=9·1 wt-%), MgO–CaO(–C) refractories have better slag resistance than MgO(–C)
refractories, but in high basicity and high iron oxide content slag (C/S=3·1 and T. Fe=19 wt-%) they
exhibit poorer corrosion resistance
temperature in the refractories and/or slag increasing
viscosity and reducing corrosion.
Comparing corrosion resistance of
refractories
In many cases, phase diagrams can be used to com-
pare qualitatively the corrosion resistance of different
refractories by checking the compatibility between
the refractories and slag. A good example of this is
the comparison of corrosion resistance of MgO(–C)
and MgO–CaO(–C) refractories.
The MgO–FeO (Ref. 11), MgO–Fe O (Ref. 11),
2 3
CaO–FeO (Ref. 28), and CaO–Fe O (Ref. 28)
2 3
phase diagrams are shown in Fig. 24. After MgO
absorbs 70 wt-% FeO or 70 wt-% Fe O , the liquid
2 3
formation temperature is still higher than 1600 or
1700°C (Fig. 24a and b), but after CaO absorbs
only <15 wt-% FeO or a small amount of Fe O ,
2 3
the liquid formation temperature falls to ~1160 or
1438°C (Fig. 24c and d), and after CaO absorbs about
60 wt-% Fe O , all of it becomes liquid at ~1450°C
2 3
(Fig. 24d).
Comparing Fig. 24 with Fig. 23, reveals that after
the MgO–CaO refractory (A) takes up ~22 wt-%
FeO or 3 wt-% Fe O , liquid develops at 1500°C
2 3
(Fig. 23), however, after MgO refractory absorbs the
same amount of FeO or Fe O , the liquid formation
2 3
temperature remains higher than 2300 or 2700°C
(Fig. 24a and b).
The above differences indicate that with higher Fe
oxide content slags, the MgO(–C) corrosion resistance
is better than that of MgO–CaO(–C) refractories.
The corrosion behaviour of MgO(–C) is also
different from that of MgO–CaO(–C) refractories in
slags with different basicities. As shown in Fig. 6, in
a slag with low basicity, because MgO has high
(c)
saturation solubility, its dissolution in the slag is a
serious problem. Increasing the CaO (decreasing
MgO) content in the refractories usefully decreases
their dissolution. Furthermore, increasing the CaO
content may lead to the formation of a C S layer
2
(Fig. 21a) at the refractory/slag interface,55,56 which
causes indirect dissolution and retards corrosion.
Therefore, in low basicity slag, the MgO–CaO(–C)
show better corrosion resistance than MgO(–C)
refractories.
Considering both the influence of Fe oxide and of
slag basicity on the corrosion resistance of MgO(–C)
and MgO–CaO(–C) refractories indicates that in
low basicity and low Fe oxide content slag,
MgO–CaO(–C) refractories will show better cor-
rosion resistance than MgO(–C) refractories, but in
the high basicity and/or high Fe oxide content slag,
the latter will show better corrosion resistance.
Induction furnace and rotary slag test results57–63
support these predictions. Figure 25, as an example,
shows the rotary slag test results of Toritani et al.57
Except for the two bricks with CaO of ~8 and
~17 wt-% in the slag with C/S=3·1 and total
Fe oxide (T. Fe)=19 wt-% (Fig. 25a), MgO–CaO
(Fig. 25a) and MgO–CaO–C refractories (Fig. 25b
and c) show better corrosion resistance than MgO
and MgO–C refractories in the low basicity (C/S=
1·2) and low Fe oxide content (T. Fe=9·1 wt-%)
slag, but exhibit poorer corrosion resistance in the
high basicity (C/S=3·1) and high Fe oxide content
(T. Fe=19 wt-%) slag.
Refractories selection for specific
applications
By checking the compatibility between refractories
and surrounding slags, the corrosion behaviour of
International Materials Reviews 2000 Vol. 45 No. 2
56 Zhang and Lee Use of phase diagrams in studies of refractories corrosion

(b)

(a)
TEMPERATURE

(c) (d)
Mol.-%

(e) (f)

Mol.-%

26 Phase diagrams of a Al O –CuO/Cu O (Ref. 64), b CaO–CuO/Cu O (Ref. 65), c ZrO –CuO/Cu O (Ref. 66),
2 3 2 2 2 2
d SiO –CuO/Cu O (Ref. 67), e MgO–CuO/Cu O (Ref. 68), and f Cr O –CuO/Cu O (Ref. 69) systems
2 2 2 2 3 2

different refractories can be predicted and compared, amounts of Cu O/CuO fluxes these oxides (i.e. lowers
2
assisting refractories selection for specific applications. the melting temperature). For example, just a tiny
A good example of this is selection of refractories to amount of Cu O/CuO will decrease the liquid forma-
2
be exposed to copper melting slags. tion temperature from 2051°C (the melting point of
Figure 26 shows the Al O –Cu O/CuO (Ref. Al O ) to 1238°C with Al O (Fig. 26a), and from
2 3 2 2 3 2 3
64), CaO–Cu O/CuO (Ref. 65), ZrO –Cu O/CuO 2730°C (the melting point of ZrO ) to 1130°C with
2 2 2 2
(Ref. 66), SiO –CuO (Ref. 67), MgO–Cu O/CuO ZrO (Fig. 26c).
2 2 2
(Ref. 68), and Cr O –Cu O/CuO (Ref. 69) phase dia- However, the cases of MgO and Cr O are quite
2 3 2 2 3
grams. As can be seen from Fig. 26a–d, CuO and different. As shown in Fig. 26e, MgO can take up
Cu O are corrosive to Al O , CaO, SiO , and ZrO 20 wt-% Cu O/CuO without liquid formation, and
2 2 3 2 2 2
refractories, because the presence of even small even after Cr O absorbs ~65 wt-% Cu O/CuO,
2 3 2
International Materials Reviews 2000 Vol. 45 No. 2
 Zhang and Lee Use of phase diagrams in studies of refractories corrosion 57
27 Composition triangle of MgO–CuO–Cr O
2 3
showing saturation solubility of MgO of
composition E and MgCr O of composition F
2 4
in liquid at this temperature is low (Ref. 3)
no liquid forms (Fig. 26f ). Consequently, MgO and
Cr O are much more resistant to Cu O/CuO than
2 3 2 on Fig. 9). A similar situation arises in MgO–CaO
Al O , CaO, SiO , and ZrO . The MgO–Cr O –
2 3 2 2 2 3
Cu O diagram at 1400°C (Ref. 3) (Fig. 27) further
2 bond system for basic castables.
reveals that the solubilities of MgO and MgCr O in
2 4
liquid (L) at 1400°C are low. The above analyses
explain why direct bonded magnesia–chrome refrac-
tories are so successful in copper smelting furnaces.70
Designing refractories composition
Proper raw materials selection and optimisation of
refractories compositions are important factors in
developing refractories with high refractoriness and
good corrosion resistance. A good example of this is
control of the C/S ratio in MgO grain materials or
refractories.71,72 The solidus surfaces of the CaO–
MgO–SiO system (Fig. 28) reveal that the liquid
2
formation temperature generally increases with
increasing C/S ratio in the MgO grain. For example,
the liquid formation temperature corresponding to
C/S(mol ratio)=1·0–1·5 is 1490°C, to C/S=1·5–2·0
is 1575°C, to C/S=2·0–3·0 is 1790°C, and to C/S>3·0
is 1850°C. Therefore, it is necessary to maintain the
C/S ratio of MgO grain or MgO based refractories
above 2·0 to retain high refractoriness and corrosion
resistance.71–73
A further example is selection of a suitable bond
system for castable refractories. Calcium aluminate
cement (CA cement) is widely used in Al O -based
2 3
castable refractories, though in recent years, cement-
free castables have been developed (e.g. Refs. 74–76).
According to the CaO–MgO–Al O phase diagram
2 3
(Fig. 9), small additions of CA cement whose main
components are CA, CA , and C A (Refs. 77, 78)
2 12 7
to Al O castable will lead on firing to formation of
2 3
CA , and in this case the liquid formation temperature
6 tories.
is ~1870°C (point Y on Fig. 9). With addition of a
small amount of CA cement to Al O –MA castable,
2 3
the liquid formation temperature remains higher than
1800°C (point X on Fig. 9). Therefore, if SiO is not
2
added, CA cement gives a highly refractory bond
28 Solidus surface of CaO–MgO–SiO system
2
shown in Fig. 3a (Ref. 27)
system in Al O -based castables. However, if CA
cement is added2 3to an MgO–MA castable, the liquid
formation temperature is lower than 1400°C (point Q
castables. CA cement thus does not provide a suitable
To improve flowability and other properties of
castables, superfine (submicrometre) powders such
as Al O and SiO are usually added.79–81 A small
amount2 3of Al O added
2 to a MgO–CaO castable will
2 3
decrease the liquid formation temperature to lower
than 1500°C (Fig. 9). However, examining the CaO–
MgO–SiO phase diagram (Fig. 3a) shows that when
2
a small amount of SiO is added to a MgO–CaO
castable, C S will form2 and the liquid formation
temperature3 remains as high as ~1850°C. This indi-
cates that using superfine SiO powder in MgO–CaO
2
castables is better than using superfine Al O powder
if corrosion resistance is paramount. 2 3
Summary
Understanding corrosion mechanisms and comparing
corrosion resistance of refractories in various slags is
important for evaluating their service life. Phase dia-
grams provide useful information about the compati-
bility between refractories components and slags,
which can be used to interpret corrosion mechanisms
and predict corrosion behaviour. In this review, typi-
cal applications of phase diagrams to specific prob-
lems of refractories corrosion have been highlighted.
Experimental corrosion test results show good agree-
ment with the phase diagram predictions (though
phase diagrams do not contain any information re-
lating to the kinetics of the reactions involved).
Therefore, use of the information which is available
in existing phase diagrams can reduce the need for
expensive and time consuming experimentation to
evaluate the high temperature corrosion of refrac-
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