Use of phase diagrams in studies of

refractories corrosion
S. Zhang and W. E. Lee
available in existing phase equilibrium diagrams.
Although the importance of phase diagrams to studies
Typical applications of phase diagrams to specific
of refractories corrosion has been highlighted,37 and
problems of refractories corrosion are highlighted.
a few cases such as attack of Al
2
O
3
SiO
2
refractories Saturation solubilities of refractories components
in molten slags can be estimated using existing by alkali oxides well studied,4,6,7 their use is far from
phase diagrams. These can then be used to predict
ubiquitous.
the corrosion behaviour, and qualitatively compare
This paper seeks to emphasise applications of phase
the corrosion resistance, of a refractory in different
diagrams to specic refractories corrosion problems
slags or different refractories in the same slag.
using typical examples. Previously reported experi-
If the slag is not saturated with refractories
mental results which were not well explained have
components, using relevant phase diagrams, the
been re-analysed and earlier discrepancies claried
conditions under which solid reaction product
using the relevant phase diagrams.
phases form at refractories/slag interfaces can be
predicted, which assists understanding of direct
and indirect dissolution. By checking the
Significance of saturation solubility of
compatibility between impurities or additives and
refractories oxide phases in liquid slag
refractories components at high temperatures,
their influence on corrosion resistance can be
Dissolution of solid oxides in liquid slag is governed
predicted, aiding their selection. Phase diagrams
by: (a) chemical reaction (or solution) at the
also reveal that atmosphere affects refractories
refractories/slag interface or ( b) transport (or
corrosion resistance by altering the valence of
diusion) of reacting species.8 In the latter case,
some components (in particular, iron oxide) in the
dissolution rate can be expressed in terms of the
refractories and/or slags. The compatibility
Nernst equation
between refractories and slags indicates the
corrosion resistance of different refractories,
J=D(C
s
C
m
)/d . . . . . . . . . . (1)
assisting refractories selection for specific
applications. Finally, phase diagrams can be used where D is the diusion coecient (m2 s1), C
m
and
to assist design of refractories composition.
C
s
are, respectively, concentration and saturation
Repeated experimental corrosion test results show
solubility of refractory in the slag (g m3), and d is
good agreement with phase diagram predictions.
the eective boundary layer thickness (m).
Therefore, use of the information which is
Increasing D or decreasing d (i.e. increasing
available in existing phase diagrams can reduce
D/d) increases dissolution rate J. Besides this, it is
the need for expensive and time consuming
clear from equation (1) that the value of C
s
C
m
experiments to evaluate high temperature
strongly inuences dissolution rate. If the slag is
corrosion of refractories (and other ceramics).
saturated with refractory oxide, then J=0. Naturally, IMR/351
to minimise the dissolution rate, it is necessary to
2000 IoM Communications Ltd and ASM International. minimise C
s
C
m
. For example, with increasing MgO
The authors are in the Department of Engineering
content in the slag, the corrosion of the periclase
Materials, The University of Sheffield, Mappin Street,
phase in magnesitedolomite or in magnesitechrome
Sheffield S1 3JD, UK.
refractories will decrease. If C
m
=0, then the value of
C
s
C
m
reaches a maximum and thus, so does the
dissolution rate.
Fortunately, the saturation solubility of the refrac-
Introduction
tories oxide in liquid slag can be estimated using
Refractories are non-metallic materials used to line existing phase diagrams. By then checking the dier-
many industrial furnaces for high temperature pro- ence between the concentrations and saturation solu-
duction of other materials such as metals, glass, bilities of the main refractories components in the
cement, and petrochemicals. Decreased service life of molten slag, their relative resistance to slag attack
refractories is caused by damage arising from, for can be compared, and thus the inuence of refractories
example, deformation at high temperature, thermal composition on corrosion resistance can be predicted.
shock, mechanical abrasion, and chemical corrosion. Consider the inuence of MgO concentration
Among these factors, chemical attack by the slag is and saturation solubility in silicate slag on the dissolu-
often the most critical. tion of solid MgO. Matsui et al.9 examined the
To determine chemical corrosion mechanisms and dissolution rate of sintered and fused MgO grain into
to compare corrosion resistance of dierent refractor- silicate slags at 1600C by measuring the weight
ies, several test methods have evolved.1,2 However, changes of MgO grain before and after heating in the
many of these tests are expensive and time consuming, slags given in Table 1. Using the phase diagram
and in some cases, they are conducted just to (showing MgO solubility data)10 shown in Fig. 1, the
saturation solubility of MgO in each slag can be re-establish information already known and generally
ISSN 09506608 International Materials Reviews 2000 Vol. 45 No. 2 41
42 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
2 Weight loss of fused (F-1) and sintered (S-1)
MgOgrain corroded for different times at 1600?C
by slags A-0, A-5, and A-10 given in Table 1
w
t
-
%
(after Ref. 9)
1 CaOMgOFe
2
O
3
SiO
2
phase diagram at 1600?C
with MgO saturation solubilities in liquid phase:
Per. periclase, Sp. spinel (after Ref. 10)
a basicity (CaO/SiO
2
weight ratio (C/S)) of 10, then
the saturation solubilities of MgO, Cr
2
O
3
, and Al
2
O
3
estimated. The saturation solubilities of MgO in the
in the slag at the test temperature are calculated to
slags at 1600C thus obtained and the C
s
C
m
values
be ~243 wt-% (point L
1
on Fig. 3a), ~71 wt-%
are listed in Table 1, showing the C
s
C
m
values
(point L
2
on Fig. 3b), and ~632 wt-% (point L
3
on
corresponding to slags A-15, B-10, and C-10 are
Fig. 3c), respectively. Clearly, Cr
2
O
3
has the lowest
negative (-ve). These slags are thus oversaturated with
solubility in the slag whereas Al
2
O
3
has the highest,
respect to MgO at 1600C, so they cannot dissolve
so that in a CaOSiO
2
based slag (with C/S ratio
MgO at this temperature. On the other hand, the
around 10), increasing the Cr
2
O
3
content in MK will
C
s
C
m
values for slags A-0, A-5, and A-10 are
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
2
O
3
content in
of these three slags are only slightly dierent9 accord-
MK would decrease slag corrosion resistance. Finger,
ing to equation (1), the dissolution rate of solid MgO
induction furnace, and rotary slag test results1215
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 1600C, 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
2
O
3
Refractories are composed of many components
content in the brick, the corrosion is greater (Fig. 4a),
and by checking the saturation solubility of each in
and with higher Cr
2
O
3
content in the brick, the
molten slag, the inuence of refractories composition
corrosion is lower (Fig. 4b).
on corrosion resistance can be predicted. A good
Another relevant example is the inuence of carbon
example is the inuence of relative contents of Cr
2
O
3
,
(C) content and periclase crystal size in MgO grain
Al
2
O
3
, and MgO in magnesiachrome refractories
on the corrosion resistance of MgOC refractories
(MK) on their corrosion resistance. Figure 3 shows
used in basic oxygen furnaces (BOFs). Figure 5 shows
CaOMgOSiO
2
, CaOCr
2
O
3
SiO
2
, and CaO
the phase relations in the CaOMgOAl
2
O
3
SiO
2
Al
2
O
3
SiO
2
ternary phase diagrams.11 Assuming a
system at liquidus temperatures in planes of constant
test temperature of 1700C and CaOSiO
2
slag with
Al
2
O
3
spaced at 5 wt-% intervals.16 From the iso-
therms shown in Fig. 5, the saturation solubilities of
Table 1 Chemical composition and saturation MgO in CaOAl
2
O
3
SiO
2
(CAS) slags with various
solubility C
s
of MgO in various slags
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
2
O
3
but dierent basicities at
1700C. With increasing slag basicity from 10 to 30,
A-0 A-5 A-10 A-15 B-10 C-10
the saturation solubility of MgO in the slag decreases
CaO 430 401 392 369 434 474
from~29 to ~125 wt-%. The BOF slag in the early
SiO
2
215 193 208 199 152 117
stage is acid (C/S around 10), but changes to basic
Fe
2
O
3
350 327 320 299 305 313
MgO 0 48 83 124 88 88 in the late stage (C/S above 30).17 In the early stage,
C
s
~90 ~85 ~100 ~100 <80 <80
the solubility of MgO in the slag is high (Fig. 6) and
C
s
C
m
~90 ~36 ~17 -ve -ve -ve
the dissolution of MgO from the MgOC refractories
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 43
wt-%
(a)
wt-%
(c)
wt-%
(b)
3 Phase diagrams of a CaOMgOSiO
2
, b CaOCr
2
O
3
SiO
2
, and c CaOAl
2
O
3
SiO
2
systems (Ref. 11)
into the slag is a dominant factor aecting their ( lower corrosion index), but in a basic slag (slag B,
C/S=33), increasing the graphite content from 5 to corrosion resistance. So in this case, increasing the
content of C (which is an inert component to silicate 20 wt-% does not obviously improve corrosion resist-
ance, and increasing its content to above 20 wt-% slag) or using MgO with larger crystal size (e.g. fused
MgO) will be expected to improve the corrosion lowers corrosion resistance. Figure 8 shows that, in
an acid slag (C/S=12), increasing C content (from resistance of the MgOC refractories. However, in
the late stage, the saturation solubility of MgO in the 5 to 15 wt-%) and use of MgO with larger crystal
size ( B), increases the corrosion resistance, but in a slag becomes low (Fig. 6), so dissolution of MgO in
the slag is not a serious problem. In this case, C basic slag (C/S=25) these changes have little eect.
oxidation becomes the dominant factor aecting the
corrosion resistance so that increasing the C content
or using MgO with larger crystal size will not greatly Direct and indirect dissolution:
improve the corrosion resistance of the MgOC
prediction of formation of reaction
refractories. In some cases using too much C decreases
products at refractories/slag
the corrosion resistance because of the oxidation of
interfaces
C and the weak nature of the resulting bond. These
conclusions are supported by rotary slag test results Dissolution of refractory oxide into silicate slag gener-
ally can be homogeneous (congruent or direct) or (Figs. 7 and 8). Figure 7 shows that in a more acid
slag (slag A, C/S=15), increasing the graphite con- heterogeneous (incongruent or indirect). The former
occurs between refractory oxides and molten slag tent in the brick improves the corrosion resistance
International Materials Reviews 2000 Vol. 45 No. 2
44 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
invariant point E corresponding to DCAS
2
ACA
6
is
~1500C, with a test temperature above 1500C, CA
6
layer formation is not expected in this slag. In other
words, if CA
6
is observed in the microstructure, it has
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 dierent (~1720, 1780, and
1810C, respectively). Assuming a test temperature
of 1600C and a composition of 90 wt-% solid
Al
2
O
3
+10 wt-% slag, then the amounts of precipi-
tated CA
6
corresponding to the slags b, c, and d are
calculated to be ~156, 278, and 397 wt-%, respect-
ively. These results indicate that increasing the
basicity of the CAS slag will favour the formation of
solid CA
6
at high temperature, i.e. favour the indirect
dissolution of Al
2
O
3
in the slag.
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
MgOAl
2
O
3
(Fig. 9)27 and CaOMgOAl
2
O
3
SiO
2
phase diagrams (with 515 wt-% MgO) (Fig. 10).28
Although the CaOMgOAl
2
O
3
phase diagram is too
simple to predict the detailed corrosion process of
Al
2
O
3
in the CMAS slag, it provides some useful
information regarding the formation of solid CA
6
or
MA at high temperature. Draw a straight line between
the Al
2
O
3
apex (A) and invariant point (X) corres-
ponding to DACA
6
MA in Fig. 9. The CaO/MgO
(a)
(b)
ratio corresponding to this line is ~44. Therefore, if 4 Wear index (rotary slag test) of MgOCr
2
O
3
brick
as function of a Al
2
O
3
content12 or b Cr
2
O
3
the CaO/MgO ratio in the CMAS slag is above ~44,
content,13 showing that increasing brick Al
2
O
3
then, the joint line between the point A and slag
content increases corrosion, but increasing
composition point will hit the boundary curve (XY)
Cr
2
O
3
content decreases corrosion: slag
between the Al
2
O
3
primary eld and the CA
6
primary
composition (A) C/S=10, Al
2
O
3
=10 wt-% and
eld. Consequently, a CA
6
layer is expected to form
(B) C/S=10, Al
2
O
3
=30 wt-%
adjacent the solid Al
2
O
3
. If the CaO/MgO ratio in
the CMAS slag is below ~44, then the joint line
when ions from the refractory oxides dissolve directly
will hit the boundary curve (XZ) between the Al
2
O
3
into the melt, while the latter occurs when one or
primary eld and the MA primary eld, so that in
more solid reaction products form at the refractory
this case an MA layer is expected adjacent the solid
oxide/slag interface separating the oxide from the
Al
2
O
3
.
slag.2,2026 Because of the formation of a solid
If more components are included in the system, the
interface product layer (or layers) in the latter case,
critical CaO/MgO value will be a little dierent from
the dissolution rate will be decreased. Obviously, to
the value (44) estimated above. For example, if SiO
2
understand the corrosion mechanism clearly and
is included in the system, based on the CaO/SiO
2

evaluate the corrosion resistance, it is necessary to

Al
2
O
3
MgO phase diagrams given by Kitai,29 the
know the conditions under which solid reaction prod-
critical CaO/MgO value is calculated to be ~45
ucts form at the refractories/slag interface at high
when the C/S ratio of the slag is between 10 and 30.
temperature. The following two examples, dissolution
The above CaO/MgO ratio (~45) can be used to
of Al
2
O
3
and MgO in CAS (or CMAS) slag, illustrate
predict experimental results approximately. Sandhage
how to use phase diagrams to predict formation of
and Yurek21 found a CA
6
layer formed adjacent to
reaction product layers at high temperatures.
solid Al
2
O
3
in a slag with CaO/MgO=70, but an
MA layer formed adjacent solid Al
2
O
3
in slags with
Corrosion of Al
2
O
3
by CAS or CMAS slag CaO/MgO<~45. The present authors examined
the dissolution of Al
2
O
3
in a Fe
x
O and MnO contain-
Consider the dissolution of Al
2
O
3
in four CAS slags
ing CMAS slag with CaO/MgO=60, so a CA
6
layer
with the same Al
2
O
3
content (25 wt-%) but dierent
formed adjacent the solid Al
2
O
3
.30
C/S ratios (05, 10, 15, and 20). These four slags are
The fact that increasing MgO concentration in indicated on the CaOAl
2
O
3
SiO
2
phase diagram
CMAS slag favours the formation of solid MA spinel (Fig. 3c) by points a, b, c, and d, respectively. Draw
at high temperature is also reected in the phase a straight line between each of these points and the
diagrams shown in Fig. 10 which shows that the area Al
2
O
3
apex (A). Because the line aA does not hit
of MA liquidus surface increases with increasing MgO the boundary curve (EF) between the CA
6
primary
eld and Al
2
O
3
primary eld, and the temperature of content in the system.
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 45
(a)
(b) (c)
(d) (e)
(f) (g)
a 5 wt-%Al
2
O
3
; b 10 wt-%Al
2
O
3
; c 15 wt-%Al
2
O
3
; d 20 wt-%Al
2
O
3
; e 25 wt-%Al
2
O
3
; f 30 wt-%Al
2
O
3
; g 35 wt-%Al
2
O
3
5 Phase relations at liquidus temperature in different Al
2
O
3
content planes (535 wt-%) of CaOMgO
Al
2
O
3
SiO
2
system (Ref. 16)
International Materials Reviews 2000 Vol. 45 No. 2
46 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
7 Influence of graphite content on corrosion of
MgOC bricks in acid (A, C/S=15) and basic
(B, C/S=33) slags at 1650?C (rotary slag test),18
6 Saturation solubility of MgO in CAS slag as showing that in acid slag (A) increasing graphite
function of slag basicity at 1700?C (calculated content in brick decreases corrosion, but in
from Fig. 5), showing saturation solubility of basic slag (B) increasing graphite content from
MgO in acid slag is much higher than in basic 5 to ~20 wt-% has little effect on corrosion
slag resistance and further increasing graphite
content from 20 to 30 wt-% lowers corrosion
resistance
Now consider the inuence of slag basicity and
MgO content in the slag on the dissolution of Al
2
O
3
.
that increasing the slag MgO content will greatly
Figure 11 shows the saturation solubilities of Al
2
O
3 decrease the dissolution of Al
2
O
3
in the slag. Finger
at 1600C in CM(A)S slags with 10 wt-% MgO but
test results given by Sandhage and Yurek22 (Fig. 14)
dierent basicities (calculated by using the 1600C
verify this conclusion.
isotherms shown in Fig. 10b). As shown in Fig. 11,
with increasing slag basicity, the saturation solubility
Corrosion of MgO by CAS (or CMAS) slag
of Al
2
O
3
in the slag increases. Based on this considera-
tion, increasing the basicity of the CMAS slag will Dissolution of MgO into CAS (or CMAS) slag can
also be direct or indirect, dependent on whether an be expected to increase the dissolution of Al
2
O
3
.
However, as stated above, increasing the slag basicity MA spinel layer forms at the MgO/slag interface at
high temperatures. This can be predicted using the favours CA
6
layer formation at high temperature and
makes Al
2
O
3
dissolution become indirect, which will phase diagrams shown in Fig. 5.
As shown in Fig. 5a and b, there is no liquidus decrease the dissolution rate. Therefore, the overall
dissolution rate of Al
2
O
3
is determined by the balance surface of MA in the phase diagrams with 5 and
10 wt-% Al
2
O
3
, indicating that to form an MA layer between these two contradictory factors. Miller
and Shott31 examined the inuence of CMAS slag at high temperatures, the Al
2
O
3
content in the CMAS
slag should be above 10 wt-%. In other words, if the (with 10 wt-% MgO) basicity on corrosion resistance
of Al
2
O
3
-based refractories. Their results (Fig. 12) Al
2
O
3
content in CMAS slag is below 10 wt-%, no
MA reaction layer forms at high temperatures. There showed that CMAS slag corrosiveness increases with
increasing basicity, and for fused cast alumina, the is a small area of MA liquidus surface shown in the
diagram with 15 wt-% Al
2
O
3
(Fig. 5c). The area only slag with a basicity (C/S) of 214 is 10 more
corrosive than that with a ratio of 076. These results covers small temperature (~1300 to ~1580C) and
slag basicity (C/S from ~055 to ~12) ranges, indi- suggest that for Al
2
O
3
dissolution, the inuence of
increasing saturation solubility is greater than that of cating that solid MA spinel may form only when
temperature and slag basicity are within these ranges. CA
6
layer formation, and explains why Al
2
O
3
based
castables are not successful in the slag lines of steel- When the Al
2
O
3
content in the slag increases to above
15 wt-%, the area of MA surface becomes more making ladles, where because of the high basicity
slag (in some cases, the lime content in the slag is extensive and covers a wider temperature range. In
this case, as shown in Fig. 5dg, the formation of MA >70 wt-%),32,33 basic refractories such as MgOC
(Ref. 34), and MgOAl
2
O
3
(Ref. 35) bricks are gener- solid phase is mainly controlled by the slag basicity.
For example, at 1600C, as shown in Fig. 5d and g, ally used.
Figure 13 shows the variation of saturation solu- the slag basicity (C/S) at 20 wt-% Al
2
O
3
should be
less than 11, and at 35 wt-% Al
2
O
3
less than 21. bility of Al
2
O
3
at 1600C in CMAS slag (C/S=10)
with MgO content in the slag (calculated from Based on the above analyses, increasing Al
2
O
3
content in the slag and decreasing the slag basicity Fig. 10). It can be seen that with increasing slag MgO
content, the saturation solubility of Al
2
O
3
in the slag generally will favour the formation of solid MA at
high temperature. If the slag Al
2
O
3
content is lower decreases. Since increasing the MgO content in the
slag also favours MA spinel layer formation at high than a critical value and/or the slag basicity is higher
than a critical value, then the solid MA layer at temperature (indirect dissolution), it can be deduced
International Materials Reviews 2000 Vol. 45 No. 2
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 MgOC brick in acid (C/S=12)
and basic (C/S=25) 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 CaOMgOAl
2
O
3
phase diagram (Ref. 27)
International Materials Reviews 2000 Vol. 45 No. 2
48 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
(a)
(b) (c)
a 5 wt-%MgO; b 10 wt-%MgO; c 15 wt-%MgO
10 Phase relations at liquidus temperature in different MgO content planes (515 wt-%) of CaOMgO
Al
2
O
3
SiO
2
system (Ref. 28)
high temperature will not be expected to form, i.e. to the indirect dissolution and the lower saturation
solubility of MgO in the slag. On the other hand, in direct dissolution of MgO in the slag will occur.
Furthermore, because the saturation solubility of a high basicity slag (e.g. C/S=30, Fig. 15), on increas-
ing the slag Al
2
O
3
content from 10 to 35 wt-%, MgO in the slag increases with increasing slag Al
2
O
3
content (Fig. 15),36 so will dissolution of MgO in the because no MA layers are expected to form
(Fig. 5bg), direct dissolution will occur. Nevertheless, slag. However, if slag Al
2
O
3
content is higher than
the critical value and the basicity of the slag is lower because the solubility of MgO only changes slightly
when the slag Al
2
O
3
content increases from 10 to than the critical value, then a solid MA layer at high
temperature will be expected to form, so again indirect ~25 wt-% (Fig. 15), the Al
2
O
3
content in the slag
should have little inuence on the dissolution of dissolution of MgO occurs. In this case, the dissolu-
tion rate of MgO in the slag will be determined by MgO. However, when the slag Al
2
O
3
content
increases above ~25 wt-%, the MgO solubility gre- the balance between the eect of formation of an MA
layer and that of changing saturation solubility caused atly increases with the slag Al
2
O
3
content. Since the
resulting dissolution of MgO is direct, it will increase by increased Al
2
O
3
content in the slag. As shown in
Fig. 15, in a low basicity slag, when the content of with the slag Al
2
O
3
content.
The above predictions are veried by the rotary Al
2
O
3
increases above a critical value (for example
for the slag with C/S=10, it is 30 wt-%), further slag test results given by Herzog37 ( Fig. 16). In the
slag with basicity (C/S) of 23, direct dissolution of increasing Al
2
O
3
content will greatly decrease the
saturation solubility of MgO in the slag. In this case, MgO should occur, because the slag basicity ( 23)
is higher than the upper limit ( 21) for formation the dissolution rate of MgO will greatly decrease due
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 49
11 Effect of slag basicity on saturation solubility
13 Saturation solubility of Al
2
O
3
in CM(A)S slag of Al
2
O
3
in CM(A)S slag (MgO content=
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
2
O
3
based bricks, showing that increasing slag
basicity markedly increases corrosion (in
24 h106 mm h1) (after Ref. 31)
of solid MA at the test temperature (1600C).
Consequently, increasing the slag Al
2
O
3
content from
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=10), when the content of Al
2
O
3
in the slag is
above, for example, 35 wt-%, indirect dissolution of
Al
2
O
3
should occur and the saturation solubility of
MgO becomes low ( Fig. 15), so the MgO dissolution
15 Saturation solubility of MgO in CMAS slag at
rate decreases with increasing slag Al
2
O
3
content 1700?C as function of slag Al
2
O
3
content (after
Ref. 36) from 35 to 40 wt-% (Fig. 16).
International Materials Reviews 2000 Vol. 45 No. 2
50 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
T
E
M
P
E
R
A
T
U
R
E
,

C
wt-%
17 MgOB
2
O
3
phase diagram (Ref. 11)
16 Corrosion rate of MgO brick in slags with
different basicities as function of slag Al
2
O
3
content (rotary slag test).37 In basic slag (C/S=
23), corrosion increases with increasing slag
Al
2
O
3
content due to direct dissolution and
increased saturation solubility of MgO, but in
acid slag (C/S=10), it decreases with
increasing slag Al
2
O
3
content because of
indirect dissolution
Influence of refractories purity on
corrosion resistance
Existing phase diagrams provide useful information
on the compatibility between the main refractory
MgO C
2
S
B
2
O
3
components and impurities at high temperature and
18 Composition triangle of MgOC
2
SB
2
O
3
thus can be used to predict the inuence of impurities
section of CaOMgOB
2
O
3
SiO
2
system(Ref. 3)
on corrosion resistance. Consider the inuence of
B
2
O
3
impurity in MgO refractories. Figure 17 shows
Influence of refractories additives on
the MgOB
2
O
3
phase diagram.11 Even a small
their corrosion resistance
amount of B
2
O
3
markedly decreases the temperature
of liquid formation in MgO from the melting point To improve specic properties, minor levels of addi-
tives may be made to refractories such as the use of of pure MgO (~2800C) to 1358C. Dicalcium sili-
cate, C
2
S, is commonly formed as a secondary phase antioxidants (e.g. Al (Refs. 3942)) in carbon contain-
ing refractories to improve oxidation resistance and at MgO grain boundaries. Examination of the MgO
C
2
SB
2
O
3
phase diagram3 at 1550C (Fig. 18) reveals high temperature mechanical strength. Aluminium
metal is also known to inuence corrosion resistance. that the liquid phase coexisting with periclase+C
2
S
contains some 80 wt-% C
2
S and 10 wt-% B
2
O
3
, i.e. Whether addition of Al to MgOC refractories is
benecial or harmful is the subject of some contro- in the presence of periclase, B
2
O
3
will ux some 8
times its weight of C
2
S at this temperature. Therefore, versy.43,44 Although disagreement has been attributed
to factors such as graphite purity45 or MgO grain the presence of even tiny amounts of B
2
O
3
in MgO
may disintegrate the MgO grain by uxing the C
2
S quality,46 the inuence of slag composition needs
consideration. grain boundary phase. Figure 19 shows the results of
Watanabe et al.38 in which wear increases markedly Two main factors in corrosion of MgOCrefractor-
ies are dissolution of MgO in the slag and oxidation by increasing B
2
O
3
to only ~007 wt-%.
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 51
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
2
O
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 eectively inhibits C oxidation, it has a
positive eect on corrosion resistance. Ikesue et al.49
tested the eectiveness of Al addition to MgOC
bricks in a basic slag (C/S=30). They found that
the Al addition improves the corrosion resistance. On
the other hand, Baker and Brezny50 found that Al
addition to MgOC bricks resulted in severe cor-
rosion in an acid slag (C/S=10). Asano51 used a
rotary slag test to examine the eect of Al in two
slags with basicity of 10 (slag A) and 20 (slag B). His
results (Fig. 20) show that Al addition to MgOC
19 Influence of B
2
O
3
content in MgO grain on
refractories improves their corrosion resistance
corrosion rate of MgOC bricks, showing
slightly in the more basic, but not in the acid, slag.
that slight increase of B
2
O
3
content in MgO
Silicon (or SiC) and B
4
C are also used as additives
grain markedly decreases corrosion
to carbon containing refractories.52,53 The CaOSiO
2
resistance (Ref. 38)
and CaOB
2
O
3
phase diagrams (Fig. 21)11 show a
problem when using such additives in ZrO
2
C refrac-
of C by oxidising atmosphere or Fe
x
O and MnO
tories. In these refractories, oxides (SiO
2
and B
2
O
3
)
from the slag.47,48 Addition of Al metal powder to
formed from oxidation of Si (or SiC) and B
4
C are
MgOC refractories has a positive eect on corrosion
not in equilibrium with the stabilising agents (e.g.
resistance by encouraging formation of a dense MgO
CaO) in the ZrO
2
grain at high temperature, so they
layer and inhibiting C oxidation, but it also has a
will react with each other to form CaOSiO
2
and
negative eect by increasing the saturation solubility
CaOB
2
O
3
compounds. The formation of these com-
of MgO in the slag (Fig. 15). As shown in Fig. 15, in
pounds will cause ZrO
2
destabilisation so the ZrO
2
an acid slag, the saturation solubility of MgO in the
grain disintegrates, adversely aecting the corrosion
slag is high, so MgO dissolution in the slag is the
resistance.54
dominant factor aecting the corrosion resistance. In
this case, even if a dense MgO layer forms, it will
quickly dissolve in the slag. Furthermore, Al
2
O
3 Influence of atmosphere on
formed from oxidation of Al will increase the satu-
refractories corrosion resistance
ration solubility of MgO in the slag (Fig. 15), counter-
acting the positive eect of Al addition, so that it The oxygen partial pressure in a refractory lined
enclosure may vary in service, leading to a change of may not have an overall positive eect on the cor-
20 Corrosion of MgOC bricks with and without Al addition in acid slag A (C/S=10) and more basic
slag B (C/S=20):51 Al addition slightly improves corrosion resistance in more basic slag, but does
not in acid slag
International Materials Reviews 2000 Vol. 45 No. 2
52 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
T
E
M
P
E
R
A
T
U
R
E
,

C
(a)
(b)
21 Phase diagrams for a CaOSiO
2
and b CaOB
2
O
3
systems, compositions in wt-% (Ref. 11)
valence of some components (in particular, iron oxide) (Fig. 22a), a liquid will develop at as low as 1210C
when a reclay brick consisting initially of mullite in the refractories and/or slag. This can signicantly
aect the refractories corrosion resistance. and tridymite (or cristobalite) absorbs a small amount
of iron oxide. If, however, the brick is higher in Al
2
O
3
Consider the inuence of atmosphere on corrosion
resistance of Al
2
O
3
SiO
2
refractories containing, or and originally consists of mullite and corundum, a
liquid will not form until a temperature of 1380C is in contact with, iron oxide. Figure 22 shows solidus
surfaces in the Al
2
O
3
SiO
2
FeO and Al
2
O
3
SiO
2
reached, even after a considerable amount of iron
oxide has been absorbed by the brick. In air, Fig. 22b, Fe
2
O
3
systems.27 Under strongly reducing conditions
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 53
(a) (b)
22 Projections of solidus surface in iron oxideAl
2
O
3
SiO
2
system in a reducing and b oxidising
atmospheres (Ref. 27)
(a) (b)
a in reducing atmosphere; b in oxidising atmosphere
23 1500?C isothermal sections through CaOMgOiron oxide system; MW magnesiowustite, MF
magnesioferrite, L liquid (Ref. 27)
the lowest temperatures of liquid formation for bricks cause a liquid to develop at temperatures above 1210
and 1380C, depending on the Al
2
O
3
/SiO
2
ratio of of the same compositions as above are considerably
higher. On addition of iron oxide a reclay brick the original brick (Fig. 22a). In air, on the other hand,
a substantial proportion of the iron is present as develops a liquid phase only after a temperature of
1380C or higher is reached, while a high alumina Fe3+. Hence moderate amounts of iron oxides can be
absorbed by aluminasilica refractories in air without brick with absorbed iron oxide withstands temper-
atures at least as high as 1460C before liquid starts formation of a liquid phase even at temperatures
above those of the three-phase triangles labelled 1380 forming.27
An important dierence between the two diagrams and 1460C in Fig. 22b. Composition triangles in
which liquid is one of the phases present therefore (Fig. 22a and b) is related to the manner in which
iron can be accommodated in the crystal structures extend all the way over to the Al
2
O
3
SiO
2
side of
Fig. 22a, whereas the analogous areas in Fig. 22b of the phases present. Two of the crystalline phases
present in aluminasilica refractories, mullite and terminate before reaching the Al
2
O
3
SiO
2
side.27
The above analyses indicate that Al
2
O
3
SiO
2
corundum, can accommodate iron ions in their
lattices, but only in the ferric state (Fe3+). Under refractories have better corrosion resistance in oxidis-
ing than in reducing atmosphere. Based on this con- reducing conditions, where the iron in the oxide
phases is present almost exclusively as Fe2+, incorpor- clusion, it can be deduced that C in Al
2
O
3
(SiO
2
)C
refractories may have dierent eects on the corrosion ation of Fe in the crystalline phases cannot take place.
Hence, even small amounts of iron oxide absorbed resistance of Al
2
O
3
(SiO
2
) grain phases, depending
International Materials Reviews 2000 Vol. 45 No. 2
54 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
T
E
M
P
E
R
A
T
U
R
E
,

C
T
E
M
P
E
R
A
T
U
R
E
,

C
(a)
(b)
(c) (d)
24 Phase diagrams of a MgOFeO (Ref. 11), b MgOFe
2
O
3
(Ref. 11), c CaOFeO (Ref. 28), and d CaOFe
2
O
3
(Ref. 28) systems
on the local reducing conditions. If C only reduces reducing conditions (Fig. 23a), a CaOMgO mixture
of composition A can take up about 22% iron oxide Fe
2
O
3
in the refractories or slag to FeO, then
Al
2
O
3
(SiO
2
) grains resistance to slag attack will without a liquid phase developing at 1500C. In air
(Fig. 23b), however, only 3% iron oxide can be taken be decreased. However, if C further reduces FeO to
metallic Fe, the liquid formation temperature and up before a liquid phase develops at the same temper-
ature. Hence, maintaining strongly reducing con- the slag viscosity are expected to increase so improv-
ing the resistance of the Al
2
O
3
(SiO
2
) grains to slag ditions within a dolomite refractory body exposed to
iron oxide attack is desirable.27 The carbon in attack.
Now consider the inuence of atmosphere on the MgOCaOC or tar bonded MgOCaO bricks for
oxygen steelmaking vessels is believed to serve this corrosion resistance of MgOCaO refractories con-
taining, or in contact with, iron oxide. The MgO purpose. In addition, however, carbon probably plays
other important roles in the chemistry involved during CaOFeO and MgOCaOFe
2
O
3
phase diagrams at
1500C (Fig. 23)27 reveal a large dierence in the use of such bricks. For example, the carbon reduces
some iron oxide in the refractories and/or in the slag extent of the area where no liquid phase is present at
the two dierent oxygen pressures. Under strongly to metallic iron, which enhances the liquid formation
International Materials Reviews 2000 Vol. 45 No. 2
Zhang and Lee Use of phase diagrams in studies of refractories corrosion 55
(a) (b) (c)
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 MgOCaO(C) refractories (Ref. 57). In low basicity and low iron oxide slag
(C/S=12 and T. Fe=91 wt-%), MgOCaO(C) refractories have better slag resistance than MgO(C)
refractories, but in high basicity and high iron oxide content slag (C/S=31 and T. Fe=19 wt-%) they
exhibit poorer corrosion resistance
temperature in the refractories and/or slag increasing saturation solubility, its dissolution in the slag is a
serious problem. Increasing the CaO (decreasing viscosity and reducing corrosion.
MgO) content in the refractories usefully decreases
their dissolution. Furthermore, increasing the CaO
Comparing corrosion resistance of
content may lead to the formation of a C
2
S layer
refractories
(Fig. 21a) at the refractory/slag interface,55,56 which
causes indirect dissolution and retards corrosion.
In many cases, phase diagrams can be used to com-
Therefore, in low basicity slag, the MgOCaO(C) pare qualitatively the corrosion resistance of dierent
show better corrosion resistance than MgO(C) refractories by checking the compatibility between
refractories.
the refractories and slag. A good example of this is
Considering both the inuence of Fe oxide and of the comparison of corrosion resistance of MgO(C)
slag basicity on the corrosion resistance of MgO(C) and MgOCaO(C) refractories.
and MgOCaO(C) refractories indicates that in
The MgOFeO (Ref. 11), MgOFe
2
O
3
(Ref. 11),
low basicity and low Fe oxide content slag, CaOFeO (Ref. 28), and CaOFe
2
O
3
( Ref. 28)
MgOCaO(C) refractories will show better cor- phase diagrams are shown in Fig. 24. After MgO
rosion resistance than MgO(C) refractories, but in
absorbs 70 wt-% FeO or 70 wt-% Fe
2
O
3
, the liquid
the high basicity and/or high Fe oxide content slag, formation temperature is still higher than 1600 or
the latter will show better corrosion resistance. 1700C (Fig. 24a and b), but after CaO absorbs
Induction furnace and rotary slag test results5763
only <15 wt-% FeO or a small amount of Fe
2
O
3
,
support these predictions. Figure 25, as an example, the liquid formation temperature falls to ~1160 or
shows the rotary slag test results of Toritani et al.57 1438C (Fig. 24c and d), and after CaO absorbs about
Except for the two bricks with CaO of ~8 and
60 wt-% Fe
2
O
3
, all of it becomes liquid at ~1450C
~17 wt-% in the slag with C/S=31 and total (Fig. 24d).
Fe oxide (T. Fe)=19 wt-% (Fig. 25a), MgOCaO Comparing Fig. 24 with Fig. 23, reveals that after
(Fig. 25a) and MgOCaOC refractories (Fig. 25b
the MgOCaO refractory (A) takes up ~22 wt-%
and c) show better corrosion resistance than MgO FeO or 3 wt-% Fe
2
O
3
, liquid develops at 1500C
and MgOC refractories in the low basicity (C/S= (Fig. 23), however, after MgO refractory absorbs the
12) and low Fe oxide content (T. Fe=91 wt-%) same amount of FeO or Fe
2
O
3
, the liquid formation
slag, but exhibit poorer corrosion resistance in the temperature remains higher than 2300 or 2700C
high basicity (C/S=31) and high Fe oxide content
(Fig. 24a and b).
(T. Fe=19 wt-%) slag. The above dierences indicate that with higher Fe
oxide content slags, the MgO(C) corrosion resistance
is better than that of MgOCaO(C) refractories.
Refractories selection for specific
The corrosion behaviour of MgO(C) is also
applications
dierent from that of MgOCaO(C) refractories in
slags with dierent basicities. As shown in Fig. 6, in By checking the compatibility between refractories
and surrounding slags, the corrosion behaviour of a slag with low basicity, because MgO has high
International Materials Reviews 2000 Vol. 45 No. 2
56 Zhang and Lee Use of phase diagrams in studies of refractories corrosion
(a)
(e) (f)
(b)
Mol.-%
T
E
M
P
E
R
A
T
U
R
E
(c) (d)
Mol.-%
26 Phase diagrams of a Al
2
O
3
CuO/Cu
2
O (Ref. 64), b CaOCuO/Cu
2
O (Ref. 65), c ZrO
2
CuO/Cu
2
O (Ref. 66),
d SiO
2
CuO/Cu
2
O (Ref. 67), e MgOCuO/Cu
2
O (Ref. 68), and f Cr
2
O
3
CuO/Cu
2
O (Ref. 69) systems
dierent refractories can be predicted and compared, amounts of Cu
2
O/CuO uxes these oxides (i.e. lowers
the melting temperature). For example, just a tiny assisting refractories selection for specic applications.
A good example of this is selection of refractories to amount of Cu
2
O/CuO will decrease the liquid forma-
tion temperature from 2051C (the melting point of be exposed to copper melting slags.
Figure 26 shows the Al
2
O
3
Cu
2
O/CuO (Ref. Al
2
O
3
) to 1238C with Al
2
O
3
(Fig. 26a), and from
2730C (the melting point of ZrO
2
) to 1130C with 64), CaOCu
2
O/CuO (Ref. 65), ZrO
2
Cu
2
O/CuO
(Ref. 66), SiO
2
CuO (Ref. 67), MgOCu
2
O/CuO ZrO
2
(Fig. 26c).
However, the cases of MgO and Cr
2
O
3
are quite (Ref. 68), and Cr
2
O
3
Cu
2
O/CuO (Ref. 69) phase dia-
grams. As can be seen from Fig. 26ad, CuO and dierent. As shown in Fig. 26e, MgO can take up
20 wt-% Cu
2
O/CuO without liquid formation, and Cu
2
O are corrosive to Al
2
O
3
, CaO, SiO
2
, and ZrO
2
refractories, because the presence of even small even after Cr
2
O
3
absorbs ~65 wt-% Cu
2
O/CuO,
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 MgOCuOCr
2
O
3
showing saturation solubility of MgO of
28 Solidus surface of CaOMgOSiO
2
system
composition E and MgCr
2
O
4
of composition F
shown in Fig. 3a (Ref. 27)
in liquid at this temperature is low (Ref. 3)
system in Al
2
O
3
-based castables. However, if CA
cement is added to an MgOMA castable, the liquid
no liquid forms (Fig. 26f ). Consequently, MgO and
formation temperature is lower than 1400C ( point Q
Cr
2
O
3
are much more resistant to Cu
2
O/CuO than
on Fig. 9). A similar situation arises in MgOCaO
Al
2
O
3
, CaO, SiO
2
, and ZrO
2
. The MgOCr
2
O
3

castables. CA cement thus does not provide a suitable

Cu
2
O diagram at 1400C (Ref. 3) (Fig. 27) further
bond system for basic castables.
reveals that the solubilities of MgO and MgCr
2
O
4
in
To improve owability and other properties of
liquid (L) at 1400C are low. The above analyses
castables, superne (submicrometre) powders such
explain why direct bonded magnesiachrome refrac-
as Al
2
O
3
and SiO
2
are usually added.7981 A small
tories are so successful in copper smelting furnaces.70
amount of Al
2
O
3
added to a MgOCaO castable will
decrease the liquid formation temperature to lower
Designing refractories composition than 1500C ( Fig. 9). However, examining the CaO
MgOSiO
2
phase diagram (Fig. 3a) shows that when
Proper raw materials selection and optimisation of
a small amount of SiO
2
is added to a MgOCaO
refractories compositions are important factors in
castable, C
3
S will form and the liquid formation
developing refractories with high refractoriness and
temperature remains as high as ~1850C. This indi-
good corrosion resistance. A good example of this is
cates that using superne SiO
2
powder in MgOCaO
control of the C/S ratio in MgO grain materials or
castables is better than using superne Al
2
O
3
powder
refractories.71,72 The solidus surfaces of the CaO
if corrosion resistance is paramount.
MgOSiO
2
system (Fig. 28) reveal that the liquid
formation temperature generally increases with
Summary
increasing C/S ratio in the MgO grain. For example,
the liquid formation temperature corresponding to Understanding corrosion mechanisms and comparing
C/S(mol ratio) =1015 is 1490C, to C/S=1520 corrosion resistance of refractories in various slags is
is 1575C, to C/S=2030 is 1790C, and to C/S>30 important for evaluating their service life. Phase dia-
grams provide useful information about the compati- is 1850C. Therefore, it is necessary to maintain the
bility between refractories components and slags, C/S ratio of MgO grain or MgO based refractories
which can be used to interpret corrosion mechanisms above 20 to retain high refractoriness and corrosion
and predict corrosion behaviour. In this review, typi- resistance.7173
cal applications of phase diagrams to specic prob- A further example is selection of a suitable bond
lems of refractories corrosion have been highlighted.
system for castable refractories. Calcium aluminate
Experimental corrosion test results show good agree-
cement (CA cement) is widely used in Al
2
O
3
-based
ment with the phase diagram predictions (though
castable refractories, though in recent years, cement-
phase diagrams do not contain any information re-
free castables have been developed (e.g. Refs. 7476).
lating to the kinetics of the reactions involved).
According to the CaOMgOAl
2
O
3
phase diagram
Therefore, use of the information which is available
(Fig. 9), small additions of CA cement whose main
in existing phase diagrams can reduce the need for
components are CA, CA
2
, and C
12
A
7
(Refs. 77, 78)
expensive and time consuming experimentation to
to Al
2
O
3
castable will lead on ring to formation of
evaluate the high temperature corrosion of refrac-
CA
6
, and in this case the liquid formation temperature
tories.
is ~1870C (point Y on Fig. 9). With addition of a
small amount of CA cement to Al
2
O
3
MA castable,
References
the liquid formation temperature remains higher than
1800C (point X on Fig. 9). Therefore, if SiO
2
is not
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1982, 2, (2), 513. added, CA cement gives a highly refractory bond
International Materials Reviews 2000 Vol. 45 No. 2
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s. x:1:ox:: Taikabutsu (Ref ractories), 1988, 40, 535542. 4. . novN r: in Phase diagrams in advanced ceramics, (ed.
A. M. Alper), 4384; 1995, New York, Academic Press. 44. 1. xoi1o, :. n:i1:, x. ix:iin:, x. icnixi:, and x. xix:c:i:
Taikabutsu (Ref ractories), 1982, 34, 336341. 5. :. n:xnis1 and . vrns1r: in Steelmaking in the basic arc
furnace, 171176; 1964, London, The Iron and Steel Institute. 45. n. isnii, i. 1sicnix:, x. ocicni, 1. x:v:x:xi, and n. 1:x:n:sni:
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T rans., 1987, 86, 7476. 46. . icnixi:, x. xix:c:i, i. onisni, x. oc:s:n::, and
1. xoixo1o: Interceram, 1985, Special Issue, 6366. 7. . :. x. vannorx, r. . . vanioo, and . xr1sri::: in Proc. of
Int. Ceramics Conf. AUSTCERAM 90 (Australasian Ceramic 47. s. 1:x:N:c:: Taikabutsu Overseas, 1993, 13, ( 4), 814.
48. :. x:1sio, s. xix:c:v:, x. oc:s:n::, x. xoxoi, . icnixi:, Society), (ed. P. J. Darragh and R. J. Stead), 111119; 1991,
Brookeld, VT, Trans Tech Publications. and x. xix:c:i: Taikabutsu Overseas, 1985, 5, (2), 36.
49. :. ixrsir, n. x:x:xo1o, n. snix:No, x. ni:cisni, and 8. N. xcc:iiix and i. . n:r11: Br. Ceram. T rans., 1952,
51, 523548. s. x:1:ox:: Taikabutsu (Ref ractories), 1988, 40, 535542.
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