technology trends

Mineralogy and Thermodynamics in Refractories

A. Buhr
Dedicated to the 10th Anniversary of refractories WORLDFORUM

This paper summarises the main content of a presentation given at the 53 Annual Symposium on Re­
rd

fractories sponsored by The St. Louis Section and Refractory Ceramics Division of the American Ceramic
Society when receiving the T. J. Planje St. Louis Refractories Award in 2017.
Mineralogical approaches including the work with phase diagrams can be very useful tools for the assess­
ment of hot temperature properties and reactions occurring during wear of refractories. It does not require
sophisticated computer programs to work with the diagram but only a ruler and a calculator. The paper
describes the benefit of phase diagram work in the assessment of high alumina refractories by selected
examples from high alumina castables for steel applications. The investigation of wear mechanism from
Andalusite based castable as tundish permanent lining is another example provided.

1 Introduction
The basics of thermodynamics are included
in the curriculum of almost all material
sciences. This includes the principles and
function of phase diagrams. However, the
lectures often focus only on the theoretical
background, which includes rather com­
plicated formulas, but the practical work
with the diagrams often falls short. Conse­
quently, many engineers remember the the­
or­etic­al formula challenges with bad feel­
ings when considering thermodynamic, but
never apply practical working with phase
diagrams.
For the practical work with the diagrams it
requires only the knowledge of the phase
rule and some basic principles but no com­ Fig. 1 Tools for the classical work with phase diagrams
plicated mathematics. This shall be briefly
discussed using the ternary (three compon­ most refractory applications it does not vary system is not in equilibrium and reac­
ent) phase diagram CaO–Al2O3–SiO2 as an in relevant ranges and can be considered as tions will occur to achieve the equilibrium
example [1]. The tools are simple as shown constant. The phase rule changes accord­ stage.
in Fig. 1. ingly to P + F = C + 1.
In a ternary system (C = 3), three phas­ Andus Buhr
2 Basic principles es can occur when the temperature is Almatis GmbH
The phase rule defines the number of variable (F = 1), for example three solid 60528 Frankfurt
phases and degrees of freedom which ap­ phases or two solid and one liquid phase Germany
ply for a system in equilibrium. It says: (P = 3). Four phases, e.g. three solid and
P + F = C + 2, where P is the number of one ­liquid, can only occur in equilibrium, E-mail: Andus.Buhr@almatis.com
phases, F is the degrees of freedom (chem­ when the temperature is fixed (F = 0). www.almatis.com
ical composition, temperature, pressure), These points in a diagram are called “in­
and C is the number of components (e.g. variant points” and are marked with the Keywords: phase diagrams,
CaO-Al2O3-SiO2). The pressure is relevant specific temperature in the diagram. If high alumina refractories, steel
for geological systems (kbar range) but for more phases occur in a given sample, the

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SiO2

7 % CaO

Anorthite

Mullite

44 % Al2O3

Fig. 2 Position of a given composition in the phase diagram [1] Fig. 3 Single, binary, and ternary compounds and conodes connecting
(7 % CaO, 44 % Al2O3, 49 % SiO2) co-existing phases

A few basics for the work with the diagrams can co-exist in equilibrium, e.g. SiO2 – mul­ this will happen. This level of the diagram is
will be discussed. Fig. 2 shows how to place lite. Triangles connect co-existing phases in therefore named the liquidus. The name of
a given position in the diagram. The points on a ternary system, e.g. SiO2 – mullite – anor­ the primary phase is given in each primary
straight lines are either single compounds at thite. Only triangles are possible in a ternary crystallisation field.
the edges (e.g. SiO2), or binary compounds system (Fig. 3). The points where three primary crystallisa­
(e.g. mullite 3Al2O3 · 2SiO2), or ternary com­ The curved lines in the diagram show the tion fields meet are the solidus. At this tem­
pounds (e.g. anorthite CaO · Al2O3 · 2SiO2). primary crystallisation fields of all phases perature, the melting of all compos­itions
Straight lines (conodes) show the phase (compounds) in the diagram (Fig. 4). These inside the according subsolidus tri­angle will
relations in the subsolidus which means all fields indicate which phase will crystallise start. If this solidus point lies inside the tri­
phases are solid, nothing is molten. They first when a liquid of a given composition angle, it is eutectic melting behaviour (e.g.
connect phases (resp. compounds) which is cooled down and at which temperature at 1345 °C for the triangle SiO2 – mullite

a b
SiO2 Corundum
Mullite Mullite
Anorthite Anorthite

1345 °C 1512 °C

Fig. 4 a–b Primary crystallisation fields and eutectic and peritectic melting behaviour – a) triangle anorthite – SiO2 – mullite,
b) triangle anorthithe – mullite – corundum

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Fig. 5 Constituents of high alumina castables

– anorthite), if it lies outside, it is peritec­

tic melting behaviour (Fig. 4). In case of
peritectic melting behaviour compounds do
not simply melt but transform into a higher
melting compound of this triangle and a
liquid phase, e.g. mullite + anorthite = co­
rundum + liquid at 1512 °C (Fig. 4).

3 Hot properties of
high alumina castables
Fig. 5 shows the constituents of high alu­
mina castables, and Fig. 6 shows the com­
pos­itions of 48 high alumina castables in
the phase diagram. The melting behaviour
from phase diagram evaluation of these
castables was compared with the hot prop­
erties such as creep resistance and hot
crushing strength [2].
Here, two corundum and two andalusite Fig. 5 Constituents of high alumina castables
castables are used as examples. Their com­
position is given in Tab. 1. Shape
The theoretical solidus temperature is de­ 1345 °C
rived from the phase diagram and gives the
onset of melting. The presence of even small
amounts of liquid phase has a significant
effect on the thermomechanical proper­ CA6 – Corundum
ties of the castables, because it works as a 1512 °C (peritectic 1875 °C)
lubricant in the microstructure and has an
immediate effect on the strength at high Corundum – Anorthite – Mullite
temperatures. This shows in the hot crush­ (peritectic 1512 °C)
ing strength and the creep resistance at
Mullite – Anorthite – Cristobalite
high temperature.
(eutectic 1345°C)
The cement phases in high alumina castables
react with the other components in the tem­
perature range from 1100–1500 °C to form
higher alumina calcium-aluminates such as
CA2 and CA6, or anorthite if SiO2 is pres­
Shape
ent. These sintering reactions also show in Think alumina, think Almatis. Page 14

refractoriness under load testing unless the

samples are pre-fired at high temperature as Fig. 6 Position of high alumina castables and according equilibrium phase assembly
can be seen in Fig. 7. At 1000 °C pre-firing,
Tab. 1 Composition and hot strength of high alumina castables
the corundum low cement castable shows
an intermediate softening before the cement Andalusite Corundum
sintering reactions have taken place. After­ 1 2 1 2
wards, the creep rate at 1500 °C is identical SiO2 [mass-%] 38 36 3,6
when compared to 1500 °C pre-firing. Al2O3 [mass-%] 58 61 97 93
The samples in this study [2] were normally
TiO2 [mass-%] 0,7
pre-fired for 12 h at 1000 °C in order to
CaO [mass-%] 2,3 1 2,5 1,5
simulate the conditions in steel ladles and
tundishes which are typically pre-heated in Alkalies [mass-%] 0,3 0,3 0,3 0,2
this temperature range. Theoretical solidus temperature [°C] 1345 1345 1875 1512
The castable corundum 1 has a sol­ id­us Hot Crushing Strength @ 1500 °C [MPa] 1 11 48 0
temperature of 1875 °C, whereas the sol­ Silica fume + + +
id­us of corundum 2 is considerably lower at
Matrix aluminas + +
1512 °C due to the addition of silica fume
(about 3,5 %) in the formulation (Fig. 8). Theory vs. practice OK ? → OK OK OK

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into mullite and SiO2 when fired at tem­

pera­ tures above 1200 °C. Therefore, mullite
Temperature range Cor. ++++
ß-Al. +
of cement reactions CA6 ++
is the phase to be considered for the phase
CA2 +
diagram evaluations in this paper.
Pre-fired 1500 °C Both andalusite low cement castables 1 and
2, should show a solidus at 1345 °C due
Length change %

to their composition in the triangle SiO2–

Time h mullite–anorthite (Fig. 10). However, the
thermomechanical testing shows a different
picture (Fig. 11). The behaviour of andalu­
Temperature °C site 1 is in line with the theory as it shows
Pre-fired 1000 °C no creep resistance at 1500 °C. In contrast,
andalusite 2 shows an unexpected creep
Corundum ++++
ß-Alumina + resistance after the cement reactions have
CA +
K2 castable CA2 +
taken place. This seems to be in conflict with
C12A7 (+)
the theory from the phase diagram, because
Fig. 7 Impact of pre-firing temperature on creep under compression of
the onset of melting should be at 1345 °C.
a corundum low cement castable (0,2 MPa, 1500 °C) The obvious discrepancy between the the­
or­etical and practical behaviour of anda­
lusite 2 can be explained when the matrix
1512 °C composition of the castables is taken into
account instead of focussing only on the
bulk composition of the castables. The mat­
rix composition is of special importance
because some constituents of the castables
only occur in the matrix fines, such as the
cement and the fine fillers silica fume and
matrix aluminas.
Andalusite 1 and 2 are quite different in
Fig. 10 Position of Andalusite low cement castables
the matrix composition, because andalu­
1a
site 2 has an addition of matrix aluminas
temperature for both at 1345 °C
including reactive alumina. The matrix has
Corundum 2 (+ SiO ): 1512 °C been defined as the particle size fraction
Corundum 1: 1875 °C 2

Fig. 8 Solidus temperatures for corundum low cement castables 1 and 2

K9 w/o fume K5 w/ creep 1500°C

Corundum 1: 1875 °C Corundum 2 (+ SiO2) 1512 °C

Fig. 9 Creep under compression of corundum low cement castables (0,2 MPa, 1500 °C, 24 h)

The creep under compression at 1500 °C lies and the 0,7 % TiO2 for corundum 2 are
of corundum 1 shows a stable behaviour taken into account. TiO2 plus Na2O form a
whereas corundum 2 has no creep resist­ liquid already at 1300–1350 °C [3, 4].
ance at that temperature due to liquid phase Andalusite is a metamorphous mineral
formation (Fig. 9). This is in line with the formed under pressure at elevated tem­
theory especially when the small amounts perature in the earth crust. It is not stable Fig. 10 Position of andalusite low cement castables 1
of additional contaminants such as alka­ under atmospheric pressure and transforms and 2, solidus temperature for both at 1345 °C

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Fig. 11 Creep under compression of Andalusite low cement castables 1
and 2 (0.2 MPa, 1500 °C, 24 h)
below 0,12 mm, because it enabled an easy
screening for analytical purposes.
Fig. 12 shows the position of the matrix
composition of castables andalusite 1 and
2. Whereas the matrix composition of anda­
lusite 1 remains in the triangle SiO2 – mul­
lite – anorthite (solidus at 1345 °C), the
matrix composition of andalusite 2 shifts
into the triangle corundum – mullite – an­
orthite (solidus at 1512 °C).
The addition of matrix aluminas leads to a
higher solidus temperature for the matrix
when compared to the bulk composition of
andalusite castable 2. Poirier et al. [5] have
shown that the silica released during the
Fig. 11 Creep under compression of andalusite low cement castables 1 and 2
mullitisation of andalusite forms a highly
(0,2 MPa, 1500 °C, 24 h)
viscous molten phase inside the previous
andalusite crystals at elevated tempera­ 160–170 mm andalusite low cement cast­ Samples from four different tundishes were
tures. This liquid phase does not interfere able as permanent lining and 30–50 mm taken for investigation of the wear mech­ 22

with the matrix around the previous anda­ wet sprayed, water glass bonded magnesia- anism. The residual cold crushing strength
lusite crystals, especially when this matrix olivine wear lining. The wear lining was was between 50–70 MPa, comparable
itself has a high refractoriness due to the removed through tilting the tundish upside to the new castable pre-fired for 12 h at
addition of reactive matrix aluminas. This down after each casting campaign of typ­ 1000 °C in the laboratory. The mechanical
explains the unexpected high creep resist­ ic­ally 4 heats, sometimes up to 15 heats. stresses due to tilting the tundish and ther­
ance and hot crushing strength at 1500 °C Afterwards, the tundish cooled down to be­ mal cycling between each campaign are an
(Tab. 1) of andalusite castable 2. low 100 °C before a new wear lining was important challenge to the tundish castable.
applied. However, mechanical and thermal spalling
4 Wear mechanism of Once per year after about 1200 heats, the could be excluded as major wear mech­
andalusite tundish castable tundish castable was replaced. The remain­ anism due to the high thermal shock resist­
The wear mechanism of tundish castable ing thickness was typically between 100– ance and sufficient mechanical strength of
was investigated at the Dortmund steel­ 150 mm but in higher challenged areas such the low cement andalusite castable. This
Source file Fig 12
works [2]. The size of the tundish was
about 40 t. Fig. 13 shows the lining with
as in the impact zone and around the well
Fig. 13
blocks it could be down to 80–90 mm.
investigation focuses on the chemical-min­
Tundish with Andalusite castable
eralogical reactions at the hot face of the
perma
sprayed basic wear lining (II+III)

1345 °C

1512 °C
Andalusite 1
Andalusite 2

Fig. 12 Composition of andalusite castables 1 and 2, solid points are Fig. 13 Tundish with andalusite castable permanent
bulk composition, circles are matrix composition as size fraction lining (I), and wet sprayed basic wear lining (II+III)
24
below 0,12 mm 24

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Fig. 14 Tundish Andalusite castable after use (1172 heats) with adhering
wear lining layer; chemical composition of different layers
ing times due to an abnormally long tundish
sequence without adjusting the spray mix
thickness in advance. The chemical-miner­
alogical composition was measured for dif­
ferent layers. At the hot face of the tundish
castable the andalusite was transformed
to mullite which indicates temperatures in
the range of 1300–1400 °C in that area. In
general higher alkali contents in the range
of 2–7 % were found in a 3–7 mm thick
layer at the hot face of the castable samples
(Fig. 15). This is much more than originally
Cold Hot contained in the tundish castable (0,2–
face face
Distance from cold face in mm 0,3 % K2O and Na2O) and the water glass
26 bonded spray mix (around 0,4 % Na2O and
Fig. 14 Tundish andalusite castable after use (1172 heats) with
K2O). X-ray diffraction (XRD) showed spinel
adhering wear lining layer; chemical composition of different layers
Fig. 15 Alkali enrichment at hot face of Andalusite tundish castables (MgAl2O4) in the reaction layer between
after use castable and spray mix, and nepheline
([Na, K]AlSiO4) in the alkali enriched hot
face layer of the castables.
The spinel reaction layer formed during
sintering between spray mix and castable
is about 300 µm thick (Fig. 16). As shown
in the ternary system MgO–Al2O3–SiO2 [1],
mullite and periclase (MgO) are not com­
patible and react to spinel and cordierite
(Fig. 17) respectively MgO-containing al­
kali-aluminium-silicate glassy phase due to
the high alkali contents present in the cur­
rent case and measured by electron micro­
probe analysis.
Independent from the spinel formation,
Fig. 15 Alkali enrichment at hot face of andalusite tundish castables after use 27 which only occurs in cases of sintering
taking place between the castable and
tundish castable, which eventually lead to a ly such sintering between the basic wear the spray mix, the mullite in the hot face
reduction of lining thickness. lining and the tundish castable shall not layer is decomposed by the alkalies en­
Fig. 14 shows a sample from tundish cast­ occur and it indicates too high temperature riched in this zone. It reacts to corundum
able after use with an adhering layer of sin­ in the contact zone due to insufficient lining (bright ledges in Fig. 18), and nepheline as
tered magnesia-olivine wear lining. Normal­ thickness of the spray mix or extended cast­ detected by XRD and electron microprobe
Source file Fig 16
analysis respectively a glassy phase of simi­
lar composition at elevated temperature
during service. Fig. 19 shows the reaction
in the ternary system Na2O–Al2O3–SiO2 [1].
The sample containing 7 % alkalies in the
hot face layer of the castable shows com­
MgO - plete decomposition of the mullite and just
Olivine corundum ledges in a matrix of nepheline
wear Andalusite
lining composition (Fig. 20). In the next layers to­
castable
permanent wards the cold face of the castable, alkali
lining contents are quickly decreasing and at the
cold face the alkali contents are the same
as for the new castable. At lower alkali con­
tents, the matrix besides mullite (or anda­
Spinel reaction layer at contact lusite transforming into mullite) consists of
29
anorthite respectively a glassy phase with
Fig. 16 Spinel formation on andalusite castable similar composition.

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The chemical-mineralogical wear mech­an­

ism of the tundish castable can be summar­
ized as alkali diffusion from alkalies in the
spray mix at temperatures around 1500 °C
towards the cold side into a thin layer of less Mullite + MgO =
than 10 mm at the hot face of the castable. Spinel + MgAl-Silicate
Here, the alkalies accumulate, first due to
solid solution formation with the anorthite Cordierite
in the matrix and then through reaction
with the mullite to corundum and nephe­
line at higher alkali contents. This reaction
is accompanied with a volume expansion of Mullite
about 20 %, which could lead to spalling
(alkali-bursting).
However, no evidence for such spalling
was found in the samples from the tundish
castables, even for alkali contents as high MgO
as 7 % in the hot face, where mullite was Fig. 18 Mullite decomposition through alkali attack Spinel at hot face from
completely decomposed. At service temper­ tundish castable
Fig. 17 Mullite decomposition through MgO
atures in the tundish the nepheline forms
a glassy phase which releases the stresses
necessary for the occurrence of alkali-burst­
ing.
A second wear mechanism is the spinel
formation through intense sintering with
the basic spray mix, which only occurs oc­
casionally when temperature in the contact
between castable and spray mix lining be­
comes too high. When removing the wear
lining after use, this strongly sintered and
densified layer will often be removed as
well, leading to reduction of castable thick­
ness. The sample shown in Fig. 14 with
adhering spinel reaction layer and residual
sintered spray mix can be considered an ex­
ceptional case here as the layer sticks to the Fig. 18 Mullite decomposition through alkali attack at hot face from tundish castable
32
castable.
Calculations have shown that such strong
sintering and spinel formation cannot oc­
cur during every casting sequence of the
Mullite + Na2O =
tundish. Otherwise long lining life of one
year or about 1200 heats, respectively Nepheline + Corundum
300 casting sequences would not be pos­
sible. Nevertheless, when comparing the
effect of both wear mechanisms it is the
strong sintering accompanied with spinel
formation between the layers which finally Nepheline
leads to wear of the tundish castable requir­
ing a renewal each year. Mullite

5 Conclusion
For the practical work with phase diagrams
no sophisticated calculations and theory
are required. The understanding of a few Na2O
Corundum
basic principles and sufficient training dur­
ing the scientific education provides the Fig. 19 Mullite decomposition by alkalies (here Na2O)

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Fig. 20 Mullite completely transformed; Corundum ledges in matrix of
Nepheline composition

relevant chemical components. Therefore a

special focus should always be given on the
matrix composition.
The addition of matrix aluminas, especially
high performance reactive aluminas im­
proves the thermo-mechanical properties
of high alumina refractories and enhances
their overall performance in application.

References
[1] Levin, E.M.; Robbins, C.R.; McMurdie, H.F.:
Phase diagrams for ceramists. Amer. Ceram.
Soc., Columbus, OH, 1964
[2] Buhr, A.: Tonerdereiche Feuerfestbetone für
den Einsatz in der Stahlindustrie (High alumina
Fig. 20 Mullite completely transformed, corundum ledges in matrix of
35 refractory castables for use in the steel indus­
nepheline composition
try). PhD Thesis 1996 and publication in Stahl
und Eisen 116 (1996) [9] 59–66
necessary skill set for refractory engineers grams such as FactSage® [6] is convenient [3] Schlegel, E.: Auswertung von Phasendiagram­
to apply work with phase diagrams in their and, given a reliable data base, extends the men hinsichtlich der Alkalibeständigkeit feu­
daily work. Phase diagram evaluations can thermodynamic work in more complex sys­ erfester Baustoffe, Teil 1. Keram. Z. 61 (2009)
be very helpful to assess the behaviour of tems or areas, where no phase diagrams are [2–3] 94–97
refractories at high temperatures. This in­ available for the practical approach briefly [4] Morgan, P.E.D.; Koutsoutis, M.S.: Phase studies
cludes also their stability in contact with described in this paper. However, they concerning sintering in aluminas doped with
other materials e.g. slags or reactions be­ should not simply replace the basic under­ Ti4+. Amer. Chem. Soc. 68 (1985) [6] C156–
tween different layers in a lining, which has standing of the work with phase diagrams. C158
been briefly discussed for a tundish lining Without any plausibility check, the results of [5] Poirier, J.; et al..: Andalusite: An attractive raw
in this paper. such modern tools can be misleading. material for its excellent thermal shock resist­
Each refractory engineer and metallur­ The matrix composition of refractories is ance. refractories WORLDFORUM 1 (2009) [1]
gist should be able to do work with phase often defining the thermomechanical be­ 93–102
diagrams. The use of modern computer pro­ haviour, because the matrix contains all the [6] www.factsage.com

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