Under the Auspices of the

Arab Union for Cement and Building Materials (AUCBM)

G&W Training Course Series on

Scientific and Industrial Aspects of the Cement Industry

Course II: Refractories in the Portland Cement Industry

June, 9-14, 2007, Cairo, Egypt

Technical Cooperation

NCC - Egypt Refratech - Germany

Part 1
Prof. Dr. Mohamed A. Serry
Refractories Department, National Research Center,
12311-Dokki, Cairo, Egypt
 7. Refractory Materials (III):
Composition and Properties of Shaped
and Unshaped Types
The following tables and figures exhibit the
chemical and phase composition as well as
microstructure and technological properties of
varieties of Egyptian and international grades of
shaped and unshaped refractory products, which
are usually used for lining the different industrial
furnaces:
 7.1 Composition and Properties of Shaped
Refractories:

7.1.1 Alumino-silicate bricks:

These include siliceous fireclay, fireclay, aluminous fireclay and

high alumina types according to the following diagram:
 Figure 1: Ranges of composition, properties and service temperatures of
different grades of the alumino-silicate refractories on the Al2O3-SiO2 system
 Table 1: Chemical composition of some German fireclay bricks

Typical material
Al2O3 % SiO2 % Fe2O3 %
grades
A 40 t 40-45 50-55 1-2

A 35 t 35-40 55-60 1.5-2.5

A 30 t 30-35 59-64 1.7-3.0

A 25 t 20-30 64-75 1.6-3.0

 Table 2: Physico-mechanical properties of the German fireclay bricks

Typical material Bulk density Apparent porosity Cold crushing

grades g/cm3 Vol % strength N/mm2

A 40 t 2.20-2.30 15-18 40-70

A 35 t 2.10-2.22 16-19 30.50
A 30 t 2.05-2.20 15-19 30-50
A 25 t 2.05-2.17 1-18 35-90
Table 3: Thermal and refractory properties of the German fireclay bricks

Typical Refracto- RUL Thermal TC at TSR

material riness oC T05 oC expansion 1,000 water
grades 1,000 oC oC quenching
% W/mK
A 40 t 1,740-1,760 1,380-1,450 0.60 1.4 20-25

A 35 t 1,730 1,360 0.55 1.4 15-20

A 30 t 1,680 1,340 0.55 1.4 15-20

A 25 t 1,580 1,260 0.50 1.4 5-15

 Table 4: Technological properties of some high-alumina bricks

Bulk Apparen CCS RUL RUL ta oC Therm. TC TSR

density t N/mm2 T05 oC expan. at1,000
g/cm3 porosity 1,000 oC

Vol % oC % W/mK
Standard Grades

pure fused corundum brick 3.14 20 60 <1,700 <1,740 0.8 3.3 15

sintered corundum brick 3.0-3.2 13-17 100-180 <1,700 <1,740 0.8 2.5-3.3 20-25

Bauxite bricks 2.8 20 80 1,480 1,580 0.7 1.8 <30

fused mullite brick 2.6 16 80 <1,700 0.6 1.75 <30

sintered mullite brick 2.55 16 100 1,650 <1,740 15

andaluiste and sillimanite 2.5-2.6 15-16 70-80 1,590 1,680 0.55 1.75 <25
bricks
bricks containing corundum 2.4-2.55 17-18 60-80 1,420-1,500 1,500-1,650 0.5 1.6-1.9 20

Bricks out of mullitized raw 2.3-2.4 13-19 60-100 <1,400 <1,500 0.5 1.7-1.9 25
materials
 Table 5: Chemical and phase composition of some Egyptian (ACR) shaped
alumino-silicate bricks

Types of Bricks (Al2O3%) Chemical Composition, (W/O)

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O
Fireclay (40-45%) 49.68 44.88 1.78 2.50 0.55 0.14 0.22 0.13
Aluminous fireclay
31.80 63.24 1.70 2.00 0.94 0.31 0.25 0.15
(60-65%)
High Al2O3 (75-80%) 14.37 76.50 1.98 3.22 0.56 0.22 0.26 0.16

Types of Bricks (Al2O3%) Phase Composition, (W/O)

Quartz Cristobalite Mullite Corundum Glassy
phase
Fireclay (40-45%) 3.5 19.0 37.5 - 30.0
Aluminous fireclay 0.0 1.50 34.0 36.0 28.5
(60-65%)
High Al2O3 (75-80%) 0.0 0.0 22.5 61.0 16.5
 Table 6 : Technological properties of the Egyptian (ACR) shaped alumino-silicate bricks

Types of Technological properties

Bricks
(Al2O3%) Bulk Apparent Cold Thermal Thermal Permanent
Refractorin
density, porosity, crushing expan at shock Linear
ess under
(g/cm3) (%) strength, 1500ºC, resistance Change,
load, (ºC)
(kg/cm2) (%) No. of (%)
Ta Te
Cycles
Fireclay
(40-45) 2.24 18.20 450 0.70 >50 -0.20 1440 >1600

Aluminou
s fireclay
(60-65) 2.49 18.50 560 0.95 >50 0.60 1470 >1600

High
Al2O3 2.65 19.10 780 1.70 >50 0.80 1520 >1600
(75-80)
Figure 2: RUL curves of the Egyptian fireclay (FC), aluminous-fireclay (AFC) and
high-alumina (HA) bricks
Figure 3: TLM-Microstructure of the Egyptian fireclay (a,b), aluminous-
fireclay (c,d) and high-alumina (e,f) bricks
7.1.2 Shaped basic refractories:
These include periclase, magnesite and its derivatives (magnesia
dolomite, -spinel, -chrome, -hercynite and -zirconia) as well as
dolomite and lime refractories according to the following diagram:

Figure 4: Ranges of composition of the MgO-CaO basic bricks

Table 7: Technological properties of Egyptian dense lime and dolomite briquettes doped with
La2O3

Measured value
Property Lime Dolomite
(1.0 mole %) (0.5 mole %)
Bulk density, (g/cm3) 3.14 3.33
Relative density (%) ≈ 93 ≈96
Apparent porosity, (%) 0.43 0.41
Linear shrinkage (%) 25.8 25.5
Crushing strength (N/mm2) 930 790
Refractoriness under load:
>1500 >1500
Ta (ºC)
Ca(OH)2 formed after 24h,
38 3.2
steam curing (%)
Figure 5: Rate of hydration of Egyptian fired lime and zircon-bearing lime
briquettes
Fig. 6: RLM Microstructure of the fired lime refractory grains
(a) undoped and (b) doped with 1.0% zircon.
Fig 7: RLM- Microstructure of the fired dolomite refractory grains
a) undoped and (b) doped with 1.0% zircon.
Figure 8: RLM- Microstructure of the fired MgO- dolomite refractory grains
(a) undoped and (b) doped with 1.0% zircon.
 Table 8: Calculated phase equilibrium data of Egyptian MgO-dolomite
refractories

Phase Composition in the Solid Liquid Phase Contents Solid and Liquid
State (w/o) (w/o) Phases Coexisting
Mix. at
No. 1555°C (w/o)
Liquid
MgO CaO C3S C4AF 1295°C 1400°C 1500°C 1550°C MgO CaO
Phase
I 39.80 55.10 3.04 2.06 2.99 4.35 4.74 5.64 39.39 54.97 5.64

II 50.12 42.48 3.72 3.68 5.42 7.18 7.99 8.50 49.35 42.15 8.50

III 60.36 30.06 4.36 5.22 7.57 10.44 11.19 11.83 59.21 28.96 11.83

IV 70.40 17.42 4.98 7.20 10.43 13.87 14.78 15.59 68.83 15.58 15.59

V 80.32 4.93 5.62 9.13 13.23 17.55 18.69 19.63 78.27 2.10 19.63
 Table 9: Technological properties of the Egyptian MgO-dolomite refractories

Refractoriness under load Free Lime Content (w/o) Hydration

Linear Bulk Resistanc
Mix.
shrinkage density e Loss in
No. Beginning of Subsidence
(%) (g/cm3) Calculated Determined Weight
subsidence (°C) 1h at 1500°C
(%)
I 2.26 2.97 1400 2.7 55.10 54.65 9.47
II 5.81 3.04 1400 4.0 42.48 41.70 8.56
III 6.77 3.23 1400 3.8 30.06 29.04 6.82

IV 6.45 3.18 1450 2.5 17.42 16.20 4.20

V 6.13 3.14 1500 1.0 4.93 3.78 3.02

 Table 10: Chemical composition and technological properties of varieties of
German magnesia –spinel, -hercynite, -zirconia and -zircon bricks
Brick grade MgO % Al2O3 Fe2O3 CaO SiO2 ZrO2
magnesia–spinel bricks
90-94 3-7 0.3-0.8 0.8-2 0.3-1
<7% Al2O3, <1% Fe2O3
<7% Al2O3, >1% Fe2O3 65-90 3-6 3-4 2-16 1-9
>7% Al2O3, <1% Fe2O3 82-87 9-18 0.2-0.6 0.8-2 0.3-0.8
>7% Al2O3, >1% Fe2O3 82-89 14-18 1-4 0.6-1 0.3-1.2
spinel bricks 28-33 64-70 0.1-2 0.5-0.8 0.2-1.5
magnesia –zirconia bricks 76-95 < 0.2 <1 1-6 < 0.5 1.5-15
magnesia–zircon bricks 75-78 0.1-0.5 0.1-0.5 1-2 8-10 13-14

Brick grade bulk apparent KDF1 KBF2 E-modules DE3 thermal WLF4 TWB5
density porosity, N/mm2 N/mm2 kN/mm2 T0.5 expansion 1,000°C Air
(g/cm3) (Vol. %) °C 1,000°C W/mK quenching
%
magnesia– 2.9-3.05 16-20 30-60 3-6 12-70 1500-1700 1-1.2 2.5-3 100-150
spinel
bricks
(all grades)
spinel 2.85-3.0 18-21 20-100 6 1500-1700 0.8-1.0 2.5-2.9 25
bricks
magnesia – 2.9-3.19 14-18 45-67 6-7 40-60 > 1700 1.14-1.4 3-4.2 100-200
zirconia
bricks
magnesia– 3.0-3.12 13-18 40-100 8-10 1600-1650 1.07-1.22 (2.7) > 30
zircon
bricks
1= cold crushing strength, 2= cold modulus of rupture, 3= refractoriness under load (differential), 4= thermal
conductivity, 5= thermal shock.
 Table 11: Refractory properties of Egyptian MgAl2O4-spinel refractories

Batch
RUL*(°C)
Type PLC** at 1700°C(%) TSR***No. of cycles
To Ta T
S1 1500 1650 >1700 0.00 >50
CMS 1500 1630 >1700 -0.55 >50
CAS 1500 1620 >1700 -0.65 >50
7.2 Composition and Properties of Unshaped Alumino-
Silicate Castables:
7.2.1 Conventional alumino-silicate castables:
Conventional alumino-silicate castables with alumina contents ranging between
40 and 95 % are produced and used allover the world since mid of the 20th
century till now. They are processed by mixing well-graded volume-stable
calcined fireclay, sillimanite, bauxite and sintered alumina aggregate and high
alumina cement (HAC) with suitable alumina content.

The content of the HAC hydraulic bond is usually ranging between 10 and 30
weight %. Such high level of refractory cement requires high amount of water
to pour these castables. Hence, a controlled pre-heating schedule should be
designed and applied after their casting in order to minimize their drying
defects.
The following tables and figures illustrate the different grades
of the HAC (aluminous cement (AC)) and the hydration
reactions of their phases. Also illustrated are the effect of
composition and water content as well as curing time and
temperature on the technological properties of the conventional
alumino-silicate castables.
Table 12: Chemical composition of the different grades of the refractory
calcium aluminate cement (HAC or AC)
Groups 1 2 3 4
SiO2 17-26 4-9 4-6 0.1-1.4
Al2O3 5-12 35-45 50-65 68-85
Fe2O3 1.7-2.7 10-16 1-2 0.1-1.0
CaO 53-65 38-39 29-40 17-25
Figure 9: The hydration reactions of the HAC phases as a function of temperature
Figure 10: Hydration-dehydration diagram of a highly pure calcium-aluminate-
cement-based alumina castables
Figure 11: Effect of water ratio on aggregate grain packing and
workability of the castables.
Figure 12: Effect of water ratio on the physical and mechanical properties of
the castables.
Figure 13: Effect of curing time and temperature on strength development of
conventional castables.
Figure 14: An example of a rate of dehydration of a conventional castable during
its pre-heating
Figure 15: Reversible linear expansion and permanent linear change of a
preheated conventional castable
Figure 16: Cold and hot modulus of rupture (MOR) of a conventional castable
 Table 13: Chemical composition and technological properties of varieties of
high-alumina and fireclay conventional castables
Material Alumina High alumina High alumina Fireclay
Test item (# 40) (# 40) (KL MIX) (# 27)

Chemical Al2O3 95 70 56 40
Compositions (%) SiO2 - 22 36 50
Weight to place (T/m3) 2.60~2.70 2.35~2.45 2.10~2.20 1.85~1.95
Modulus of 110ºC 85 60 65 50
rupture 1000ºC 70 45 40 25
(Kg/cm2) 1300ºC 60 40 50 45
1500ºC 110 90 120 -
Permanent 110ºC -0.1 -0.1 -0.1 -0.1
linear 1000ºC -0.2 -0.2 -0.3 -0.3
change (%) 1300ºC -0.3 -0.3 -0.4 -0.6
1500ºC -0.2 -0.6 +1.0 -
Coefficient of thermal
8.5 7.0 6.0 6.0
expansion (x10-4/C)
Thermal conductivity
1.08 0.64 0.59 0.78
(500ºC, kcal/m. h. ºC)
 Table 14: Chemical composition and technological properties of varieties of
high-alumina and fireclay plastic castables

Material High alumina High alumina Fireclay

Test item (PR90AB) (PBALXAB) (PB FAB)
Chemical Al2O3 87 72 43
Compositions (%) SiO2 10 19 47
Weight to place (T/m3) 2.90~3.10 2.70~2.80 2.30~2.40
Modulus of 110ºC 60 30 25
rupture 1000ºC 60 35 30
(Kg/cm2) 1300ºC 10 60 45
1500ºC 100 55 50
Permanent 110ºC -1.2 -1.2 -1.2
linear 1000ºC -1.1 -1.3 -1.3
change 1300ºC -1.0 -1.4 -1.3
(%) 1500ºC -0.3 -0.4 -0.3
Coefficient of thermal
8.0 7.1 5.7
expansion (x10-4/C)
Thermal conductivity
1.10 0.64 0.64
(500ºC, kcal/m. h. ºC)
 Table 15: Chemical composition and technological properties of varieties
of high-alumina and fireclay developed vibratable castables

Material High Fireclay based High

Alumina Fireclay -
alumina alumina-
based SiC based
based (MIX 726) (MIX 740) SiC based
(MIX 724) (MIX 797)
Test item (MIX 725) (MIX 760)
Chemical Al2O3 92 82 48 40 68 38
Compositions (%) SiO2 6 10 47 55 SiC 20 SiC 17
Weight to place (T/m3) 3.05~3.15 2.85~2.95 2.45~2.55 2.30~2.40 2.70~2.80 2.40~2.50
Modulus of 110ºC 150 140 130 85 50 70
rupture 1000ºC 200 140 130 100 35 60
(Kg/cm2) 1300ºC 340 180 190 130 50 90
1500ºC 380 160 160 - 60 150
Permanent 110ºC -0.1 -0.1 -0.1 -0.1 -0.1 -0.1
linear 1000ºC -0.2 -0.1 -0.2 -0.2 -0.1 -0.2
change (%) 1300ºC -0.2 -0.1 -0.2 -0.5 -0.1 +0.1
1500ºC -0.5 +0.5 +0.4 - +0.1 +0.4
Coefficient of thermal
9.6 7.9 5.5 5.9 - -
expansion (x10-4/C)
7.2.1 Developed alumino-silicate castables:

As shown in the following table, development of the conventional (CC) castables

into the LCC, ULCC and NCC types includes minimizing HAC content to 0.0-5.0%
due to the addition of ultra-fine silica and/or alumina powders as well as
admixtures. This leads to minimize water of consistency, drying defects with
significant improvement of the thermo-mechanical properties.

The following characteristics should be tested and discussed:

¾ Hydraulic properties, i.e. Water of consistency, initial and final setting
times as well as CCS of the cementing materials.
¾ Cold and hot CCS & MOR and RUL of the hydrated castables.
¾ Phase composition and microstructure of the hydrated and fired
castables.
 Table 16: Development of High-Alumina Castables

Components of
No. Type of Castables % WOC Type of Aggregate
Binding Matrix
10-30% HAC,
1. Conventional Castables (CC) 10 - 20 Calcined Bauxite
Admixtures.
4-6% HAC,
Calcined Bauxite,
Ultra-fine Alumina,
Low-Cement Castables (LCC) and/or Tabular,
2. 4–6 Mullite, Spinel
Vbrational or self-flowing and/or Electro-
and/or SiC &
Fused Alumina
Admixtures.
1-4% HAC,
Calcined Bauxite,
Ultra-Low Cement Castables Ultra-fine Alumina,
and/or Tabular,
3. (ULCC) Vbrational or self- 4-6 Mullite, Spinel
and/or Electro-
flowing and/or SiC &
Fused Alumina
Admixtures.
0.0% HAC,
Calcined Bauxite, Ultra-fine fumed
No-Cement Castables (NCC)
and/or Tabular, silica and Alumina
4. Vbrational or 4-6
and/or Electro- Mullite, Spinel
self-flowing
Fused Alumina and/or SiC &
Admixtures.
Figure 17: Cold crushing strength of hydrated traditional (RC), medium-and low-
(LCC) cement content castables as a function of firing temperature
Figure 18: SEM-microstructure of fractured surfaces of hydrated A-50 –CC and –
LCC (A&B) as well as A-80 –CC and –LCC (C&D) castables
Figure 19: Cold crushing strength of the hydrated A-50 –CC and –LCC (A&B) as
well as A-80 –CC and –LCC (C&D) castables
Figure 20: Hot modulus of rupture of the hydrated A-50 –CC and –LCC (A&B) as
well as A-80 –CC and –LCC (C&D) castables
Figure 21: Refractoriness under load curves of the hydrated A-50 –CC and –LCC
(A&B) as well as A-80 –CC and –LCC (C&D) castables
Thank you for your attention