Basic Knowledge about Refractories

Titan Cement Egypt – Alexandria Portland Cement Co.

Alexandria, November 12, 2012
Lars Vieten, Refratechnik Cement GmbH
Contents

1. Introduction
2. Classification features for refractories
3. Classification by the bonding types of refractories
4. Classification by the main mineral phases of refractories
5. The system SiO2-Al2O3
6. Basic refractory materials
7. Special products, mortars and insulating materials
8. Classification of unshaped refractories
1. Introduction – Refractoriness

Refractory products are non-metallic ceramic materials (incl. some that

contain a share of metals).

A product is called „REFRACTORY“,

if the Seger cone is > 18 (1520 °C)

A product is called „HIGHLY REFRACTORY“,

if the Seger cone is > 37 (1830 °C)

Seger cone ~ pyrometic cone equivalent

Determination of refractoriness by Seger cones
Global Refractory Consumption

2% 3% Iron and Steel 68 %

3% Lime 2 %
3% Cement 7 %
3%
Non Ferrous 4 %
3% Glass 3 %
Ceramic 3 %
4%
Energy 3 %
Chemistry 3 %
Incineration 3 %
7%
Others 2 %

2%

68%
Reaction process in a precalciner kiln
Stresses on the Refractory Lining in Rotary Cement Kilns
Half quantitative description of the development
of bricks for cement kilns
2. Classification features of refractories

- Chemical/ main constituent

Mineralogical

- Porosity dense refractories (< 45 % porosity)

insulating refractories (> 45 % porosity)

- Manufacturing shaped materials (bricks)

unshaped materials (castables, concretes)

- Kind of bonding ceramic - chemical - hydraulic - organic

- Industrial use cement, steel, glass, metals, ceramics,

chemical, waste burning, other uses
3. Classification by the bonding types of refractories

Type of bonding process bonding agent

Ceramic bonding hardening by burning process eutectic melts, sintering

Hydraulic bonding hardening by hydraulic setting high alumina cement

at room temperature calcium aluminates

Chemical bonding hardening by chemical reaction phosphates, sulphates,

at room temperature or at other chlorides, chromates
temperature lower than for
ceramic bonding

Organic bonding Hardening or bonding resin, tar, pitch,

at room temperature dextrin, linseed oil
4. Classification by the main mineral phases of refractories

refractories

basic materials materials of the SiO2-Al2O3-system special products

fireclay bricks andalusite bricks bauxite bricks

If the main component of the raw material is known,

most properties can be concluded.
5. The system SiO2 - Al2O3
Classification of dense shaped refractory products
– according to ISO 1109

Product group share of comment

main component(s)

Fireclay 30 % < Al2O3 < 45 % A complete

description of these
Acid fireclay bricks 10 % < Al2O3 < 30 % products must
SiO2 < 85 % indicate either the
raw materials used,
Dinas clay 85 % < SiO2 < 93 % or define the
mineralogical
Silicate bricks SiO2 > 93 % structure of the
finished product
Fireclay Bricks

Fireclay Bricks contain 30 - 45 % Al2O3, acidic fireclay bricks contain 10 - 30 % Al2O3.

Raw material for fireclay bricks is fired refractory clay. the chemical composition is
characterized by the formula Al2O3 • 2SiO2 (kaolinite).
Fireclay bricks generally show a good thermal shock resistance. Dense Grades show
a high abrasion resistance. Acidic fireclay bricks are resistant against alkali attack. A
high amount of glassy phase limits the temperature during service to values of max.
1200 °C in the kiln.
Classification of Fireclay Bricks Manufacturing process
A 40 > 40 % Al2O3 12 - 16 % water ⇒ p (= plastic)
A 35 30 - 40 % Al2O3 4 - 6 % water ⇒ h (= half dry)
A 30 30 - 35 % Al2O3 3 - 5 % water ⇒ t (= dry)
A 25 < 30 % Al2O3
A 30 T ⇒ dry pressed Fireclay brick (3 - 5 % water is used during
manufacturing, Al2O3-content is 30 - 35 %)
 Property values of mechanically pressed and burnt
fireclay bricks for general industrial uses (brick group A up to 45 % Al2O3)

Grade Al2O33) Fe2O34) Bulk density Parts of open pores Crushing strength at room Refractoriness under
temperature load
Mean Standard Mean Standard Mean Standard Value Mean Standard
µ deviation µ deviation µ deviation µ deviation
δ δ δ5) δ
g/cm³ % N/mm² ta °C
% % min. max. min. min. min.
A 40 t 2,15 0,05 20 30 15 20 1450
A 40 h > 40 < 2,5 2,10 0,05 21 2 25 15 15 1420 40
A 40 p 1,90 0,06 26 15 10 10 1380
A 35 t 2,10 0,05 19 30 15 20 1400
A 35 h 35–40 < 2,5 2,05 0,05 20 2 25 15 15 1380 40
A 35 p 1,90 0,06 25 15 10 10 1350
A 30 t 2,05 0,05 19 30 15 20 1370
A 30 h 30-35 < 3,0 2,05 0,05 20 2 25 15 15 1350 40
A 30 p 1,90 0,06 24 15 10 10 1320
A 25 t 2,05 0,05 18 35 15 25 1340
A 25 h < 30 < 3,0 2,05 0,05 19 2 30 15 20 1320 40
A 25 p 1,90 0,06 22 20 10 15 1300
2)
Regarding manual made bricks, special agreements are necessary.
3)
The content of Al2O3 only serves the classification but it is not a quality characteristic.
4)
The values are valid for 95 % of the determined values in the single lot or for (n-1)-single values, referring to the single lot (n is the quantity of
samples, referring to the single lot).
5)
With increasing value of the mean value the standard deviation increases as well.
Classification of dense moulded refractory products
– according to ISO 1109

Product Group Proportion of General Comments and

Major Component(s) Characteristics
High-Alumina A complete description of
Refractories Al2O3 > 56 % these products must
Group 1 indicate either the raw
materials used, or define
High-Alumina the mineralogical
Refractories 45 % < Al2O3 < 56 % structure of the finished
Group 2 product with an
indication of how the
latter was obtained.
High alumina bricks

High alumina bricks of Group 1 containing > 56 % Al2O3

High alumina bricks of Group 2 containing 45 - < 56 % Al2O3
High alumina bricks show a good thermal shock resistance and a high abrasion resistance.
Raw materials for high-alumina bricks
Natural raw materials
Sillimanite
Kyanite Al2O3 • SiO2 ≈ 60 % Al2O3 Melting temperature
Andalusite of Al2O3-containing
Bauxite Al2O3 • H2O 80 - 90 % Al2O3 products increases
with increasing
Synthetic Raw materials Al2O3-content up to
2050 °C (phase
Sintered mullite 3 Al2O3 • 2SiO2 ≈ 72 % Al2O3
diagram SiO2-Al2O3)
Fused mullite 2 Al2O3 • SiO2 ≈ 80 % Al2O3
Calcined alumina up to 99 % Al2O3
Corundum 95 - 97 % Al2O3
Fused corundum 95 - 99 % Al2O3
Tabular alumina > 99 % Al2O3
System SiO2 - Al2O3

KRONEX® -
REFRALUSITE® -
series

+SiC:
KRONAL® 50 AR
KRONAL® 60 AR
KRONAL® 63 AR
6. Basic refractory materials REFRATECHNIK

fireclay and basic fireclay and

high alumina materials high alumina
materials materials

The cement burning process

Classification of dense moulded refractory products
– according to ISO 1109

Product Proportion of General Comments and

Group Major Component(s) Characteristics
Basic In view of the latest as well as possible
Refractories future developments, new classification
characteristics may become necessary.
- Magnesite Products with Magnesite as principal
MgO > 80 %
constituent
- Magnesite- Products with Magnesite and Chromite
55 % < MgO < 80 %
Chrome as principal constituents
- Chromite Cr2O3 > 25 % Products with Chromite as principal
MgO < 25 % constituent
- Forsterite Products with Magnesium Silicate as
MgO, SiO2
principal constituent
- Dolomite Products with Dolomite as principal
CaO, MgO
constituent
Classification of Basic Refractory Bricks
– according to “Stahl-Eisen-Werkstoffblatt 913” (basic bricks),
(modified by Dr. H.-J. Klischat)
Brick grade Abbreviation MgO Groups
Magnesia (Magnesite) M 98-95-90-85
Magnesia-Carbon MG 90-85-80-70-60-50-40-30
Magnesia-Dolomite-Carbon MDG C after coking > 7 %)
Dolomite-Carbon DG
Magnesia-Chromite
Magnesite-Chrome and Chrome MC 80-70-60-50-40-30
Magnesia)
Chromite (Chrome ore) C < 30 (Cr2O3 > 30)
Magnesia-Dolomite MD 80-70-60-50
Dolomite D 40-30
Forsterite F 50-40
Magnesia-Spinel
S 80-70-60
MgO-MgO.Al2O3, MgO-MgO.Cr2O3
Magnesia-Hercynite H 80-90
Magnesia-Pleonaste P 80-90
Magnesia-Zirconia MZ 95-90-85
Lime CA (CaO > 70)
Important basic refractory products for
the cement industry (I)

Bricks with magnesium oxide as main mineral phase

Refractory bricks made from sintered or fused magnesia are characterized by

high hot strength and high resistance against basic slags and cement clinker

Raw material for magnesia bricks:

1. Natural magnesite: coarse crystalline
(MgCO3) fine crystalline

2. Synthetic sea water magnesia

magnesia: magnesia from salt brines

Main mineral of magnesia bricks is periclase (MgO)

Important basic refractory products for
the cement industry (II)
There are no natural deposits of pure MgO on the earth, because
MgO + CO2 (atmosphere) ⇒ MgCO3
MgO + H2O (atmosphere) ⇒ Mg(OH)2

Products for the cement industry:

Magnesia spinel bricks
Magnesia chromite bricks
Magnesia hercynite bricks

Properties of periclase:
- melting temperature: ~ 2800 °C
- thermal conductivity at 1000 °C: 3 - 4 W/mK
- thermal expansion at 1000 °C: ~ 1.4 %

Depending on the chemical composition, beneath periclase various silicates and ferritic
compounds can form
System MgO - Al2O3
Composition of basic refractory bricks

Magnesia + porosity + modifier

elastifier like
grain size distribution / densification spinel, chrome ore,
hercynite, zirconia
Thermal:
operation temperature, thermal shock,
thermal gradients

REFRACTORY
MATERIALS

Chemical: Mechanical:
kiln feed, weight of the lining,
atmosphere, abrasion,
products of chemical cyclic stresses, ovality
reactions, infiltrations
Use of fused spinel in the magnesia spinel brick
grade ALMAG® AF

Sintered
Magnesia

Fused
Spinel
Mineral phases in magnesia bricks (I)

Mineral Formula Abbr. Fusion Temperature

Periclase MgO M 2800 °C
Forsterite 2 MgO•SiO2 M2 S 1890 °C
Monticellite CaO•MgO•SiO2 CMS 1495 °C
Merwinite 3CaO•MgO•2 SiO2 C3MS2 1575 °C
Dicalcium Silicate 2 CaO•SiO2 C2S 2130 °C
Magnesium Ferrite MgO•Fe2O3 MF 1750 °C
Dicalcium ferrite 2 CaO•Fe2O3 C2F 1435 °C
Mineral phases in magnesia bricks (II)

The CaO/SiO2 and CaO/Fe2O3 ratio determines the resultant mineral composition:

CaO/SiO2 Silicate Ferrite

< 0.94 M2S + CMS MF
= 0.94 CMS MF
0.94 – 1.47 CMS + C3MS2 MF
= 1.47 C3MS2 MF
1.47 – 1.87 C3MS2 + C2S MF
= 1.87 C2S MF
> 1.87 C2S(C3S) C2F, MF
oxide brick function corrosion reaction consequence demand
component
MgO brick matrix stable balanced; on
----- component demand as high
as possible
Al2O3 improvement of 12CaO + 7Al2O3 decrease of sufficient for
the thermal shock 12CaO • 7Al2O3 refractoriness; elastification of
resistance spallings the brick; as low
mayenite is formed by
elastifying as possible
a reaction with CaO
component
from the kiln feed due
to overheating Brick components of
Fe2O3 secondary MgFe2O4 + CO structural Fe2O3-content in
component destruction; the brick as low
basic magnesia spinel
3(Mg, Fe)O + CO2
2(Mg, Fe)O + CO
spallings as possible bricks, their most
MgO + Fe + CO2 important reactions with
Fe2O3 the kiln feed and volatile
2CO CO2+C
Mn2O3 secondary Mn2O3 + CO structural Mn2O3-content components from the
component 2MnO + CO2 destruction; in the brick as kiln atmosphere and the
spallings low as possible
CaO/SiO2- secondary I. C/S >> 1.87 decrease of
resulting demands on
ratio component CaOfree + MgAl2O4 refractoriness; the bricks.
(C/S-ratio) abrasion;
calcium aluminates
infiltration
CaOfree+SO3 CaSO4
II. C/S = 1.87 formation of CaO/SiO2 in the
highly brick approx.
refractory 1.7 - 2.2, if
compounds; Σ(C+S) > 1.25
few reactions
III. C/S << 1.87 decrease of
2MgO•SiO2+2CaO•SiO2 refractoriness
2(CaO•MgO•SiO2)
System MgO - CaO
7. Special products, mortars and insulating materials

Product group major component(s) general comments and characteristics

Special Products * / * on the basis of

- carbon
- graphite
- zirconium silicate
- zirconium dioxide (zirconia)
- silicon carbide
- carbides (excluding silica carbide)
- nitrides
- borides
- spinels (excluding chromite)
- several oxides (excluding basic products)
- pure oxides (alumina, silica, dioxides,
magnesia, zirconium)
- extremely pure products
Refractory mortars

AG-R mortar for the grades:

ALMAG®, MAGPURE®, REFRAMAG®, FERROMAG®, TOPMAG®,
MAGNUM®

PX-R-mortar for PERILEX® grades

KX-R-mortar for all fireclay and alumina bricks like:

KRONEX® 87, KRONEX®85, KRONEX® 70, KRONEX® 60, KRONEX® 50,
REFRALUSIT ® 63, KRONAL® 50 AR, KRONAL® 60 AR, KRONAL® 63 AR

CX-R-mortar for all fireclay bricks like:

KRONEX® 40, KRONEX® 30

OX-R-mortar for REFRATHERM® 150

Insulating bricks – according to ISO 2245 (1972)

Insulating refractory bricks are formed products with a porosity of at least 45%.
Classification corresponds to formed dense products.

Insulating bricks are classified into 2 categories:

1. Refractory products with a Seger cone temperature of at least 1500 °C.
In some cases they can be installed as a working lining as well.
2. Refractory Products with a Seger cone temperature of less than 1500 °C.
As these products are installed as an insulating back-up lining, their
mechanical and thermal properties are insufficient for severe working
conditions.

Because of the large pore volume the thermal conductivity is determined by the
thermal conductivity of air.
Bricks with finer pores are preferred, as in larger pores a convection takes place above
temperatures of 500 °C which increases the thermal conductivity.
Classification of lightweight refractory bricks
– according to ASTM C 155 and DIN EN 1094

ASTM C 155 Draft standard DIN – EN 1094 - 2

test temperature at test temperature at which no upper limit of
which no more than 2 % bulk
grou more than 2 % permanent median bulk
group permanent linear change density p linear change may occur density1) of products
may occur after 24 hours less than after 24 hours in group L
°F °C g/cm3 °C g/cm3
75 750 0.40
80 800 0.50
*16 ÷ 875 °C 1550 845 0.54 85 850 0.55
90 900 0.60
95 950 0.65
100 1000 0.65
20 ÷1.000 °C 1950 1070 0.64 105 1050 0.65
110 1100 0.70
115 1150 0.70
23 ÷1.260 °C 2250 1230 0.77 120 1200 0.70
125 1250 0.75
130 1300 0.80
135 1350 0.85
26 ÷1.430 °C 2250 1400 0.87 140 1400 0.90
28 ÷1.540 °C 2750 1510 0.96 150 1500 0.95
30 ÷1.650 °C 2950 1620 1.09 160 1600 1.15
32 ÷1.760 °C 3150 1730 1.52 170 1700 1.35
33 ÷1820 °C 3250 1790 1.52 180 1800 1.60
Ceramic insulating materials

- Heat resisting materials for application temperatures of maximum 800 °C:

mineral wool, foamed concretes, etc.
- Heat resisting materials for application temperatures of maximum 1000 °C:
calcium silicate, kieselgur, vermiculite
- Refractory materials for application temperatures of maximum 1400 °C:
fireclay materials, alumina fibers
- Highly refractory materials for application temperatures of maximum 1700 °C:
mullite materials, alumina fibers, bubble alumina materials
- Highly refractory materials for application temperatures of maximum 2000 °C:
zirconia fibers, non-oxidic materials, carbon
8. Classification of unshaped refractories

Refractory Castables

Type of bonding system: Installation method:

- hydraulically (with HA-cement) - ramming
- chemically (with phosphates) - casting
- organically (with resins) - self casting (self-flowing)
- vibrating
- dry gunning
Type of raw material:
- wet gunning (JETCAST®)
- fireclay (system Al2O3-SiO2)
- basic (with MgO)
Water content at delivery:
- high alumina (Al2O3) - dry
- special material - semi dry
- wet (plastic)
Classification of REFRATECHNIK refractory concretes
for non-gunning installations (vibrating & self-flowing)

insulating castable dense castable

REFRALITE 40

chem. bonded castable hydraulic bonded castable

"REFRALINE"-conception "REFRALINE" AR-conception

without SiC with SiC

deflocculated castable regular-cement castable

without deflocculant system

medium-cement low-cement ultra-low-cement no-cement REFRACORUND 95

castable castable castable castable REFRAMULLITE 70
REFRACLAY 50
vibration-method self-cast-method REFRACLAY 40
REFRACLAY 30
REFRABAUXITE 85 SC X
REFRACORUND 95 LCC REFRACORUND 95 LCC AR X
REFRACLAY 40 SC X
REFRABAUXITE 85 LCC REFRABAUXITE 85 LCC AR
REFRACLAY 40 SC AR X
REFRABAUXITE 85 LCC X REFRABAUXITE 85 LCC AR X
REFRAMULLITE 70 LCC REFRAMULLITE 70 LCC AR
REFRAMULLITE 63 LCC REFRAMULLITE 63 LCC AR
REFRAMULLITE 63 LCC AR X
REFRACLAY 40 LCC REFRACLAY 40 LCC AR
REFRACLAY 40 LCC X REFRACLAY 40 LCC AR X
REFRA-SiC AR
Classification of REFRATECHNIK refractory concretes
for wet- and dry-gunning installations

dense gunning insulating gunning

mix [DG] mix [IG]
REFRALITE 40 G

regular-cement medium-cement low-cement

gunning mix [G] gunning mix [MCG] gunning mix [JC]
dry gunning method dry gunning method wet gunning method
JETCAST-method

REFRACLAY 50 G REFRAMULLITE 63 MCG AR REFRABAUXITE 85 JC AR

REFRACLAY 40 G REFRACLAY 40 MCG AR REFRAMULLITE 63 JC AR
REFRACLAY 30 G REFRA-SiC MCG AR REFRAMULLITE 63 JC
REFRACLAY 40 JC AR
REFRACLAY 40 JC

addition of water: indefinable indefinable definable

15 – 20 % 8 – 12 % 5.5 – 7.5 %
rebound losses: 10 – 15 % 5 – 10 % <5%
dust development: high middle no
apparent porosity: 30 – 35 % 20 – 25 % 15 – 20 %
cold crushing strenght: 15 – 40 N/mm2 40 – 50 N/mm2 50 – 100 N/mm2
max. temperature of application: 1300 – 1400 °C 1400 – 1500 °C 1500 – 1650 °C