Refractory Materials: Industrial Standards, Classification and

Properties
Holger Wirsing
Program

1.Introduction and Definition

2.Classification Features of Refractories
3.Binary Phase System Al2O3-SiO2
4.Basic Materials Systems
5.Lightweight- and Insulating Materials
6.Unshaped Products
1 Introduction and Definition
1 Historical Sources

Production of
unburned mud-
bricks (Adobe) for
building
construction in late
neolithic age

Drying of mud-bricks in Bolivia, Source: Wikipedia

1 Technical Development

Antique Melting Furnace, Source: think-ing.de

Empirical Experience

Knowledge of Deposits

Accumulation of Knowlege

Origin of natural sience background

Demand and Possibilites growing with Technical

Progress
 Refractoriness
Refractories were first introduced into metallurgy by
Vannocio Biringuccio in his book „De La Pirotechnia“ in 1540

and by

Georg Agricola in his book „De Re Metallica“ in 1556

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)
Determination of Refractoriness by Seger cones
Refractory Material Consumption with Regard to the
Different Industrial Branches

Iron & Steel Industry 70 %

Cement Industry 7%
Non-Ferrous Metal Industry 5%
Glass Industry 4%
Ceramic Industry 3%
Energy Industry 3%
Chemical Industry 3%
Waste Incineration 3%
Others 2%
Reaction Process in a Precalciner Kiln
Stresses on the Refractory Lining in Rotary Cement Kilns

Successful performance
only is possible, if
combination of properties
fits to all demands
resulting from place of
installation.
 Half Quantitative Description of the Development of
Bricks for Cement Kiln Burning Zones
Fireclay
High alumina

Magnesia
Dolomite

Magnesia-Chromite

Magnesia-Spinel

Magnesia-Zirconia

Magnesia- Magnesia-
Hercynite Galaxite

Magnesia-
Pleonaste

Magnesia-
Forsterite

1900 1950 2000 2010

2 Classification Features of Refractories
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
DivisionHardening

Ceramic bonding Hardening by burning process

Hydraulic bonding Hardening by hydraulic setting

at room temperature
Chemical bonding Hardening by chemical reaction at
room temperature or at other temperature
lower than for ceramic bonding
Organic bonding Hardening or bonding at room temperature
or slightly increased temperatures
Bonding Types for refractories

Class of Bond Bonding Agent

Ceramic bonding Eutectic Melts, Sintering

Hydraulic bonding High Alumina Cement,
Calcium Aluminates
Chemical bonding Phosphates, Sulphates,
Chlorides, Chromates
Organic bonding Resin, Tar, Pitch,
Dextrin, linseed oil
Quantitative Distribution of Chemical Elements in the Earth Crust

Sortation by geological mechanisms

leading to technically suitable
deposits, f.e.:
•SiO2-Al2O3
•MgCO3
•(Mg, Ca)CO3
•2(Mg, Fe)SiO2

Distribution of Elements, Source: Wikipedia

3 Binary Phase System Al2O3-SiO2
Binary Phase 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
Acidic 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
Classification of fireclay bricks according to Al2O3 content
(according Routschka, G. (ed.), Pocket Manual Refractory Materials, Vulkan Verlag, 3rd Ed. (2008))

% Al2O3 Designation according to

DIN EN 12475-1 Iron and Steel Material Sheet 917
40 ≤ Al2O3 < 45 FC 40 A 40
35 ≤ Al2O3 < 40 FC 35 A 35
30 ≤ Al2O3 < 35 FC 30 A 30
10 ≤ Al2O3 < 30 LF10 A 25
(SiO2´< 85 %)
85 ≤ SiO2 < 93 SS 85 (siliceous fireclay bricks)

FC = fireclay
LF = low alumina fireclay
SS = siliceous = siliceous fireclay
Fireclay Bricks
Fireclay Brick
main components

Refractory Clay
fresh an plastically
+ Fireclay
burned an crushed Refractory Clay

%? %?
Classification of Fireclay Bricks Manufacturing process
A 40 > 40 % Al2O3 12 - 16 % water ⇒ p (= plastic) ⇒high clay
A 35 30 - 40 % Al2O3 4 - 6 % water ⇒ h (= half dry) ⇒medium clay
A 30 30 - 35 % Al2O3 3 - 5 % water ⇒ t (= dry) ⇒low clay
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.
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
characterised 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 to alkali attack.

• A high amount of glassy phase limits the temperature during service to values of
max. 1200°C in the kiln. ⇒ Transition to High Alumina Materials
Classification of Dense Moulded Refractory Products
According to ISO 1109, Modified by Refratechnik Cement

Product Group Proportion of General Comments and

Major Component(s) Characteristics
High-Alumina
Refractories Al2O3 > 56 % A complete description of
Group 1 these products must
indicate either the raw
High-Alumina
materials used or define
Refractories 45 % < Al2O3 < 56 %
the mineralogical
Group 2
structure of the finished
High-Alumina product with an
Refractories with Al2O3 > 45 % indication of how the
special additions SiC > 3 % latter was obtained.
like SiC
High Alumina Bricks High Alumina Brick
main components

Refractory Clay
low contents
+ Natural Rocks with high Tf / synthetic
materials / mixtures

Natural Raw materials

Sillimanite
Kyanite Al2O3 · SiO2 ≈ 60 % Al2O3
Andalusite
Bauxite Al2O3 · H2O 80 - 90 % Al2O3 Melting temperature of
Al2O3-containing products
Synthetic Raw materials increases with increasing
Sintered mullite 3 Al2O3 · 2SiO2 ≈ 72 % Al2O3 Al2O3-content up to 2050 °C
Fused mullite 2 Al2O3 · SiO2 ≈ 80 % Al2O3 (phase diagram SiO2-Al2O3)
Calcined alumina up to 99 % Al2O3
Corundum 95 - 97 % Al2O3
Fused corundum 95 - 99 % Al2O3
Tabular alumina > 99 % Al2O3
Classification of Dense Moulded Refractory Products According to ISO 1109

Product Group Major Component(s) General Comments and Characteristics

Special Products on the basis of
- Carbon
- Graphite
- Zirconium silicate
- Zirconium dioxide
- 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
Correlation of Product Properties and Composition

System extensions: SiC, Zircon

(for improvement of alkali resistance)
Clinker Forming Reactions

Smooth Conditions Burning and Transition Zones

(calcination) (clinker phase formation)

• 1200 °C to 1300 °C • 1300 °C to 1450 °C

• Free from liquid phases or... • Reactions between raw meal
components become intesified
• ... chemical reactions are
avoided by low reaction • CaO containing agressive melts will
surfaces and rates be formed (clinker melt), impact on
refractory lining

Fireclay together with High Alumina Demand for higher resistance

bricks are fitting to demands very against basic melts...
well
... use of basic refractory materials
4 Basic Materials Systems
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 Magnesia as principal
MgO > 80 %
constituent
- Magnesite- 55 % < MgO < 80 % Products with Magnesia and Chromite
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 CaO, MgO Products with Dolomite as principal
constituent
Classification of Basic Refractory Bricks According to Stahl-Eisen-
Werkstoffblatt 913 (Basic Bricks), modified by Refratechnik Cement
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
Magnesia-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/ Pleonaste H/ P 80-90
Magnesia-Forsterite MF 90
Magnesia-Zirconia MZ 95-90-85
Lime CA (CaO > 70)
Magnesium Oxide
There are no natural deposits of MgO on the earth because
MgO + CO2 (atmosphere) ⇒ MgCO3
MgO + H2O (atmosphere) ⇒ Mg(OH)2

Therefore:
Magnesia-spinel brick
Magnesia-chromite brick
Magnesia http://www.magspecialties.com/students.htm

Properties of periclase:
- Melting temperature: ~ 2800 °C
- Thermal conductivity at 1000 °C 3 - 4 W/mK
- Thermal expansion at 1000 °C ~ 1.4 %
- Resistance against basic melts very high

Depending on the chemical composition, next to periclase various silicates and ferritic
compounds can form.
Important Refractory Products for the Cement Industry

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 Magnesia : Sea Water Magnesia

Magnesia from Salt Brines

Main mineral of magnesia bricks is periclase (MgO).

Binary Phase System MgO - Al2O3

Not completed
projection of
magnesia-spinel brick
within this diagramm!
Use of Fused Spinel in the Magnesia Spinel Brick TOPMAG® AF

Magnesia
Sinter

Fused
Spinel
Binary Phase System MgO - Al2O3
Mineral Phases in Magnesia Bricks

Mineral Formula Abbr. Fusion Temperature

Periclase MgO M 2800 °C
Forsterite 2 MgO·SiO2 M2S 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
Secondary Phases in Magnesia Bricks

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

CaO/SiO2 Silicates Ferrites

< 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
Fe2O3 secondary MgFe2O4 + CO structural Fe2O3-content in
Brick components of
component ⇒ 3(Mg, Fe)O + CO2 destruction; the brick as low basic magnesia-spinel
spallings as possible
2(Mg, Fe)O + CO bricks, their most
⇒ MgO + Fe + CO2
Fe2O3
important reactions with
2CO CO2+C the kiln feed and volatile
Mn2O3 secondary Mn2O3 + CO structural Mn2O3-content
component ⇒2MnO + CO2 destruction; in the brick as components from the
spallings low as possible kiln atmosphere and the
CaO/SiO2- secondary I. C/S >> 1.87 decrease of resulting demands on
ratio component CaOfree + MgAl2O4 refractoriness;
(C/S-ratio) ⇒ calcium aluminates
abrasion; the bricks.
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)
Strength Loss of Basic Bricks due to Redox Loads
Binary Phase System MgO - CaO

All minerals phases from

that system are showing
high fusing temperatures.
Coupled to this system is
the danger of high
hydration rates even under
smooth climatic conditions.
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 high alumina bricks like
KRONEX® 87, KRONEX® 85, KRONEX® 70, KRONEX® 60, KRONEX® 50,
REFRALUSIT ® 63, REFRALUSIT® 61, KRONAL® 50 AR, KRONAL® 63 AR,
KRONAL® 60 AR
CX-R-mortar for all fireclay bricks like
KRONEX® 40, KRONEX® 30, KRONEX® 20
OX-R-mortar for all insulating bricks like REFRATHERM® 150
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
Insulating Bricks According to DIN EN 1094 (ISO 2245)

Insulating refractory bricks are shaped products with a porosity of at least 45 %.

Classification corresponds to shaped 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.
These products are installed as an insulating back-up lining, because 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.
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
6 Unshaped Refractories
Refractory Concretes

General Classification Features: Additional Features for Concretes:

Type of bonding system
Installation method
- hydraulically (with HA-cement)
- ramming
- chemically (with phosphates)
- self casting (self-flowing)
- ceramically (by sintering)
- vibrating
- organically (with resins)
- dry gunning
- wet gunning (JETCAST®)
Type of raw material
- fireclay (system Al2O3-SiO2) Water content at delivery
- high alumina (Al2O3) - dry
- basic (with MgO) - semi dry
- special material - wet (plastic)
Classification of refractory products

refractory products

SiC
doloma magnesia corundum bauxite mullite andalusite fireclay silica zircon light weight

brick monolithic

ceramic organic hydraulic chemical

RC: >2.5 % CaO MC: >2.5 % CaO LC: 2.5-1 % CaO ULC: 1-0.2 % CaO NC: <0.2 % CaO
regular cement medium cement low cement ultra low cement no cement

deflocculated

mortar plastic ramming pre-cast castable gunning

brickwork self-cast vibration dry gunning wet gunning

dense product insulating product

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