C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S

CEMENT TECHNOLOGY CEMENT TECHNOLOGY

Cement Chemistry Cement Chemistry
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Cement Process - Key Trends
Capital Intensive, ~$200/t, 1mtpa, ~$200,000,000
Environmental Pressure (ISO 14001)
Quarry
Dust
Noise
SOx, NOx, CO
2
, VOC
Leachates
~15% of capital is for environmental protection.
Energy intensive
0.1-0.2 tonnes of coal per tonne of cement
100-130 kWhs per tonne of cement
Relatively low price commodity , say $40-100/tonne
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Cement Process
Raw material extraction (or procurement)
Proportioning
Grinding
Blending
Drying - Preheating - Calcining - Sintering
Cooling
Cement Grinding
Cement Storage
Cement Despatch
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Raw Material Source of
Limestone or Chalk, CaCO3 CaO
Shale or Clay Al
2
O
3
.Fe
2
O
3
.SiO
2
Iron Oxide Fe
2
O
3
Bauxite Al
2
O
3
.Fe
2
O
3
Sand SiO
2
Slag
CaO (Al
2
O
3
.Fe
2
O
3
.SiO
2
)
Raw Materials
Figure 3.
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Compound Formula Shorthand Molecular
Weight
Water H
2
O H 18.02
Carbon Dioxide CO
2
C 44.01
Lime (Calcium Oxide) CaO C 56.08
Magnesia MgO M 40.31
Silica SiO
2
S 60.09
Titania TiO
2
T 79.90
Alumina Al
2
O
3
A 101.96
Ferric Oxide Fe
2
O
3
F 159.70
Phosphorus Pentoxide P
2
O
5
P 141.94
Sulphur Trioxide SO
3
S 80.06
Soda Na
2
O N 62.00
Potash K
2
O K 94.20
Calcium Carbonate CaCO
3
CC 100.09
Magnesium Carbonate MgCO
3
MC 84.32
Sodium Carbonate Na
2
CO
3
NC 106.01
Calcium Sulphate CaSO
4
CS 136.14
Potassium Sulphate K
2
SO
4
KS 174.26
Principal Compounds and Shorthand Notation
Figure 2.
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Mineral Shorthand Name Formula Formula Typical Range
Tricalcium Silicate C
3
S Alite 3CaO.SiO
2
Ca
3
SiO
5
60% 30-70%
Dicalcium Silicate C
2
S Belite 2CaO.SiO
2
Ca2SiO4 20% 5-40%
Tricalcium Aluminate C
3
A Aluminate 3CaO.Al
2
O
3
Ca
3
Al
2
O
5
10% 5-15%
Calcium Aluminoferrite C
4
AF Ferrite 4CaO.Al
2
O
3
.Fe
2
O
3
Ca
4
Al
2
Fe
2
O
10
8% 5-15%
Figure 9.
What is cement? - Clinker Minerals
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Limestone Shale
S 3.3
A 0.7
F 0.2
C 53.5
S 52.8
A 14.2
F 8.7
C 1.0
Raw Meal
Raw Mill
Coal
Ash
Kiln
S 13.2
A 3.4
F 1.9
C 43.0
S 51.7
A 26.4
F 9.5
C 1.6
Clinker
S 20.9
A 5.6
F 3.0
C 65.7
Figure 4.
Process Chemistry
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
0
1
2
3
4
5
6
7
8
9
0 2 4 6 8 10 12 14 16
Movement of Material
R
e
l
a
t
i
v
e

W
e
i
g
h
t
700
800
900
1000
1100
1200
1300
1400
1500
0 2 4 6 8 1 0 1 2 1 4
Quartz
CaCO
3
Free Lime
C
2
S
C
3
S
Temperature Deg C
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Principal Cement Properties
Silicates
Aluminate
Ferrite
Alkalis, Total and water soluble
Sulfate, Clinker and Cement
Forms of Sulfate
Fineness, Blaine, Residues, Particle Size Distribution
Surface Properties, Carbonation, Pre-hydration, LOI
Free Lime
Clinker Crystallography, Thermal History
Cement Composition, Slag, Fly Ash, Pozzolan, Limestone
Minor Components, MgO, Cl , F, P2O5
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Silicates
Main Phase Present
Typically 70-80% total silicates
Alite (C3S) and Belite (C2S)
Strength providing phases
Higher LSF means higher C3S
Higher C3S:C2S gives higher early strength at same 28 day strength
Actual v Potential Bogue differences due to Free Lime
Crystallography also important
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Aluminate/Ferrite
Interstitial Phases
Important for clinker formation
C3A content and crystallography strongly influences concrete water demand
C3A:SO3 interaction important
Important in Flash/False Set behaviour
C4AF main cause of colour
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Alkalies
Potassium (K2O) and sodium (Na2O) salts
As sulfates or in solid solution
Alkali:Sulfate balance in clinker is important
Total and water soluble contents important
Higher clinker sulfate content produces a higher water soluble level
Higher total alkali levels reduce 28 day strength
Higher levels of water soluble alkalies increase early strength
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Water Soluble Alkalis
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
0.1 0.3 0.5 0.7 0.9 1.1
Clinker Eq. Na2O
C
l
i
n
k
e
r

S
O
3







.
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.1
0.6
0.5
0.4
0.7
0.3
0.2
Eq. Water Soluble Na2O
Clinker SO3
=0.84%
Eq. Na2O
=0.66%
Eq. Water Soluble
Na2O ~0.44%
TIS MS004.
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Sulfate
Present in clinker and as added calcium sulfate
Forms of sulfate important
Influences:
Water Demand
Setting behaviour
Early strength
Later strength
Shrinkage
Flash/false set behaviour
Silo Set
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Fineness
Measured as Air Permeability, Blaine or SSA, m
2
/kg or cm
2
/g
Residues, e.g. Alpine 45 micron
Particle Size Distribution, e.g. laser diffraction, sedimentation
Higher SSA provides higher early strength, shorter set time
Higher residues reduce 28 day strength
Higher grinding efficiency provides a narrower psd
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Cement Fineness
SSA = 350 m
2
/kg
99% < 90 microns
85-95% < 45 microns
6-10% < 2 microns
Gypsum SSA = 1000-1200 m
2
/kg
1% gypsum = 10-12 m
2
/kg
1% SO3 = 30 m
2
/kg
<2 microns = ~50% of SSA
Gypsum = ~15% of SSA
50 Billion (50,000,000,000) particles per gram
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Surface Properties
Degree of pre-hydration/carbonation can be expected to influence
Strength development
Setting Characteristics
Water Demand
Flowability (Packset)
Use of clinker stored outside can change SSA/strength relationship
LOI is a guide, 1% can equate to 4 mpa
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Cement Composition
Clinker, Gypsum, but also
Blast Furnace Slag
Fly Ash
Pozzolana
Limestone
.
Levels and quality will influence
water demand
setting
strength
SSA v kWh/tonne relationship
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Alite Sizes, Typically 15-100 microns Smaller (<40) - better strength
Larger (>60) - less reactive
Burning Temperature Lower - better crystal sizes
Cooling Regime Faster - smaller crystal size
Crystal Impurities Purer crystals - less reactive
Reduction Loss of SO3, Flowability problems
Raw Feed Fineness Coarser - difficult combinability
Raw Feed homogeneity Siliceous - lower strength
Calcareous - better strength
Heterogeneity - difficult combinability
Porosity Lower - difficult grindability
Clinker Microstructure Characteristics
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Influences on Clinker Microstructure
Raw feed Chemistry
Raw Material Mineralogy
Raw Feed Fineness
Burning Regime - Atmosphere, Temperature
Fuel Type and Fineness
Cooling
Studied by Microscopic Examination
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Influences of Minor Components
M
g
O Expansive Behaviour
Fluoride Mineralisation, Setting and Late Strength
Chloride Process, Setting, Early Strength, Corrosion
P
2
O
5
Setting, Belite Stabilisation (v. high levels)
Strontium Belite Stabilisation
Barium Belite Stabilisation
Heavy Metals e.g. Pb, Zn on environment and setting
Transition Metals e.g. Cr, V, Mn on colour
C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
Parameter Unit Incremental
change 2d 28d
MPa MPa
SSA m2/kg +10 0.30 0.30
45-micron residue % +1 -0.35 -0.40
Eq. Na
2
O % +0.1 0.80 -1.70
LOI % +1 -0.50 -3.00
C3S % +1 0.35 0.10
Free Lime % +1 0.50 -1.50
SO3 % +0.1 0.50 0.10
C3A % +1 0.50 1.00
Effect on strength
Figure 12.
Some Rules of Thumb