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1. Cement Chemistry
1.1
INTRODUCTION
1.2
R AW M A T E R I A L S
1.3
FUELS
1.4
CLINKER
1.5
GYPSUM
1.6
CEMENT
1.6.1
L S F, E T C
1.6.2
CLINKER COMPOUNDS
1.6.3
P R I N C I PA L C E M E N T C H A R A C T E R I S T I C S
1.7
contents
G Y P S U M - S O L U B L E C A L C I U M S U L P H AT E
1.7.1
INTRODUCTION
1.7.2
D I S S O L U T I O N O F C a S O4
1.7.3
O P T I M I S AT I O N O F S O L U B L E C A L C I U M S U L P H AT E
1.7.4
SLUMP LOSS/RETENTION
chapter 2
1.
CEMENT CHEMISTRY
Compound
Water
H2O
18.02
Carbon Dioxide
CO2
44.01
CaO
56.08
Magnesia
MgO
40.31
Silica
SiO2
60.09
Titania
TiO2
79.90
Element
Symbol
Atomic Weight
Alumina
Al2O3
101.96
Aluminium
A1
26.98
Calcium
Ca
40.08
Ferric Oxide
Fe2O3
159.70
Carbon
12.01
Phosphorus Pentoxide
P2O5
141.94
The first patent for Portland Cement was granted in 1824. Cements,
with a chemistry similar to today's cements, were not really
produced until the late 1800's. Shaft or bottle kilns were used.
Hydrogen
1.01
Sulphur Trioxide
SO3
80.06
Iron
Fe
55.85
Magnesium
Mg
24.31
Soda
Na2O
62.00
Manganese
Mn
54.94
Potash
K2O
94.20
Oxygen
16.00
Calcium Carbonate
CaCO3
CC
100.09
Phosphorus
30.97
Potassium
39.10
Magnesium Carbonate
MgCO3
MC
84.32
Silicon
Si
28.09
Sodium Carbonate
Na2CO3
NC
106.01
Sodium
Na
23.00
Calcium Sulphate
CaSO4
CS
136.14
Sulphur
32.06
Titanium
Ti
47.90
Potassium Sulphate
K2SO4
KS
174.26
1.1
INTRODUCTION
The production of cement can be considered as a chemical
process not so different to other chemicals such as Sodium
Hydroxide and Calcium Chloride. However there are two major
differences:
- Selling Price
- Product Complexity
Portland Cement can contain approximately 10 chemicals/minerals
and is relatively impure when compared to most "chemicals".
Part of this impurity arises from the "naturally occurring"
nature of the key raw materials, but also from the low selling
price, which is significantly lower than for most "Chemicals".
The impurities can vary quite considerably, both from one plant
to another but also within any one plant, and these can have an
important influence on the ultimate cement behaviour.
contents
chapter 1
chapter 2
For simplicity, cement chemists have traditionally used a "shorthand" for chemical symbols and these are also shown in Figure 2.
1.2
RAW MATERIALS
We shall see later that the four most important oxides in
Portland Cement are lime (CaO), silica (SiO2), alumina (Al2O3)
and iron oxide (Fe2O3). That is, in short-hand C, S, A, and F.
The principal source of lime for cement manufacture is
limestone or chalk and this constitutes typically some 80% of
the raw material mix.
In practice the actual materials used for the source of CaO
cover the complete range of geological forms. However, the
differences of most practical relevance involve:
- Chemistry (including impurities)
- Hardness
- Porosity
- Crystal Size
- Moisture
- Location
and of course
- Cost
1.
Source of
CaO
Shale or Clay
Al2O3.Fe2O3.SiO2
Iron Oxide
Fe2O3
Bauxite
Al2O3.Fe2O3
Sand
SiO2
Slag
CaO (Al2O3.Fe2O3.SiO2)
S
A
F
C
contents
chapter 1
chapter 2
CEMENT CHEMISTRY
3.3
0.7
0.2
53.2
Limestone
Shale
S
A
F
C
52.8
14.2
8.7
1.0
Raw Mill
Raw
Meal
S
A
F
C
13.2
3.4
1.9
43.0
S
A
F
C
Coal
Ash
51.7
26.4
9.5
1.6
Kiln
S
A
F
C
20.9
5.6
3.0
65.7
Clinker
1.
CEMENT CHEMISTRY
As
Limit g/t
Antimony
Sb
3000
Arsenic
As
270
Beryllium
Be
90
Cadmium
Cd
Chrome
Cr
100
10
Fluorine
500
Cobalt
Co
100
Mercury
Hg
1-2
Lead
Pb
370
Nickel
Ni
130
Selenium
Se
80
Tellurium
Te
450
Thallium
Th
0.02
Vanadium
650
Zinc
ZnO
10000
Product Quality
Strontium
SrO
5000
Barium
BaO
5000
Product Quality
Phosphorus
P205
10000
Product Quality. Extends set time, produces alite instability (high levels)
Titanium
TiO2
10000
Copper
Cu
1000
Sulphur
SO3
7500
Chloride
Cl
250
Alkali
(Eq.Na20)
Na20
10000
contents
chapter 1
chapter 2
1.3
FUELS
The primary requirement for the fuel is to provide the necessary
energy involved in the clinker manufacturing process. This
typically amounts to between 700 and 1500 kcal/kg clinker,
with some 420 kcals/kg being the theoretical heat requirement,
(i.e. the heat required to convert the raw materials into the
clinker minerals). The remainder of the heat is essentially
accounted for by removal of moisture, sensible heat of exit gases
and the shell losses.
1.
Influence on
Calorific Value
Fuel Consumption
Price
Carbon/Hydrogen ratio
Flame characteristics
Hardness
Preparation
Volatiles
Flame characteristics
Abrasivity
Preparation, Handling
Moisture
Grading, Size
contents
chapter 1
chapter 2
CEMENT CHEMISTRY
Coal replacement
limited by the impact
on:
Flowability, Preparation
SO2
Sulphur, Chloride
Process
Nitrogen
Environment
Refractories
Burning conditions
Vanadium
Viscosity
Emission limits
Typically 60% of International
Coal Price e.g. Coal at 1.8 US$ per Mill output
GJ (say 55$/tonne)
Availability
Coke at 1.2 US$ per GJ (say
35$/tonne)
Price differential
Comments:
1.4
CLINKER
In general, Portland Cement Clinker contains four principal
chemical compounds, or clinker minerals as they are usually
referred to. These are:
Tricalcium Silicate
Dicalcium Silicate
Tricalcium Aluminate
Calcium Aluminoferrite
The composition of these together with their short-hand
notation mineral name and typical levels are shown in Figure 9.
1.
Shorthand
Name
Formula
Formula
Typical
Range
Tricalcium Silicate
C3S
Alite
3CaO.SiO2
Ca3SiO5
60%
30-70%
Dicalcium Silicate
C2S
Belite
2CaO.SiO2
Ca2SiO4
20%
5-40%
Tricalcium Aluminate
C3A
Aluminate
3CaO.Al2O3
Ca3Al2O5
10%
5-15%
Calcium Aluminoferrite
C4AF
Ferrite
4CaO.Al2O3.Fe2O3
Ca4Al2Fe2O10
8%
5-15%
contents
chapter 1
chapter 2
CEMENT CHEMISTRY
21.3
LSF
96.5
Al2O3
5.6
S/(A+F)
2.45
Fe2O3
3.1
A/F
1.81
CaO
66.0
C3S
60
MgO
1.3
C2S
16
Mn2O3
0.1
C3A
10
P2O5
0.2
C4AF
TiO2
0.3
LOI
0.1
Na2O
0.8
K2O
0.2
SO3
1.0
Free Lime
1.2
contents
chapter 1
chapter 2
1.
CEMENT CHEMISTRY
1.5
GYPSUM
Although clinker contains some SO3, arising from the raw
materials and fuel, additional SO3 is required to produce cement
from the clinker.
The SO3 in the clinker is usually combined with the alkalis to
form:Alkali sulphates
K2SO4, Na2SO4
Calcium Langbeinite
2 CaSO4. K2SO4
Calcium Sulphate
CaSO4
In discussions any additional SO3 is usually referred to as
'gypsum', but in reality the source of SO3 will contain gypsum,
anhydrite and other minerals such as clay, quartz and calcite as
well as free moisture.
A full analysis is required to precisely identify the minerals
present in any source of SO3. However the most important
parameters concern the total SO3 content and the level of
gypsum and anhydrite. The latter can be derived from the SO3
content and the loss on ignition at 50, 250 and 950C.
An example of calculations for gypsum and anhydrite is
provided in Technical Information Sheet (TIS) number MS001.
It has also been traditional to refer to the 'gypsum' as a 'set
regulator' or 'set retarder'. However the main role of the added
SO3 is to prevent rapid reaction of the aluminate which would
result in early stiffening, loss of workability and early set.
In addition to preventing the rapid reaction of C3A, the
presence of added SO3 also influences the wider hydration
process, which affects setting, workability and strength
development. These in turn affect the target SO3 content of the
cement. However this is typically in the range 2.5 - 3.5%.
contents
chapter 1
chapter 2
1.
CEMENT CHEMISTRY
1.6
CEMENT
1.6.1
LSF, etc
We have already seen that Clinker, and thus cement, principally
consists of the calcium silicate minerals, and these derive from
raw materials containing the four principal oxides, namely CaO,
SiO2, Al2O3 and Fe2O3.
To assist in the proportioning of the raw materials, the excess
CaO available in the limestone (or other), together with the
CaO required to saturate the oxides in the shale (or other) needs
to be known.
Lea and Parker derived a formula (1935) from the base of
100% lime saturation, which permits the calculation of the lime
required for saturation of the other oxides, i.e.
CaO
The lime saturation factor (LSF) for any mix of raw materials is
then given by:
LSF
1.
CONTROL PARAMETERS
NO. OF RAW
MATERIALS REQUIRED
LSF
contents
chapter 1
chapter 2
10
RANGE
LSF
95
90 - 98
SILICA RATIO
2.5
2-4
ALUMINA RATIO
1.7
1-3
CEMENT CHEMISTRY
1.6.2
Clinker Compounds
The main clinker compounds can be determined by x-ray
diffraction but are typically estimated according to Bogue
(1929). These estimations are shown in TIS No. MS003.
In these calculations the iron oxide is assumed to be present in
the alumina-ferrite phase and all of the alumina not required to
contents
chapter 1
chapter 2
1.
CEMENT CHEMISTRY
11
1.6.3.7
SO3 Cement (See Also Section 1.7)
The total SO3 content of the cement influences the hydration
process and thus effects the strength development, setting and
workability. Also, as discussed, the level of "gypsum" added
influences the Blaine. Hence for a constant clinker SO3 content,
a varying cement SO3 level indicates variations in added
"gypsum". Hence there will be a direct influence on the
Blaine/mill output relationship.
As a guide, a 1% increase in cement SO3 content will equate to
around a 30m2/kg increase in Blaine (constant mill output) or
10-15% increase in mill output (constant Blaine).
In general, higher levels of SO3 content will enhance the early
strength, extend the setting items and usually decrease the
concrete workability (increase the water demand). As a guide, a
0.1% increase in cement SO3 content will equate to 0.5 MPa at
2-days and 0.1 Mpa at 28-days (EN196 mortar).
There will be an optimum level of SO3 content with respect to
the 28-day strength. This will depend on many factors
including clinker chemistry and whether derived at constant
Blaine or constant mill output.
1.6.3.8
SO3 - Forms (See Also Section 1.7)
The principal forms of SO3 in cement are:
a)
ex. clinker
b)
contents
chapter 1
chapter 2
1.
Burning Temperature
Cooling Regime
Crystal Impurities
Reduction
Porosity
CEMENT CHEMISTRY
12
contents
chapter 1
chapter 2
1.
Parameter
Unit
SSA
m2/kg +10
0.30
0.30
45-micron residue %
+1
-0.35
-0.40
Eq. Na2O
+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
LSF
S/(A+F)
A/F
MgO
Mn2O3
TiO2
P2O5
C3S
C2S
C3A
C4AF
SO3
Na2O
K2O
LOI
Free Lime
Insoluble Residue
Blaine (SSA)
Residue (e.g.. 45 micron)
CEMENT CHEMISTRY
13
1.7
'GYPSUM' - SOLUBLE CALCIUM SULPHATE
1.7.1
Introduction
The principal sources of SO3 in cement are:
a)
ex clinker, i.e.
alkali sulphates
K2SO4, Na2SO4
calcium langbeinite 2Ca SO4 .K2SO4
calcium sulphate CaSO4
Note: The calcium sulphate present in clinker, formed where
there is a large excess of SO3 over alkalis, will be equivalent to
anhydrite (anhydrite I - slowly soluble).
b)
Note:
contents
chapter 1
chapter 2
1.
CEMENT CHEMISTRY
14
Cement
3.0
3.0
3.0
3.0
Clinker
1.0
1.0
1.0
1.0
Natural Anhydrite
0.0
0.0
1.0
1.0
Gypsum
0.1
1.0
0.1
1.0
1.0
0.9
0.0
Sources of SO3:
1.7.3
Optimisation of Soluble Calcium Sulphate
The availability of soluble CaSO4 is required to 'satisfy' the
initial reactivity of the C3A. The 'optimum' supply of soluble
CaSO4 will therefore depend on the initial 'reactivity' of the
C3A. This will principally depend on:
-
1.
CEMENT CHEMISTRY
15
In general:
- the optimum level of D.SO3 will be around 1.0% SO3
(i.e. typically in the range 0.7 - 1.3% SO3).
- for more reactive clinkers the optimum D.SO3 will be higher.
- for less reactive clinker the optimum D.SO3 will be lower.
- for less reactive clinkers the curve will be flatter in the
region below the optimum D.SO3 but steeper in the
region above the optimum (i.e. tendency for false set
behaviour more important).
- for more reactive clinkers the curve will be flatter in the
region above the optimum D.SO3, but steeper in the
region below the optimum (i.e. tendency for flash set
behaviour more important).
1.7.4
Slump Loss/Retention
The preceding points mainly refer to the initial slump or
workability or water demand in concrete. However a consistent,
and predictable, slump loss behaviour over the initial period of,
say, up to one hour is more important.
contents
chapter 1
chapter 2
contents
chapter 1
chapter 2
SO3 ex. hemihydrate & soluble anhydrite has been referred as "D.SO3"
1.
CEMENT CHEMISTRY
16