C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 2

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 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

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1.1 INTRODUCTION in the tumbling action of the rotary kiln to form the well-known Compound Formula Shorthand Molecular
The production of cement can be considered as a chemical characteristic clinker. Weight
process not so different to other chemicals such as Sodium
Hydroxide and Calcium Chloride. However there are two major Chemically, clinker consists of a mixture of compounds, which Water H2O H 18.02
differences: are made up of various molecules and elements. The most
- Selling Price important elements in cement chemistry are shown in Figure 1 Carbon Dioxide CO2 C 44.01
- Product Complexity together with their atomic weights. The most relevant
compounds in Cement Chemistry are shown in Figure 2. Lime (Calcium Oxide) CaO C 56.08
Portland Cement can contain approximately 10 chemicals/minerals
and is relatively impure when compared to most "chemicals". For simplicity, cement chemists have traditionally used a "short-
Magnesia MgO M 40.31
Part of this impurity arises from the "naturally occurring" hand" for chemical symbols and these are also shown in Figure 2.
nature of the key raw materials, but also from the low selling
price, which is significantly lower than for most "Chemicals". The chemistry of raw materials, fuels and clinker are discussed Silica SiO2 S 60.09
The impurities can vary quite considerably, both from one plant in more detail in the following sections.
to another but also within any one plant, and these can have an Titania TiO2 T 79.90
important influence on the ultimate cement behaviour.
Element Symbol Atomic Weight Alumina Al2O3 A 101.96
However, customers of cement place high demands on the Aluminium A1 26.98
performance of the cement, expecting it to react in a predictable Ferric Oxide Fe2O3 F 159.70
manner with respect to its handling, workability, setting, Calcium Ca 40.08
hardening and strength development. Phosphorus Pentoxide P2O5 P 141.94
Carbon C 12.01
The first patent for Portland Cement was granted in 1824. Cements, Hydrogen H 1.01 Sulphur Trioxide SO3 S 80.06
with a chemistry similar to today's cements, were not really
produced until the late 1800's. Shaft or bottle kilns were used. Iron Fe 55.85
Soda Na2O N 62.00
Magnesium Mg 24.31
Rotary kilns were first used around 1900. These became
operated in a semi-dry manner around the 1950's and the Manganese Mn 54.94 Potash K2O K 94.20
modern dry process kiln appeared in the 1960's and 1970's with Oxygen O 16.00
the more efficient pre-calciner process appearing a little later. Calcium Carbonate CaCO3 CC 100.09
Wet, semi-wet, semi-dry, dry and pre-calciner process kilns all Phosphorus P 30.97
remain in use throughout the world today. (See Section 2). Magnesium Carbonate MgCO3 MC 84.32
Potassium K 39.10
There are also a significant number of vertical shaft kilns still in
operation, particularly in China. Silicon Si 28.09 Sodium Carbonate Na2CO3 NC 106.01

Portland Cement clinker is manufactured from a calcareous Sodium Na 23.00

Calcium Sulphate CaSO4 CS 136.14
material (e.g. limestone, chalk) and an argillaceous material (e.g. Sulphur S 32.06
shale, clay). The feed material is finely ground and carefully
Potassium Sulphate K2SO4 KS 174.26
mixed and heated to a very high temperature (~1500°C). During Titanium Ti 47.90
this heating some 25% of the mixture becomes liquid. This
assists in the chemical reactions and bonds the particles together Figure 1. Principal Elements. Figure 2. Principal Compounds.

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1.2 RAW MATERIALS When lower grade limestones or secondary materials are used Figure 3. Raw Materials.
We shall see later that the four most important oxides in the associated levels of impurities, such as sulphur, alkalis and
Portland Cement are lime (CaO), silica (SiO2), alumina (Al2O3) magnesia can become important. Raw Material Source of
and iron oxide (Fe2O3). That is, in short-hand C, S, A, and F.
Thus, in terms of tonnages, the primary and secondary material Limestone or Chalk, CaCO3 CaO
The principal source of lime for cement manufacture is are of most importance with regard to location and cost. Al2O3.Fe2O3.SiO2
Shale or Clay
limestone or chalk and this constitutes typically some 80% of
the raw material mix. However in addition to these, it maybe necessary to make Iron Oxide Fe2O3
adjustments to the mix with sources of silica, alumina and iron
In practice the actual materials used for the source of CaO oxide. These will generally be at low addition levels, but can Bauxite Al2O3.Fe2O3
cover the complete range of geological forms. However, the significantly influence the cost of the final raw material mix.
differences of most practical relevance involve: Sand SiO2
- Chemistry (including impurities) Whilst the fuel is essentially there to provide the energy for
- Hardness clinker formation, any associated ash (particularly since coal Slag CaO (Al2O3.Fe2O3.SiO2)
- Porosity remains the main source of fuel) must be taken into account
- Crystal Size when designing the raw feed mix for a given clinker chemistry.
- Moisture
- Location Some examples of raw materials are shown in Figure 3, whilst
and of course - Cost typical chemical analyses for raw material, raw mix, coal ash S 3.3 S 52.8
A 0.7
and clinker are shown in figure 4. F 0.2
Limestone Shale A 14.2
F 8.7
Some of these are discussed further in Section 2. C 53.2 C 1.0

The proportion of non-calcareous material, i.e. any siliceous or

argillaceous material in the limestone will influence the use of
secondary materials.
Raw Mill
The secondary material providing Al2O3, SiO2, Fe2O3 is
S 13.2
principally an argillaceous material like shale or clay. In general Raw A 3.4 Coal S
A
51.7
26.4
this will contain clay minerals, as well as free silica.
Meal F
C
1.9
43.0 Ash F 9.5
C 1.6
However, sometimes, the principal material may contain
sufficient levels of S, A, F to produce the desired Clinker
Chemistry (origin of Ciments Naturel). More often though, the Kiln
desired mix maybe achieved with a mix of high and low grade
limestones. That is, high grade having a high level of CaO (say
50%) and low levels of Al2O3, SiO2, Fe22O3 and a low grade
S 20.9
material having a lower level of CaO but high levels of Al22O3, A 5.6
SiO2 and Fe2O3. F 3.0 Clinker Figure 4. Typical Chemical Analyses of
C 65.7
Materials.

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Increasingly, the cement industry is considering the utilisation of Figure 5. Limits for Use of Raw Materials and Fuels
less traditional materials, which can often contain significant
levels of impurities (with respect to cement manufacture). Element As Limit g/t Principal Reason for Limitation/Notes

For these (and also for the 'traditional' materials to some Antimony Sb 3000 Environmental Emission Impact
extent) it is necessary to carefully assess their potential impact
Arsenic As 270 Environmental Emission Impact
on the industry. This may involve impact in the following areas:
- Raw Material Cost Beryllium Be 90 Environmental Emission Impact
- Availability, Quantities
- Capital Requirement Cadmium Cd 7 Environmental Emission Impact
- Public Environmental Awareness Chrome Cr 100 Product Health & Safety
- Impact on Emission Limits 10 Colour (White Cement)
- Material Health and Safety
- Influence on Flame Characteristics Fluorine F 500 Environmental Emission Impact. Increases strength at low levels (<0.5%) and
- Influence on Kiln Performance extends set time (esp. at low temp)
- Influence on Clinker/Cement Properties Cobalt Co 100 Product Health & Safety
- Influence on Emissions
- Influence on Product Health and Safety Mercury Hg 1-2 Environmental Emission Impact
Lead Pb 370 Environmental Emission Impact. Extends set time, reduces early strength
How individual materials or elements actually influence some of
these parameters can be quite complex, for example, involving Nickel Ni 130 Environmental Emission Impact
the degree to which elements are directly retained in the clinker. Selenium Se 80 Environmental Emission Impact

A list of the potentially problem causing elements is shown in Tellurium Te 450 Environmental Emission Impact
Figure 5, together with their principal concerns (i.e. Thallium Th 0.02 Environmental Emission Impact
environmental, health and safety, process operation or product
quality). Recommended maximum input levels in grams per Vanadium V 650 Environmental Emission Impact. Adverse effect on refractories
tonne of clinker equivalent are also shown. Zinc ZnO 10000 Product Quality
Strontium SrO 5000 Product Quality, produces alite instability
Barium BaO 5000 Product Quality
Phosphorus P205 10000 Product Quality. Extends set time, produces alite instability (high levels)
Titanium TiO2 10000 Product Quality, reduces early hydraulic activity
Copper Cu 1000 Product Quality, Reduces 'clinkerisation'
Sulphur SO3 7500 Process, kiln & preheater deposits
Chloride Cl 250 Process, kiln & preheater deposits
Alkali Na20 10000 Process, kiln & preheater deposits
(Eq.Na20) Increases early strength, decreases later strength

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1.3 FUELS Figure 6. Factors Influencing the Choice of Fuel. In recent years there has been particular interest in petroleum
The primary requirement for the fuel is to provide the necessary coke, waste solvents and used tyres.
energy involved in the clinker manufacturing process. This Property Influence on
typically amounts to between 700 and 1500 kcal/kg clinker, Calorific Value Fuel Consumption However, as with the primary fuels, the use of alternatives will
with some 420 kcals/kg being the theoretical heat requirement, depend on a range of factors concerning health and safety (both
(i.e. the heat required to convert the raw materials into the Price Fuel Cost/clinker tonne the material itself and resultant influence on the cement), fuel
clinker minerals). The remainder of the heat is essentially preparation, kiln operation, emissions and clinker/cement
Carbon/Hydrogen ratio Flame characteristics
accounted for by removal of moisture, sensible heat of exit gases quality and cost and availability. As an example, petroleum coke
and the shell losses. Mix proportioning, Clinker quality, (See Figure 8) often contains important levels of sulphur whilst
Ash content & chemistry
Refractories waste solvents often contain appreciable levels of chloride.
The current primary fuels for the cement industry are
Hardness Preparation
hydrocarbon fuels, their main constituents being carbon and Figure 8. Petroleum Coke.
hydrogen. Coal, oil and natural gas are the most common in Volatiles Flame characteristics
use. Coal replacement
Abrasivity Preparation, Handling Most from United States limited by the impact
The fuel consumption will of course be dependent on the energy Moisture Flowability, Abrasivity, Preparation on:
content of the fuel and the energy requirement of the kiln High Sulphur (~5%, Coal <1%) SO2
Grading, Size Flowability, Preparation
process. For example, for a coal of 7300 kcals/kg and a modern
pre-calciner kiln requiring 760 kcals/kg the fuel consumption Sulphur, Chloride Kiln build-ups, Corrosion Harder than coal Process
will simply be 760/7300 = 10.4%, i.e. 1 tonne of clinker will
require 0.104 tonnes of coal. Similarly, for a less efficient wet Nitrogen Environment
6 - 8mtpa (Prime fuel required Burning conditions
process of 1400 kcals/kg the fuel consumption would be 19.2%. Vanadium Refractories ~100-150mtpa)
Emission limits
Many factors will influence the ultimate choice of fuel for a Viscosity Handling, atomisation, Flame
Typically 60% of International
given plant. These will include any potential influence on the Coal Price e.g. Coal at 1.8 US$ per Mill output
fuel preparation (e.g. coal grinding), flame characteristics, ash Increasingly, the traditional primary fuels are being replaced (at GJ (say 55$/tonne)
chemistry (hence clinker quality), kiln build-ups (e.g. Sulphur least partially) by a large range of waste and by-product Availability
and Chloride contents), process emissions as well as, of course, materials, which have significant energy contents. A list, Coke at 1.2 US$ per GJ (say
price, calorific value, supply and consistency. The choice will be showing examples of these, is shown in Figure 7. 35$/tonne) Price differential
influenced by many of the parameters discussed for raw
materials (See Section 1.2 and Figure 5). Some of the relevant Figure 7. Examples of some Alternative Fuels. Comments:
parameters for fuels are shown in Figure 6.
Heavy Fuel Oil, Natural Gas
Petroleum Coke Significant in short term
Waste Solvents
Waste Oils, Orimulsion Less so in longer term
Refuse Derived Fuel, Biogas
Tyres, Recycled Car parts Ability to reduce clinker cost by ~2$/tonne
Raw Materials (e.g. Oil Shale)
Timber Waste
Straw
Impregnated Sawdust
Hazardous Waste
Water Purification Residues

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1.4 CLINKER Figure 9. Clinker Minerals.

In general, Portland Cement Clinker contains four principal
chemical compounds, or clinker minerals as they are usually Mineral Shorthand Name Formula Formula Typical Range
referred to. These are:
Tricalcium Silicate Tricalcium Silicate C3S Alite 3CaO.SiO2 Ca3SiO5 60% 30-70%
Dicalcium Silicate
Tricalcium Aluminate Dicalcium Silicate C2S Belite 2CaO.SiO2 Ca2SiO4 20% 5-40%
Calcium Aluminoferrite
Tricalcium Aluminate C3A Aluminate 3CaO.Al2O3 Ca3Al2O5 10% 5-15%
The composition of these together with their short-hand
Calcium Aluminoferrite C4AF Ferrite 4CaO.Al2O3.Fe2O3 Ca4Al2Fe2O10 8% 5-15%
notation mineral name and typical levels are shown in Figure 9.

The silicate minerals are largely responsible for the strength

development characteristics of Portland Cement. However, the
reaction between lime and silica is difficult to achieve, even at
high temperatures. The reaction (Chemical Combination) is
facilitated by the presence of alumina and iron oxide, as these
assist in the formation of a molten flux through which the lime
and silica are able to partially dissolve and then react to form
C3S and C2S.
Figure 10. Sequence of
The sequence of reaction is illustrated in Figure 10. A typical
Formation of Calcium
full clinker chemistry is shown in Figure 11.
Silicates in a Rotary Kiln.
Clinkers designed for sulphate resistance require materials with
low levels of Al2O3 so that the clinker contains a low (or zero)
level of C3A. In general the C3A content will be less then 1%
whilst the C4AF will be higher at 15-20%.

For White Cements materials with low levels of Fe2O3 are

required so that the clinker contains a low (or zero) level of
C4AF. As a consequence the C3A contents will usually be higher
at 12-16%, although it is possible to avoid high C3A by having
very high total silicates. In addition the clinker has to be
produced with materials low in Mn2O3 and Cr2O3.

The influence of chemistry is discussed in Section 1.6. However

clinker properties can also directly influence:
- Materials Handling
- Mill Performance
- Storage

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It should also be noted that many plants use stored clinker in Size grading will be a function of raw materials, kiln process
addition to the 'fresh' kiln clinker. Sometimes these maybe from and kiln operation. In general hard burning conditions can be
external sources. Therefore the main characteristics influencing expected to produce a dusty clinker (large proportion less than
the above can vary significantly. 1mm). In fact, it has been shown that free lime can be linked to
the clinker fines content, with low free limes (associated with
Materials handling will most notably be influenced by the hard burning) leading to a high fines content. This in turn can
clinker size grading and the temperature. For stock clinker, the result in difficult handling and a hard grindability.
degree of degradation (i.e. ageing/hydration) will also be
important
Conversely, underburned clinkers with a very high free lime can
Figure 11. Example of EN197 CEM I Clinker Chemistry. also contain a high fines content.
SiO2 21.3 LSF 96.5
Besides the degree of burning (and cooling), that influence the
Al2O3 5.6 S/(A+F) 2.45 microstructure, the grindability is strongly influenced by the
Fe2O3 3.1 A/F 1.81 levels of C2S and SO3. The latter will affect the level of gypsum
CaO 66.0 required to produce a target SO3 content in the cement. Hence
the perceived grindability will be influenced by the proportion
C3S 60
of 'softer' gypsum present.
MgO 1.3 C2S 16
Mn2O3 0.1 C3A 10 Clinkers with a wide size grading will be subject to more
P2O5 0.2 C4AF 9 segregation during storage and hence the material sizes in the
clinker feed to a mill can be variable. This in turn can result in a
TiO2 0.3
variable mill performance.

LOI 0.1 Because of the natural size grading of clinkers, sampling is a

Na2O 0.8 difficult task. For this reason extreme caution should be taken
when taking samples (See Section on Cement Grinding) of
K2O 0.2 clinker (and Gypsum).
SO3 1.0

Free Lime 1.2

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1.5 GYPSUM The level of SO3 additive ('Gypsum') required is simply

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 950°C.
An example of calculations for gypsum and anhydrite is
provided in Technical Information Sheet (TIS) number MS001.
calculated by a mass balance using the 'gypsum', clinker and
cement SO3 contents. This is described in TIS No: MS002.
The above calculation often needs to be modified to allow for
non-clinker components, and this is also shown in TIS No:
MS002.
Combining the calculations of "gypsum" addition level and
gypsum/anhydrite contents provides the levels of added
anhydrite and gypsum in the cement.
Whilst the anhydrite (natural anhydrite) remains unaffected
during cement grinding, the gypsum largely dehydrates. The
resultant levels of anhydrite and gypsum dehydration products
(i.e. hemihydrate and soluble anhydrite) can have a marked
influence on cement performance, particularly regarding
concrete water demand and workability.
The sources of SO3 in cement, their dissolution rate, the
optimisation of soluble CaSO4 and concrete slump behaviour
are discussed in more detail in Section 1.7.

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%.

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1.6 CEMENT Control of LSF will however not control the resultant levels of
1.6.1 LSF, etc aluminate or ferrite. To assist in their control, and targeting, it
We have already seen that Clinker, and thus cement, principally is usual to use the parameters of silica ratio and alumina ratio.
consists of the calcium silicate minerals, and these derive from Thus there can often be three target control parameters, i.e.
raw materials containing the four principal oxides, namely CaO,
SiO2, Al2O3 and Fe2O3.
NO. OF RAW
CONTROL PARAMETERS
To assist in the proportioning of the raw materials, the excess MATERIALS REQUIRED
CaO available in the limestone (or other), together with the
CaO required to saturate the oxides in the shale (or other) needs 1 LSF 2
to be known.
2 LSF, SILICA RATIO 3 allowance for the combination of some of the SO3 with alkalis
Lea and Parker derived a formula (1935) from the base of
LSF, SILICA RATIO,
100% lime saturation, which permits the calculation of the lime 3 4
ALUMINA RATIO
required for saturation of the other oxides, i.e.
CaO = 2.80 SiO2 + 1.18 Al2O3 + 0.65 Fe2O3 As you can see for 1 parameter, 2 materials are required, for 2
parameters, 3 materials, and for 3 parameters, 4 materials, and
The lime saturation factor (LSF) for any mix of raw materials is so on.
then given by:
Additional target control parameters, like alkalis, magnesia, will
LSF = CaO / (2.80 SiO2 + 1.18 Al2O3 + 0.65 Fe2O3) therefore require more than 4 raw materials.
The ratio is usually expressed as a percentage. It is also applied Typically, clinker will have:
to the clinker and the cement, although the calculation can be
complicated by the presence of CaSO4, free lime, alkalis, etc. MEAN RANGE
For clinker the above formula is usually used, although this can LSF 95 90 - 98
be misleading if there is a high SO3 content in which some of
the CaO has combined with the SO3 to leave calcium SILICA RATIO 2.5 2-4
langbeinite and calcium sulphate.
ALUMINA RATIO 1.7 1-3
For cement it is usual to deduct the lime present in the CaSO4,
before calculating the LSF (See TIS No. MS003).
1.6.2 Clinker Compounds
In proportioning raw materials, at least two materials will be The main clinker compounds can be determined by x-ray
required to achieve a target LSF. In 'Ciments Natural', a single diffraction but are typically estimated according to Bogue
raw material chemistry will lead to variation in the clinker (1929). These estimations are shown in TIS No. MS003.
chemistry (and hence LSF). Two materials permit control to a
single target LSF, by varying the component proportions. In these calculations the iron oxide is assumed to be present in
the alumina-ferrite phase and all of the alumina not required to
satisfy the iron oxide in this is assumed to be present as C3A. The
remaining lime is then proportioned between the C3S and C2S.
Again, for cement, the quantity of lime present as CaSO4 needs
to be taken into account. In addition, for cement, the lime
present which is uncombined (free lime) can also be deducted to
provide a more realistic calculation. However some estimations
are for potential Bogue composition (e.g. ASTM), in which the
total lime is used.
It is possible to refine these calculations further, for example by
rather than CaO.
Calculations according to Bogue should be treated only as the
estimation that they are. One area often giving rise to errors is
the assumption of an alumina/iron oxide ratio of 1 for the
ferrite phase. It is known that this can be variable in the
presence of some minor compounds in the clinker (e.g. fluorine).
1.6.3 Principal Cement Characteristics
1.6.3.1 Introduction
The most important cement characteristics which are known to
have a significant influence on cement, mortar and concrete
performance include:
- Silicates
- Aluminate
- Ferrite
- Alkalis
- SO3, Clinker
- SO3, Cement
- Forms of SO3
- Free Lime
- Fineness (Blaine, PSD)
- Microstructure (Crystallography, Burning, Cooling)
- Surface Properties (Hydration, Carbonation)
- Composition (Non-Clinker components)
In addition, minor components, such as fluoride, chloride, heavy
metals can also be important (See Figure 5).

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The following sections deal with these in more detail.
Additional information concerning cement performance is
provided in Section 7.
1.6.3.2 Silicates
The total silicate level directly influences the strength potential.
A higher lime saturation factor (LSF) will result in a greater
ratio of C3S to C2S and this will tend to produce a higher early
strength (up to 7 days) for a given 28-day strength. As a guide,
a 1% change in C3S content will be equivalent to around 0.35
MPa at 2-days and 0.10 Mpa at 28-days (EN196 mortar).
Note should be taken of whether the data for C3S, etc is
"potential" Bogue composition or reflects the actual level of free
lime. Higher levels of free lime result in a lower C3S / C2S ratio.
1.6.3.3 Aluminate
The principal influence of the C3A content (and its
crystallography) is on the water demand, workability and
setting behaviour. The interaction between C3A and SO3 is
important and directly influences the water demand and
workability characteristics.
In general high levels and/or reactive forms of C3A could lead to
a tendency for "flash set" behaviour. Both of these, which also
depend on the supply of soluble calcium sulfate, can have a
negative influence on the workability and slump retention
behaviour, which can often be more pronounced when concrete
admixtures are used.
Statistically C3A has been seen to influence strength. As a guide,
a 1% change in C3A content will be equivalent to around 0.5
MPa at 2-days and 1.0 Mpa at 28-days (EN196 mortar).
1.6.3.4 Ferrite
In general, the influence of ferrite content will not be as
significant as other parameters. The most notable effect
concerns colour and cements are manufactured with low levels
for "off-white" cements and very low levels in white cements.
The C4AF content can however create a barrier to silicate
hydration and hence reduce the strength development potential.
The effect depends on the burning, cooling and grinding history
of the clinker. Hence, in some cement, the enhancement of
ferrite hydration can contribute to increased silicate hydration.
The role of cement additives is known to be important in this
respect ("facilitated transport mechanism").
1.6.3.5 Alkalis
The alkali oxides K2O and Na2O have a very strong influence
on cement properties, notably concerning early and late
strength, workability properties and bleeding.
Where there is sufficient or excess SO3 present in the clinker the
resultant alkali sulfates will be readily soluble and this has an
important influence on calcium ion solubility and hence on the
rate of hydration. (See TIS MS004). As a guide, the early
strength (1-3 days) will be increased by around 0.8 MPa
(EN196 Mortar) for every 0.1% increase in the equivalent
Na2O level (Na2O + 0.658K2O). At the same time the late
strength (28-days) will be decreased by around 1.7 MPa.
1.6.3.6 SO3 Clinker (See Also Section 1.7)
As discussed above, the level of SO3 in the clinker is important
with respect to the alkali level and whether these are readily
soluble (as sulfate) or enter into the clinker minerals (and affect
reactivity).
The level of SO3 in the clinker also directly influences the
amount of "gypsum" required to achieve the target cement SO3
content. This in turn will directly influence the "grindability"
and hence the SSA (Blaine)/mill output relationship. As a guide
a 1% increase in "gypsum" addition equates to around 5%
increase in mill output at constant Blaine, (or 12m2/kg increase
in Blaine at constant mill output).
Since the level of clinker SO3 influences the amount of
"gypsum" added, the levels of the various forms of SO3 in the
cement can also be influenced (see below).
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 - alkali sulfate, K2SO4, Na2SO4
- calcium langbeinite,
2CaSO4 .K2SO4
- calcium sulfate, CaSO4
b) ex. added 'gypsum' -natural anhydrite, CaSO4
- gypsum, CaSO4 .2H2O
- hemihydrate, CaSO4 .1/2H2O
- soluble anhydrite, CaSO4
The major difference between these forms concerns their rate of
dissolution and hence the level of available soluble calcium
sulfate in the cement.

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The level of soluble calcium sulfate principally influences the
following:
- concrete water demand (concrete slump,
workability)
- slump retention or rate of slump loss
- silo set or pack set
- rate of strength development
1.6.3.9 Free Lime
The level of free lime itself can influence the initial reactivity
and setting behaviour, but more importantly, is a guide to the
level of burning (see below). It can also alleviate problems of
silo set (acts as a desiccant). (See also section 1.6.3.2 - Silicates).
Free lime target is typically between 1 and 2%. Higher levels
represent incomplete reaction between lime and silica (hence less
silicates for strength development), whilst lower levels indicate a
more complete reaction, but usually at the expense of hard
burning conditions and reduced strength development potential.
(See also section 1.6.3.11).
1.6.3.10 Fineness - Blaine, PSD
The cement fineness is naturally influenced by the mill output
but, as already discussed, can be influenced by other
parameters, such as SO3 level, filler level, etc. The principal
measure is the Blaine (m2/kg) but a more important one is the
particle size distribution (PSD). Often, this is not available but
the Blaine, in combination with a residue level (e.g. Alpine 45-
micron), can provide a good estimate of the PSD. (See TIS no.
MS005 and Section 3.3)
It should be noted that if influenced by parameters such as SO3,
prehydration, filler, etc, than these guidelines will not be valid.
It has also been noted that the more efficient milling systems
will result in a narrower PSD, i.e. lower 45-micron residue for a
given Blaine. (See also section 3).
1.6.3.11 Microstructure
The clinker microstructure can have a very strong influence on
cement performance but is less well defined on a routine basis.
It is influenced principally by:-
- raw material mineralogy
- raw feed fineness
- burning regime and temperature
- fuel type and fineness
- cooling
The microstructure is studied by microscopic examination.
As a guide, hard burning and/or slow cooling will lead to large
crystal sizes which can adversely influence both strength
development and grindability. In the extreme, for clinkers with a
high MgO content, the burning and cooling regime could lead
to expansive properties, due to large periclase crystals.
Clinker Microstructure Characteristics:
Alite Sizes, Typically 15- Smaller (<40) - better strength
100 microns Larger (>60) - less reactive
Burning Temperature Lower - better crystal sizes
1.6.3.12 Surface Properties
The cement surface characteristics can be expected to influence
the early age performance, for example, water demand,
workability, setting and early strength.
Significant levels of prehydration or carbonation, e.g. due to the
utilisation of outside stock clinker or high water injection rates
can result in a high fineness, but with a misleading influence on
strengths.
The only guide to surface properties readily available is the loss
on ignition (LOI). In general a 1% increase in the LOI will lead
to around a 3 Mpa reduction in 28-day strength and a 0.50
Mpa reduction at 2-days (EN 196 mortar).
The absence of any moisture can lead to high initial reactivity (a
possible contribution to the high reactivity of cements produced
in a finish roll press) and resultant reduced workability.
1.6.3.13 Cement Composition
Naturally, besides the clinker, other components can have a
significant influence on the final cement properties. Variations in
level and quality of non-clinker components could directly
influence setting, workability and strength performance. For
example, as a guide, a 1% change in limestone can influence 28
day strength by around 1%. See also section 9.
Non-clinker components can also effect the fineness/mill output
relationship and hence influence the evaluation of mill
performance.

In general, high levels of fineness will result in enhanced Cooling Regime Faster - smaller crystal size Insoluble residue (IR) can provide a guide to the presence of
strengths. The Blaine is a better indication of early strength, Crystal Impurities Purer crystals - less reactive some non-clinker components.
whilst the residue is a good guide to the 28-day strength.
Reduction Loss of SO3, Flowability problems
As a general guide, for OPC type cements (Type I), a 10m2/kg Raw Feed Fineness Coarser - difficult combinability
increase will be equivalent to around 0.30 Mpa (all ages) and a
1% increase in 45-micron residue will be equivalent to around - Siliceous - lower strength
0.35 Mpa at 2-days and -0.40 Mpa at 28-days. (See also TIS no. Calcareous - better strength
Raw Feed homogeneity
MS006). Heterogeneity - difficult
combinability

Porosity Lower - difficult grindability

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1. CEMENT CHEMISTRY

1.6.3.14 Other Properties Figure 12. "Rules of Thumb" Relationships.

Other parameters that can also have an influence on cement
performance include: Effect on
Incremental strength
Parameter Unit
MgO (e.g.. an expansive behaviour) change 2d 28d
Fluoride (e.g.. on setting and late strength) MPa MPa
Chloride (e.g.. on setting, early strength and
SSA m2/kg +10 0.30 0.30
corrosion)
P2O5 (e.g.. on setting behaviour) 45-micron residue % +1 -0.35 -0.40
Strontium, Barium (e.g.. on C2S stabilisation)
Eq. Na2O % +0.1 0.80 -1.70
Heavy Metals (e.g.. Pb, Zn) (e.g. on setting
behaviour) LOI % +1 -0.50 -3.00
Transition Metals (e.g. Cr, V, Mn) (e.g.. on colour)
C3S % +1 0.35 0.10
(See also Figure 5). Free Lime % +1 0.50 -1.50
SO3 % +0.1 0.50 0.10
Apart from MgO (and Mn2O3 and P2O5 where XRF analysis is
available) it is not common to have this data readily available. C3A % +1 0.50 1.00

However there are specific examples where trace levels can be Data concerning important properties, such as the clinker
important and relevant. microstructure, surface properties and the forms of SO3 in the
cement will be virtually impossible to readily acquire.
1.6.3.15 Conclusion
It will not always be possible to acquire all of this data, but the It is therefore recommended, where possible, that when samples
following should usually be readily available: are received and during plant trials data including the full
- Silicates (either as C3S, C2S or calculated from chemical analysis is recorded. This will usually be in the form:-
SiO2, Al2O3, Fe2O3 and CaO, SO3
SiO2 LSF Composition (e.g. non clinker levels)
and free lime)
Al2O3 S/(A+F) Gypsum details (e.g. Gypsum, anhydrite)
- C3A (either as C3A or calculated as above)
Fe2O3 A/F
- C4AF (either as C4AF or calculated as
CaO
above)
- Alkalis (Na2O and K2O) MgO C3S
- SO3 (for the cement and possibly the Mn2O3 C2S
clinker) TiO2 C3A
- Free Lime P2O5 C4AF
- Fineness (Blaine and possibly the Alpine, or SO3 Free Lime
other, residue) Na2O
- Composition (i.e. non-clinker components) K2O
The alkalis, SO3, fineness, silicates and composition are likely to LOI
be the most relevant parameters in understanding relative Insoluble Residue
cement performance. A table of the typical relationships for Blaine (SSA)
some of these parameters is shown in Figure 12. Residue (e.g.. 45 micron)

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1. CEMENT CHEMISTRY

1.7 'GYPSUM' - SOLUBLE CALCIUM SULPHATE It is difficult to distinguish between soluble anhydrite and natural Cement B: No anhydrite, moderate milling temperature -
1.7.1 Introduction anhydrite by analysis. (XRD can provide some indication). produces a moderate level of D.SO3.
The principal sources of SO3 in cement are: Cement C: Anhydrite present, high mill temperature - produces
a) ex clinker, i.e. alkali sulphates K2SO4, Na2SO4 As a guide, the following is likely: a moderate level of D.SO3.
calcium langbeinite 2Ca SO4 .K2SO4 Cement D: Anhydrite present, low milling temperature -
calcium sulphate CaSO4 In cement milling, below 80°C, little gypsum will dehydrate. produces a low level of D.SO3.
Between 80-100°C, up to around 50% of the gypsum will
Note: The calcium sulphate present in clinker, formed where dehydrate. Between 100-120°C, more than 50% will dehydrate 1.7.2 Dissolution of CaSO4
there is a large excess of SO3 over alkalis, will be equivalent to and some soluble anhydrite will be formed. Above 120°C, little The principal differences between the various forms of CaSO4
anhydrite (anhydrite I - slowly soluble). or no gypsum will remain and a greater proportion of soluble present in cement concern their rate of solubility.
anhydrite and hemihydrate will be found.
b) ex the added calcium sulphate ('gypsum'), which can be Gypsum gradually dissolves up to the level that represents a
present as: natural anhydrite CaSO4 In storage, any retained gypsum (ex the cement mill) can slowly saturated solution of CaSO4. Natural anhydrite dissolves more
gypsum CaSO4 .2H2O dehydrate at temperatures above around 70°C. slowly. Hemihydrate or soluble anhydrite dissolve very rapidly
hemihydrate CaSO4 .1/2H2O and form a super-saturated solution with respect to CaSO4. The
soluble anhydrite CaSO4 Thus a combination of relatively low milling temperatures but rates of solubility are shown in Figure 13b.
moderately high storage temperatures (e.g. milling at 100°C,
Note: (1)Natural anhydrite or anhydrite II. storage above 70°C) can result in silo problems as a result of Figure 13b. Dissolution Rates for Calcium Sulfate Forms
(2)Hemihydrate and soluble anhydrite (anhydrite III) gypsum dehydration, water migration and cement hydration
can be present as α and β forms. The β forms are (i.e. silo set and lump formation).
more reactive (in plaster properties terms).
Figure 13a provides a range of scenarios for a cement SO3
The β forms predominate where gypsum is processed content of 3.0% and a clinker SO3 content of around 1.0%
in a less than water saturated atmosphere at (assuming a typical level of alkalis of around 0.6 eq. Na2O).
atmospheric pressure, although some α forms will
also be present. Figure 13a. Examples of Cement Sulfate Forms.

To produce only the α forms, processing has to be Cement Type: A B C D

carried out at elevated pressures or at atmospheric Sources of SO3:
pressure in a water-saturated atmosphere.
Cement 3.0 3.0 3.0 3.0 Dissolution rates can be influenced by the presence of certain
Hence it follows that in cement milling the β forms Clinker 1.0 1.0 1.0 1.0 concrete admixtures and by other sources of SO4, e.g. from the
will be preferentially produced. alkalis.
Natural Anhydrite 0.0 0.0 1.0 1.0
Natural anhydrite is unaffected by the temperatures involved in
Gypsum 0.1 1.0 0.1 1.0
cement milling and storage.
Hemihydrate + Soluble Anhydrite 1.9 1.0 0.9 0.0
Gypsum will dehydrate to hemihydrate and soluble anhydrite.
The degree of this conversion will principally depend on Cement A: No anhydrite, high mill temperature - produces high
temperature, residence time and atmosphere. level of D.SO3 (i.e. hemihydrate + soluble
anhydrite).

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C E M E N T T E C H N O L O G Y N O
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:
- level of C3A (actual, rather than just according to Bogue)
- fineness
- surface freshness (e.g. presence of prehydration)
- alkali/sulphate balance
- crystal size (burning, cooling, etc.)
An excess of alkalis in the clinker can result in alkali modified
C3A which is more reactive.
Balanced retardation of the C3A will result in the formation of
fine grained ettringite (C3A.3CaSO4.32H2O). This provides
maximum mobility in fresh concrete thereby optimising
workability:
- BALANCED RETARDATION
An excess of soluble CaSO4 over that necessary will provide a
supersaturated solution of CaSO4 and resultant precipitation of
gypsum crystals. The morphology of these will not provide
maximum mobility and hence workability (initial) will not be
optimised. This can be more pronounced where the cement
content is high. Prolonged mixing is generally accepted as a
means to counter this loss of workability:
- FALSE SET
Insufficient soluble CaSO4 will allow the formation of
monosulphate (as opposed to tri-sulphate [= ettringite]) or even
C3A hydrates (4CaO.Al2O3.13H2O). Again, the morphology of
these will prevent maximum mobility being obtained. More
importantly, the rate of slump loss will be severe:
- FLASH SET
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T E S 2 0 0 5 15
A schematic of the above scenarios is shown in Figure 14.
Figure 14. Optimisation of Cement Sulfate.
Therefore, for any clinker, there is an optimum level of soluble
CaSO4 (i.e. D.SO3) which provides maximum initial workability
(or minimum water demand). This relationship is illustrated in
Figure 15 showing concrete water demand versus D.SO3.
Figure 15. Concrete Water Demand versus Soluble Calcium Sulfate.
1. CEMENT CHEMISTRY
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.
In general, low levels of D.SO3 and/or reactive clinkers (e.g.
excess alkalis over SO3) will result in a moderate to low initial
slump and severe rate of slump loss.
Conversely high levels of D.SO3 and/or less reactive clinkers,
whilst also producing a moderate to low initial slump, can
provide an overall better retention of slump behaviour.
With very high levels of D.SO3 (i.e. false setting) the initial
slump can be very low. But after mixing the slump can be
substantially improved.
In general, high w/c ratios (e.g. as a result of poor initial slump)
result in less of a slump loss. Conversely low w/c ratios can
produce a more severe slump loss.
Figure 16 shows slump behaviour over 60 minutes for two
cements. Slumps were determined at 6, 20, 40 and 60 minutes,
in each case after a short period of re-mixing.
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1. CEMENT CHEMISTRY

Figure 16. Slump Loss. slump of only 16mm. However, the slump at 60 minutes is now
18mm, i.e. back to the level of the first cement.

A summary of the principal points concerning cement SO3 are

shown in Figure 17.

Figure 17. Key Points concerning Soluble Calcium Sulfate.

1 SO3 present in cement as:
Ex. clinker -
alkali sulfate
calcium langbeinite
calcium sulfate
Ex. added "gypsum" -
natural anhydrite
gypsum
hemihydrate
soluble anhydrite
A - Cement with Mill temperature ~100°C D.SO3 ~ 1.0%
2 Gypsum dissolves slowly
B - Cement with Mill temperature ~80°C D.SO3 ~ 0.4%
Natural anhydrite dissolves very slowly
C - Laboratory heat treated Cement B D.SO3 ~ 1.6%
Hemihydrate & soluble anhydrite dissolve very rapidly

The cement milled at 95-100°C had a level of D.SO3 of around
1.0% and gave slumps of 40 and 17mm at 6 and 60 minutes
respectively. In order to achieve slumps of 40mm, w/c ratios of
0.60 and 0.64 respectively would be necessary. Therefore the
slump loss was equivalent to an increase in water demand of
7%.
The cement milled at 80-85°C had a lower level of D.SO3 of
around 0.4% and gave slumps of 25 and 7mm respectively.
Again, to achieve slumps of 40mm, w/c ratios of 0.62 and 0.69
respectively would be necessary. Therefore the slump loss was
equivalent to an increase in water demand of 11%.
The third curve shows the results of this latter cement after
laboratory heat treatment. The D.SO3 was raised to around
1.7%. The cement now false sets and there is a very low initial
3 SO3 ex. hemihydrate & soluble anhydrite has been referred as "D.SO3"
4 Clinker reactivity is strongly influenced by:
C3A level
Cement fineness
Surface "freshness"
Alkali:sulfate balance
Thermal history (e.g. crystal sizes)
5 Excess alkalis over sulfate results in a more reactive clinker
6 Need to consider availability of soluble calcium sulfate
Need to consider clinker "reactivity"
Need to match sulfate availability to clinker reactivity
7 Balanced retardation of C3A provides optimum water demand
Excess D.SO3 produces "FALSE SET" tendency
Insufficient D.SO3 produces "FLASH SET" tendency
"FLASH SET" tendency probably more negative

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