CEMENT and CONCRETE

Production and Quality

Principles and Practices

Ahmed Saad
Cement and Concrete Expert 1
Introduction
Dear brothers and distinguished colleagues
I prepared this course due to the importance of the topic we are talking about, which is
the cement and concrete industry, and trying to understand the principles of these
industries and the influences that affect them so that we can succeed in the important
and vital goals for all of us, which are reducing costs and reducing emissions. Due to the
high cost of fuel, the lack of raw materials and their consumption, and also the high
amount of carbon dioxide emissions, the search for alternatives to fuel and raw materials
has become the main concern of those in charge of these industries. This will only happen
by beginning to understand the principles of these industries so that all work is on an
accurate scientific basis. Therefore, I began preparing this course to be of assistance to
researchers, students, and those interested in these industries. I have provided a
simplified explanation of most of the influences that affect these industries in terms of
quality, operation, production and process, and I would almost claim that it is a unique
course in terms of addressing each influence and its effect on quality and operation
together, and even the effect of quality on operation and vice versa for each factor Of
these factors.
2
Contents

3
Table of Contents
A. Raw materials for Cement Production-------------------------------------------------------------------------------------6
1. Raw Materials Evaluation---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------7
2. Chemical and Physical Properties of Raw Materials------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------11
3. Raw Mix Design and Setting of Targets---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------15
B. Factors affecting Clinker, Cement and Concrete Properties-------------------------------------------------------17
1. Raw Mix Fineness---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------18
1.1. Importance of Raw Mix Fineness------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------19
1.2. Effect of Raw Mix Fineness---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------20

2. Thermal Profile-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------21
2.1. Thermal Profile and Short Burning Zone Effect----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------22
2.2. Effect of Thermal Profile on Calcination Degree and Fuel Consumption -----------------------------------------------------------------------------------------------------------------------------------------------------------------23
2.3. Temperature profile ( Gas and Material Temperature)------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------24
2.4. Effect of Thermal Profile on Clinker Grindability --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------25

3. Volatilization-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------26
3.1. Volatilization Process-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------27
3.2. Identification of Volatilization Phenomena---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------28
3.3. Cl % and SO3 % in hot meal-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------29
3.4. E-factor ( Evaporation Factor)-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------30
3.5. Important Equation for understanding Volatilization process -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------31
3.6. The Affinity of Volatiles Oxides--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------32
3.7. Sulphur Volatilization and Ring Formation ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------33
3.8. Types of Rings---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------37
3.9. Solving of Sulphur Volatilization-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------39
3.10. Solving of Alkalis and Chloride Volatilization ( Effect of By-pass)---------------------------------------------------------------------------------------------------------------------------------------------------------------------------43
3.11. Effect of Alkalis and Sulfates on Quality--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------51
3.12. Effect of Combustion and Flame on Volatilization ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------57
3.13. Effect of Combustion Air------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------61
-4
3.14. Combustion Sensors------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------64
4. Clinker Reactivity and Strength Development----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------68
4.1. Effect of Burning and Cooling regimes on Clinker Phases --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------69
4.2. Reactions in the kiln system-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------72
4.3. Clinker Phases Investigation-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------86
4.4. Real and Potential Clinker Phases-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------97
4.5. Clinker Phases Polymorphism---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------101
4.6. Derivations of some equations and Bogue equations-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------106
4.7. Clinker Phases Characteristics---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------107
4.8. Liquid Phase---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------110
4.9. Free Lime--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------114

5. Cement Hydration and its effect on Cement and Concrete properties---------------------------------------------------------------------------------------------------------------------------------------------------124

5.1. Cement Hydration Process--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------125

5.2. Products of Cement Hydration Process---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------133
5.3. Properties of Hydration Products----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------143
5.4. Effect of Minor Phases and Gypsum on Hydration Process----------------------------------------------------------------------------------------------------------------------------------------------------------------------------149
5.5. Effect of Gypsum on Cement Setting-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------154
5.6. Dehydration of Gypsum-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------162
5.7. Effect of Alkalis on Cement and Concrete----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------165
5.8. Heat of Hydration---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------173

6. Alternative Raw Materials( AFR) and Supplementary Cementitious Materials(SCMs)----------------------------------------------------------------------------------------------------------------------182

6.1. Slag as AFR and SCMs--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------183

6.2. Classification of Slag and its Applications----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------188
6.3. Air Cooled Slag Utilization in Cement Production----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------196
6.4. GGBFS (Ground Granulated Blast Furnace Slag)-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------201
6.5. Properties of GGBFS----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------209
6.6. Standards and Specifications of GGBFS-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------214
6.7. Blended Cement and GGBFS in Concrete----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------219
6.8. GGBFS Concrete----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------234
6.9. Pozzolana-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------245
6.10. Pozzolana Reaction and Reactivity------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------257
6.11. Properties of Portland Pozzolana Cement PPC--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------264
5
7. Alternative Fuels--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------269
7.1. Refused Derived Fuel (RDF) as an example for AF--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------279

References--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------288

6
A. Raw Materials for Cement Production

7
1. Raw Materials Evaluation
Minerals of natural origin as well as industrial products/by-products can be used for cement production as long as the main components of
cement (Cao, SiO2,Al2O3,Fe2O3)are present in a required proportion on mixing and the impurities or undesirable components like
alkalies, sulfur, chlorides, MgO etc. are below the allowable levels to ensure cement quality and operational stability.
Cement mixes vary from 'natural cement rock', a single component which, as mined, contains appropriate proportions of all the
required minerals, to 2- or 5 component mixes comprising one or two grades of limestone, shale or clay/ silcastone
, and one or more additives to augment SiO2, Al203 or Fe2O3 levels.
Raw meal typically contains 78-80% CaCO3 so that limestone can only fall close to this level to the extent that it also contains
the other ingredients.
It is essential to have sufficient flux/liquid (Al, Fe, Mg, F) to promote fusion in the kiln, but MgO should not exceed 4-5% or the cement
may be expensive. Excess alkalies (K, Na) affect both kiln operation (build-ups) and product quality (alkali-aggregate reactivity).
Excess sulfur causes kiln build ups and limits the addition of gypsum which may result in setting problems.
The stoichiometric ratio of alkalies to sulphur is normally kept between 0.8-1.2.
Excess Cl causes serious build-up problems for preheater operation.
Apart from chemistry, grindability is also a factor in selecting raw materials. In particular, silica additives containing large-grain quartz are
very difficult to grind and can result in hard burning and high fuel consumption. If quartz silica is employed it should, preferably, have a
natural grain size of less than 50% µ. Generally, cement plants are located on limestone deposits and shale or clay is sufficiently abundant
for most plants to mine this locally. Additives are usually brought in small quantities.

8
Main Components of Cement

1- Lime Component ( Calcareous)

Limestone:
Common forms of calcium carbonate used as raw material for cement manufacturing are limestone and chalk. Limestone is of predominantly fine grained
crystalline structure, its hardness is between 1.8 to 3.0 of the Mohs scale of hardness and specific gravity 2. To 2.8. Limestone usually contains admixtures of
clay substance or iron compounds, which influences its color. Only the purest varieties of limestone are white.
Chalk:
Unlike limestone chalk is characterized by a soft earthy texture. It is a sedimentary rock which was formed during the cretaceous period in geological time, it is
relatively young geologically.
Marls:
Limestone with admixtures of silica, clay substance and iron oxide are called marls. Marls form the transition element to the clay. Because of the wide
distribution of marls, they are frequently used as raw material for cement production.

2- Clay Component ( Argillaceous)

The second important raw material for cement production is clay. The main component of clay is formed by hydrous aluminum silicates. The chemical
composition of clay may vary from those close to the pure clay, to that containing a significant amount of admixtures as iron hydroxide, iron sulfide, sand,
calcium carbonate, etc. Clay is used as an argillaceous component of raw mix.

3- Corrective Ingredients
If the primary components needed in the cement raw mix are not present in the required percentage, the corrective materials are used as additives. For
example to augment SiO2 component, sand, high silica clay, etc., is used as additive. Similarly to augment Alumina content in raw mix , bauxite or alumina rich
clay is used and to augment for iron component, Iron Ore, pyrite cinders, etc. are used as additives.

9
Minor Components
1- Magnesium Oxide (MgO) 0-5%:
MgO combines up to 2% by weight with clinker phase and beyond that it appears as free MgO (periclase). Crystalline matured periclase reacts
with water to form Mg(OH)2, but this reaction is proceeds slowly, while the other hardening reactions are already concluded. Since the Mg(OH)2
occupies a large volume than the MgO and is formed on the same spot where the periclase particle is located, it can split apart the binding of the
hardened cement paste, resulting in expansion cracks. Fast cooling of clinker (quenching) in cooler helps to freeze MgO in a glassy form which
remains as it is and does not get hydrated to give expansion problem in cement paste.

2- Alkalies (Na2O and K2O) :

Some of the Na2O (Sodium oxide) and K2O (Potassium oxide) is built into the clinker menials C3A, C4AF and C4AF.Most of the remaining will
remain water soluble. An increased percentage of alkalies, particularly water soluble alkalies influences adversely the strength (28 Day). Low alkali
cements should have Na-equivalent below 0.6% by weight. If alkalies are not balanced by sulfates, they will remain highly volatile and can
accumulate in the circulation between kiln and preheater increasing troubles of kiln inlet, kiln riser coatings. Main sources of alkalies are raw
materials and coal.

3- Sulphur (SO3):
Sulphates may be present in clinker up to about 3%. Sulphur in raw materials increases SOx emission and cause build-up in preheater. Sulphate can
form a stable compound with Potassium (K2SO4) and to lesser extent Sodium (Na2SO4). The sulphates in the clinker comes from raw materials
and fuel. Sulphates must be balanced with alkalies otherwise an excess or deficiency of sulphates with respect to alkalies will increase volatile
circulation phenomena.

4- Cl Chlorides:
Chlorides form stable compounds with the alkalies and are more volatile than sulphates. About 1% in hot meal is considered maximum for smooth
operation. Clinker can contain about 0.012 to 0.023% Cl. A bypass generally known as alkali bypass may be required to vent out chlorides from kiln
system. 10
Calcium Silica Alumina Iron
Limestone Quartzite Bauxite Iron ore
Marble Rice-hull ash Clay Mill scale
Shale Sand Copper slag Ore washings
Chalk Sandstone Fly ash Pyrite cinders
Marl Clay Fuller’s earth
Aragonite Fly ash Granodiorite
Calcite Fuller’s earth Loess
Cement-kiln Loess Ore washings
dust Marl Slag
Fuller’s earth Ore washings Staurolite
Alkali waste Shale
Seashells Slag

11
2. Chemical and Physical properties of Raw Materials
CaO is supplied by the calcareous (carbonatic) component and SiO2 Al2O3 and Fe2O3 by the argillaceous (siliceous) components.

Calcareous Component :
The calcareous component is usually classified according to its chemical Composition i.e. according to its carbonate content ("titration value").
The carbonate content - expressed as CaCO3 content is normally higher than 80 %, the sought after CaCO3 content of the cement raw mix.

Argillaceous Component:
The term "argillaceous" covers the field of cement raw materials with those chemical constituents which are contained in insufficient quantities in the
calcareous component, i.e. argillaceous materials basically supply SiO2, Al2O3 and Fe2O3 ("silica", "alumina" and "iron"). Because of the various
mechanisms in the formation of argillaceous rock, a large number of these rock types are considered as potential cement raw materials.
Crystallographic Characteristics:
Minerals with strong lattice forces which impair the burnability are : quartz and feldspars.
Minerals with weaker lattice forces and thus better burnability are : clay minerals.
Materials with a highly disordered structure, showing high reactivity are : amorphous and glassy rocks such as tuff, lava, amorphous silica, etc.
Mineralogical Characteristics:
In many cement raw mixes, the minerals are in a stable condition with low free energy, and therefore, a low reactivity. To produce clinker minerals much
energy is needed to destroy the structure of the raw materials and to form new structures (clinker minerals). The following phenomena improve the
reactivity of minerals: · impurities (atoms, ions, molecules) disturbing the ideal crystal lattice · lattice defects They give the crystal structure a higher degree
of disorder which is equal to a lower degree of crystallinity: ideal crystal real crystal glass (ordered lattice) (partially disordered lattice) (strongly disordered
lattice).
Reactivity is opposite to degree of crystallinity

12
Chemical Parameters of Potential Cement Raw Materials

Components Parameters to be checked Limits (guide lines)

Carbonate titration as CaCO3 >80 %

MgO content
<4 %
Calcareous materials
SO3 content Examples of Chemical Analysis of Potential Cement Raw Materials
(Limestone, etc.) <1 %
P2O5 content
<1 %
Cl content <0.1 %
depending on materials
Total alkali as Na2O equivalent
cement type
(Na2O + 0.66+ K2O)
Argillaceous materials > 10 %
Al2O3 content
(Clay-Marl)
SO3 content
<1 %
Cl content <0.1 %
Correctives

For Aluminium (Bauxite, Laterite)

Al2O3 content >25 %

Fe2O3 content
For Iron ore (Pyrites Ash) >60 %
SO3 content
<5 %
For Silicon (Quartz, Sand) SiO2 content
>80 %

CaCO3 content >90 %

For Calcium (High-grade Limestone)
MgO content <2 %

Additives

Gypsum SO3 content 13

>35 %
Calcium Carbonate Minerals
Mineral names Crystal System Common Specific gravity Dissociation
with formulae Substitution temperature
(°C, at 760 mm
pressure and
100% CO2
removal)
Calcite Hexagonal Mn, Fe, Mg 2.72 898
(CaCO3) rhombohedral
Aragonite Ortho-rhombic Sr, Pb, Zn 2.94 425 (to calcite)
(CaCO3) 898
Dolomite Hexagonal Fe, Mn, Co, Zn 2.86 725 (MgCO3)
(CaMg(CO3)2) rhombohedral 890 (CaCO3)

 Highly crystalline limestone dissociates at

higher temperature than amorphous variety.
Aragonite Dolomite Calcite
 The rate of dissociation and reaction
temperature are directly related to the grain size.

14
 Silicates Minerals
single tetrahedron - nesosilicates : olivine and garnet groups
double tetrahedra - sorosilicates : epidote group
rings - cyclosilicates : tourmaline, beryll
single and double chains - inosilicates : pyroxene and amphibole groups
sheets - phyllosilicates: mica and clay mineral groups
framework - tectosilicates: feldspar group

 Clay are essentially hydrous alumino-silicates constituting the

combined source of SiO2 and Al2O3.
Muscovite Montmorillonite Chlorite Illite Kaolinite  Clay are extremely variable in composition and thermal
behaviour.
 Clay under go dehydration, dehydroxilation breakdown of
crystal structure releasing Al2O3 and SiO2 in reactive form.

The mineralogical nature and characteristic of silica

have a
Silica strong influence on the reactivity of cement raw mix.
Silica of Silica of
Quartz Chalcedony Opal Cristobalite Tridymite from
Feldspar Mica
Slag Silicates reacts more readily than free silica or
uncombined
silica such as quartz, flint, chert.

15
3. Raw Mix Design and Setting of targets
Raw mix design refers to the raw materials' quantitative proportions to achieve clinker with the desired chemical and
mineralogical composition and cost.
The aim is producing reactive clinker through setting targets.

Impact/influence of ratios
2- Silica Modulus SM = SiO2/ ( Al2O3+Fe2O3)
1- Lime Saturation Factor LSF
= 100 * Cao/ ( 2.8* SiO2+1.18* Al2O3+0.65* Fe2O3) Typical silica ratio 2.0-2.9
Usually in the range 93 - 98 Ratio of solid to liquid: SiO2 in solid phase, A+F in liquid phase
Proportions of C3S and C2S Kiln process (coating, rings) sensitive to SR changes
Ease of combinability Increase in SM:
Higher LSF more difficult to burn - Free lime
- harder burnability (more C3S)
- Decrease in nodulisation
- Protective coating on refractory decreases

3- Alumina Modulus = Al2O3/ F2O3

Typical alumina ratio 1.5-2.5
Liquid phase at high temperature promotes the formation of clinker compounds
Lower alumina ratio leads to easier burning
Increase in AM - more liquid phase initially
Higher C3A content for higher AM 16
Example for Mine Planning Tools – Raw Mix

Define unit quality

(Block Model data)

Set Quality Targets

(LSF, SR C3S...)
Results of Raw Mix
Simulation
17
B. Factors affecting Clinker,INFLUENCES
WHAT Cement and Concrete Properties
CONCRETE PROPERTIES?
Raw materials

•chem comp.
•alkali, MgO Raw meal
•sulphate •proportioning
•chloride of different Kiln Cooling Grinding Storage
•metals raw materials
•fineness •atmosphere •speed of •fineness •aging
Fuels •temp. profile cooling •sulfate add.
•free-lime •mineral add.
•sulphur
•chloride
•metals

Fast Track Block 2 - Week 1 - 1999 / QC/SPC/QA / Institut Cimentier / 17

1- Raw Mix Fineness

19
1.1. Importance of Raw Mix Fineness
The principle is :
• Reducing raw mix rejects lowers burning temperature and grinding energy. This is particularly the case with siliceous rejects.
• This action is also beneficial to strength properties.
• This is not only in clinker or cement, but you will find this principle in most industries that depend on Burning, as the raw mix that is introduced into the
kiln, the softer it is, the easier the burning, the easier the reaction, and the grinding of the clinker also after burning is easier, and therefore the mechanical
properties of the cement and compressive strength will be higher.
There are some questions that may come to mind when talking about the fineness of the Raw Mix and its importance in the industry:
1- How is the fineness of the Raw Mix controlled?
2- How does the fineness of the Raw Mix contribute to clinker grinding?
3- How does the fineness of the Raw Mix affect Carbon and Cost reduction?
The answer to these questions is as follows:
• The first question:
The fineness of the Raw Mix is controlled starting from the selection of the raw materials, where accuracy must be investigated so that it is necessary to
ensure that there is no free SiO2 -or minimize it as possible as you can- in any of the raw materials, and to make sure that the SiO2 present is all in the form of
compounds either combined with Al2O3 or with CaO or F2O3 or any other oxides.
With regard to operation and its effect on fineness, work must be done to raise the efficiency of Separator and grinding efficiency in terms of the correct
distribution of grinding media in the Ball mills or the stability of the material bed in the Vertical mills.
• Second question:
When the Raw Mix is finer, the reaction inside the Kiln will be easier, and the Clinker produced will be more homogeneous, and therefore there will be no
Clusters in it which will enhance the grindability.
• The third question:
When the Raw Mix is finer, it is easier to burn, and therefore there is an opportunity to reduce the Fuel used, which leads to lower Carbon and lower Costs.
Also, when improving the strength of Cement and the mechanical properties of Cement by improving the fineness of the Raw Mix, then it is possible 20
to reduce
the fineness of Cement by increasing production or by reducing the grinding energy inside the cement mill, all of which reduces the cost.
1.2. Effect of Raw Mix Fineness
58.5
Oil
58
(l/t Raw mix) kWh/t

70
57.5

57

56.5
60

56
% > 100 µm residue
>100m residue (%) 55
55.5 12 14 16 18 20 22
8 12 16 20

Raw-Mix Fineness versus Clinker T

Effect on Burnability Effect on grinding energy
Clinkering Temperature

% > 100 µm residue

Particles > 90 um % 21
Effect on clinkering temperature
2-Thermal Profile

22
2.1. Thermal Profile and Short Burning Zone Effect
This principle can be summarized as follows:
Short Thermal Profile promotes grindability and strength development. Short Burning Zone means maximum reactivity of the clinker.
The thermal profile is affected by a number of factors:
The raw mix burnability and the kiln’s heat consumption, the type of fuel and its preparation, ,the burner and its settings, cooler operation (via secondary air temperature), kiln
operation, especially the draught and fuel settings, but also, rotational speed.
The most important factor is the oxidizing conditions in the kiln , that means optimum O2 % in the kiln back end in order to ensure good combustion and the reactions are
running smoothly.
Why we must have Oxidizing conditions in the system and avoid Reducing conditions?
Because Reducing conditions will cause:
- C3S formation is hampered resulting in lower C3S content.
- Presence of FeO increase C3S instability - alite degrades to belite and free lime with slow cooling.
- Alkali sulphate are dissociated with SO2 lost from the system.
- Uncombined Alkali takes up atmospheric water upon exposure, leading to air-setting of cement in silo and poor workability.
- Increased burning temperature is required to maintain free lime.
- The iron in the reduced state will not form the C4AF but other products such as FeO, Fe2S or even Fe. The Aluminum that would have formed C4AF is now available to form more
C3A.
These causes only in the clinker quality we did not talk about kiln operation and environmental issues when you have Reducing conditions .... ( CATASTROPHES).
Let us now talk about Calcination degree ( CD ) and its effect on the length of the Burning Zone:
Most Kiln operators and Production Managers want this value to be no less than 95%.
Do you know, gentlemen, that in this case you can make clinker in the calciner and at the back end of the kiln?
Whenever the value of calcination is as low as possible (I mean here 94% or 93% or even 92%) , Of course, this depends on many factors, the most important of which is the
absence of unburned materials in the cooler (Flush), but did you know that the degree of calcination, if it is 92-93%, then the Burning Zone will be short and strong, and this of
course depends on the strength of the flame.
23
Please you can try it now , if your target for Calcination Degree is 95% , you can make it 94.5 % and see the impact and then try another steps.
 2.2. Effect of Thermal Profile on Calcination Degree and Fuel Consumption
• Through what we have referred to, it is possible for you to link all the effects together, and through that you can do some trials that will
reduce Carbon and Cost.
• There is a close relationship between Fineness of the Raw Mix , Thermal Profile , Calcination Degree, the Fuel Consumption , and the Quality
of Cement. You can link all of that.

• When you conduct any trial first, change only one factor, let it be for example feeding the Kiln, and fix the rest of the factors as much as
possible, and the change is very simple at the beginning, for example, you increase the feeding from 300 t/h to 301 t/h, and you follow up all
the factors for a period Two or three days, then you decide after that the next step is to do another increase or return to the previous number
or increase.

Two things must be mentioned here:

• The first:
It is necessary to take into account the amount of fuel in the Kiln Main Burner, which is 35-40% of the total fuel, and the amount of fuel in the Calciner
Burner, which is 60-65% of the total fuel , this is the optimum.
There must be a daily tracking of these values, and the more this percentage is in the Kiln Main Burner than 35%, the better, and in the Calciner Burner is less
than 65%, the better, as this will help reduce the Degree of Calcination and strengthen the Burning Zone, of course, with the availability of the necessary
oxygen.
I know that these percentages are difficult to achieve, but continuous attempts to improve them will give you very good results
• The second:
As we mentioned before, thinking about change is not for just change, but for a specific purpose and for a known and agreed upon target. And my talk now to
the junior engineers, you must have thinking outside the box.
For example, thinking like this:
If we change the Fineness of the Raw Mix and make it finer, then it will be easy to burn, and when it enters the Calciner and on the same Fuel used, the Kiln
Feed Rate and the I.D Fan speed, the Degree of Calcination will increase, and therefore we can increase the Kiln Feed Rate if possible and the I.D Fan is not at
full speed.
If the I.D Fan is at maximum speed, then the Fuel used in the Calciner is reduced, and with time and with the ease of Burning, a lower Degree of Calcination is
obtained, and therefore a Strong Burning Zone, Homogeneous Clinker, and Cement with considerable and developed Strength. 24
2.3. Temperature Profile ( Gas and Material Temperature)

Temp C
2000 Gas
Cooler

1000 Material

Cooling Burning Calcining Preheating Drying

zone zone zone zone zone
25
 2.4. Effect of Thermal Profile on Clinker Grindability

kWh / t

(kWh/t)
75 75

70 70

65 65

60 60

55 55

50 50

°C
45 45 Nm
1050 1100 1150 1200 1250 1300 1350 1400 1450 600 700 800 900 1000 1100 1200 1300 1400 1500
Burning zone temperature Kiln drive torque

Effect on Clinker Grindability

26
3-Volatilization

27
3.1. Volatilization Process
Burning atmosphere and volatilization:
This principle is:
Steady production requires an oxidizing atmosphere because a reducing atmosphere increases volatilization, causing both « cyclical » operations and sulfate and alkali fluctuations,
hence producing a non-uniform clinker.
Raw mix and fuel carry minor elements (sulfur, alkalis and chlorine) which volatilize in the kiln, condensate on cold areas, thus creating a circulating load of chlorides and sulfates
combined to alkalis and eventually to CaO forming build-ups that must be destroyed. Chlorine volatilizes almost entirely (volatilization coefficient > 99%), and condensates in the
upper cyclones introducing large material flow disturbances (by promoting the emergence of a liquid phase at low temperature). Combustion optimization has no effect on its
behavior and the induced effects. As chlorine intakes reach the 300 g/t of clinker level, the installation of a gas by-pass is indispensable for tower kilns.
Sulfur has a volatilization coefficient varying with the nature of the formed salts, the atmosphere and burning temperature.
The principal reactions involving sulfur, alkalis and Calcium:
- K2O +SO2+1/2O2 <====> K2SO4
- Na2O +SO2+1/2O2 <====> Na2SO4
- CaO +SO2+1/2O2 <====> CaSO4
The Calcium reaction with sulfur is produced in a significant way when the S/A molar ratio < 1. (SO3 / Alkali ratio )
CaSO4 is much more unstable under burning atmosphere and temperature than K2SO4 and Na2SO4 , wherefrom the different plant sensitiveness to volatilization problems based on
the S/A molar ratio:
- S/A < 1.2, very few volatilization problems.
- S/A > 1.2, potential volatilization problems if combustion is out of control.

Let us just to give you some important tips to understand and overcome this issue:
- If the Combustion is carefully controlled , the Volatilization problems can be overcomed.
- The Burning Atmosphere must be oxidizing.
-High sulfur cycles lead to poorly granulated clinker and therefore to dust formation. The dust carries the heat from the burning zone to the kiln inlet, so that the cycles of the volatile
elements further increase due to longer residence time at high temperatures. 28
3.2. Identification of Volatilization Phenomena
• How can the operator identify this phenomenon and if he has a volatile cycle or not:
The torque of the Kiln will be ups and down as a result of the fall down of the build-ups and rings and its formation and so on.
Analysis of Hot Meal samples where it will be noticed an increase in the SO3 % in the samples and a decrease in the clinker samples.
The situation will be very bad if this is accompanied by an increase in Cl % in the Hot Meal samples and a decrease in Cl % in the By-Pass Dust
samples
Also, the tendency of Build-ups and Coating formation in the Kiln inlet, Riser Duct and Calciner is very high. This is noticed by the Supervisors
who are working in the demolishing of the coatings and the pressures drop and temperatures that ups and down periodically. IN SIMPLE
WORDS, YOU ARE LOOSING THE KILN CONTROL. All of these parameters together are the evidence that you have Volatile Cycle.

• One of the important things that must be taken into account when dealing with this phenomenon is the calculation of
Mass Balance, meaning:
The Input equals the output, and in the attached file you will find a simple example of that for SO3 by which you can be sure of your analysis
and the system what is going on and decide upon that. The numbers in the file are approximate numbers just to understand the equations.
It must be taken into account if the Kiln dust is returned to the Kiln or is it taken out to the stake because it has SO3 % of course.

29
 3.3. Cl and SO3 in hot meal

SO3 balance

Inputs
tph % SO3 tph SO3 tpd
Kiln feed 340 0.25 85
Total Fuel 19 5 95
Raw mill dust mill 1 6 0.3 1.8
Raw mill dust mill 2 6.15 0.3 1.845
Total 371.15 183.65

Outputs
212.704
Clinker 212.7 0.78 165.9 5104.896 Clinker factor 1.598465473
By-pass dust 8.00 2 16.0 192.0 tph cyclone effy
RM 1 200 0.97
Total 181.9 RM 2 205 0.97

Difference 1.7 LOI kf 0.3544 %

LOI dust bp 0.15 %

Cl and SO3 Concentrations in the Hot Meal samples SO3 balance

30
3.4. E-factor ( Evaporation Factor)

KO Na O Cl K SO Excess
2 2 2 4

SO
Na SO 3
2 4

E 0,10-0,40 0,10-0,25 0,99-0,996 0,2-0,9 0,50-0,75

Evaporation Factor or Volatility Factor

31
3.5. Important Equations for understanding Volatilization process
1- Sulfate to Alkali Ratio:
SO3/ALK= (SO3/80)/((K2O/94)+(Na2O/62)-(Cl/71))
The favorable range of this ratio is 0.8-1.2 , below 0.8 you will have more Alkalis in the system causing Alkali Volatilization ( Operation problems , Clinker quality problems and Concrete
quality problems).
Above 1.2 , you will have Operation problems , Clinker Grindability problems and Gypsum addition in cement mill problems.
I would like here from everyone who is interested in these equations and chemical reactions from production, operation, process, quality and others engineers not to pass by these
complex equations and not to know the numbers and constants in them, for example:
The number 80 under the SO3, where did it come from? It is the molecular weight of SO3 ( 32 + 3 * 16 ) , And so on for all the other numbers.
2- Evaporation Factor or Volatility Factor: ( SO3 for example)
= 1- ( % SO3 in Clinker / % SO3 in Hot Meal)
For example :
SO3 % in clinker is 1
SO3 in hot meal is 2
so the E or V factor for SO3= 1-(1/2)=0.5
If SO3 in clinker is 0.8
SO3 in hot meal is 2.2
so the E factor for SO3 = 1-(0.8/2.2)=0.62
The Evaporation or Volatility increased by 12% . This equation is applied for all the Volatile matters ( Na2O , k2O , Cl and SO3).
3- Excess SO3 :
= 1000*SO3-850*k2O-650*Na2O (gr SO3 / 100 kg clinker)
If the SO3/ALK ratio exceeds 1.2 it is held that an amount of sulphur is present in the kiln material which is not covered by alkalis, and as "excess" sulphur will form CaSO4.
The limit on excess sulphur is given to be in the range of 250 – 600 g/100 kg clinker. For easy burning raw mix the high value 600 gram SO3/100 kg clinker should present
32
no problems for the kiln operation, but for a hard burning raw mix the lower value is the limit. Above these limits, the sulphur will give rise to coating problems in the preheater tower.
3.6. The Affinity of Volatiles Oxides
• Chloride reacts primarily with the alkalis, forming NaCl and KCl. Any chloride in excess of alkali will combine with calcium to form CaCl2.
• A part of the alkalis in excess of chloride combine with sulphur to form Na2SO4, K2SO4 and double salts such as Ca2K2(SO4)2.
• Alkalis not combined with chloride or sulphur will be present as Na2O and K2O embedded in the clinker minerals.
• Sulphur in excess of alkali combines with CaO to form CaSO4.

33
3.7. Sulphur Volatilization and Ring Formation
The addressing of the effect of these volatile elements and their compounds on the operational process is very important, and let's start with SULPHUR:
The day to day kiln operation can become seriously hampered by formation of build-ups in the system when the concentration of circulating components
increases in the kiln system. As a consequence of the build-ups in riser pipes and cyclones, the pressure drop in the system increases and maintaining the draft
in the kiln becomes increasingly difficult.
Another consequence of the reduced draft will often be that the maximum kiln production is reduced. It is very tempting to compensate for the reduced draft
in the kiln by operating with less excess air, but this will only make things worse as the circulation of sulphur increases significantly at low oxygen levels.
High levels of sulphur circulation will increase the tendency of the formation of a very dusty clinker.
The operational problems encountered with a dusty clinker are foremost linked with the moving of heat from the burning zone up towards the kiln inlet, as
the hot dust is transported with the smoke gas. This creates an undesired heating of the zones before the burning zone and has a detrimental effect on the kiln
coating, leading to the formation of an unstable coating at the burning zone inlet.
The resulting kiln operation is poor with symptoms as:
• Frequent kiln stops due to cyclone cleaning and clogging problems
• Higher heat consumption
• Reduced kiln production rate
• Short life time of refractory lining

The mechanism of Build-ups and Ring Formation:

-The hot dust particles will be sticky and tend to agglomerate on solid subjects like kiln walls , chains, or lower cyclones or preheater tower.
-The Sulphur build-up usually occurs where the temp is bet 800 and 1100 C in those build ups.
The following compounds of sulphate salts (Sedimentary Rocks Minerals) are commonly found:
Arcanite K2SO4, Anhydrite CaSO4, Glaserite K3Na (SO4)2, Ca-Langbeinite K2 Ca2 (SO4)3, And sulfate Spurrite Ca2 ( SiO4)3 CaSO4
THESE ARE ROCKS ON THE WALLS...?
The Build-ups and Rings then formed according to the circulation of Sulphur compounds.
34
 Sulphur Re-circulation
1%
in

1-4%
1%
Out

35
Condensation in the kiln system and Ring formation
STACK FUEL

PRECIPITATOR CONDENSATION
DUST ON TO
DISCARDED PRECIPITATOR
DUST
CONDENSATION
VOLATILISATION
IN KILN/PREHEATER IN BURNING
ZONE

PRECIPITATOR
DUST RETURNED

RAW FEED KILN CLINKER

FEED

FUEL RAW FEED RECIRCULATING PRECIPITATOR 37

LOAD DUST
3.8.Types of Rings ( Sulphur Rings)
1- Sulphur Ring
Sulphur-induced rings are formed when the molar sulfur to alkali ratio in the system is more than 1.2. In such cases, there is a considerable amount of free SO3
circulating in the kiln. At a certain concentration level in the kiln gas, sulfation of the free lime occurs with anhydrite formation (CaSO4). If the kiln is burning under
slightly reducing conditions, more volatile and lower melting sulfur salts may form, therefore increasing the severity of the problem. The salts, in molten state, coat the
traveling clinker dust, forcing it to stick to the kiln wall in the form of rings. Sometimes the chemical analysis of such rings does not indicate high sulphur concentrations,
proving that even a small amount of free sulfur is sufficient to cause rings.

2- Spurrite Ring
Carbonate or spurrite rings are formed through CO2 desorption into the freshly formed free lime, or even through belite re- carbonation. These rings are hard, layered,
and exhibit the same chemistry as regular clinker. Spurrite is a form of carbonated belite. When the carbonate in the spurrite is replaced with sulfur the new mineral is
called sulphated spurrite. Spurrite rings form whenever the partial pressure of CO2 above the bed of material is high enough to invert the calcining reaction.

As we have seen, the main influencer in the process of volatilization and condensation is the generation of SO2 from all the reactions, and let us talk a little about it and
its generation.

What Affects the SO2 Generation in the Burning Zone?

The composition of the kiln load
Sulphur is preferably linked with alkalis which have a higher stability and a greater chance of being found as alkali sulphate in the clinker ( K2SO4 , Na2SO4 ) themselves
being part of bigger compounds. So if the kiln load composition has a molar excess of Na2O , K2O available (not combined with chlorine) vs. SO3 , the SO2 generated
from the load will be lower (Sulfur, Alkali, molar ratio < 1.2).
The burning zone temperature
At lower temperature, less CaSO4 or alkali sulphates will decompose to form SO2 and the SO3 level in the clinker will be higher.
The residence time in the burning zone
The longer the time the material stays in the burning zone, the higher the chance for SO2 to volatilize.
Raw Materials Composition
If the raw mix contains sulphur compounds (i.e. FeS2 = pyrite), the combustion of these compounds generates SO2.

From the Analysis of the Rings in the Calcination and Transition zones in the attached , you can see the very high concentration of SO3 , K2O, Na2O and Cl as elements in
X-ray Florescence Analysis and the Volatile Compounds were found in X-ray Diffraction Analysis for the same samples. 38
Key Reasons For Ring Formation Spurrite Rings

Chemical Analysis of Rings at Diff Meters

39
 3.9. Solving of Sulphur Volatilization
1- Reducing burning zone temperature:
Volatility of the sulphur compounds and especially of CaSO4 is an increasing function of the temperature. CaSO4 will start to decompose slowly at temperatures above 1220°C and this
thermal decomposition is best avoided by lowering the burning zone temperature. This may be achieved by making the raw meal easy to burn, which means finer grinding of the raw
meal and if necessary changing the chemical composition, i.e. lowering the silica ratio, to make an easier burning raw mix. For kiln operation it also implies that unnecessary
overheating of the material has to be avoided and a higher free lime content may have to be accepted.
2- SO3/ALK Ratio Optimization: Observing the optimum SO3/ALK Ratio and ensuring minimum excess of SO3 % are important step for reducing the sulphur volatility.
3- Maintain Oxidizing Conditions in the Kiln atmosphere:
The dissociation of sulphur compounds can be described as: Alk-SO4 + heat → Alk-O + SO2 + ½ O2
The equilibrium of this balance is shifted to the left favoring the formation of Alk-SO4 with increasing O2 and SO2 partial pressure. It is therefore important that enough oxygen is
present in the kiln atmosphere.
What will happen if you have Reducing Conditions?
The presence of free carbon in the charge will give rise to the following reactions: CaSO4 + C → CaO + SO2 + CO Alk2SO4 + C → Alk2O + SO2 + CO
This significantly increases the sulphur circulation as it promotes the decomposition of the otherwise reasonably stable CaSO4, as well as the stable alkali sulphates.
It is therefore important that oxidizing conditions are maintained in the kiln.
4-Discarding EP dust:
Sometimes it can help if the cyclones efficiency is not high. Note: By-pass is not efficient for SO3 cycles.
Summary:
- Avoid (local) reducing atmosphere: Enough excess air (O2)! No CO, Burner position parallel to kiln axis.
- Avoid long and (too) hot sintering zone : Avoid overburning, i.e. maximize CaO free, Don’t burn down the dust (don’t overheat !).
- Change raw mix: Adjust molar Alkali/Sulfur ratio ~1.2, Modify Raw Mix for better burnability and granulation, Minimize fluctuations.
PLEASE REMEMBER WHAT WE HAVE SAID THAT YOU HAVE TO CONNECT ALL THE PRINCIPLES TOGETHER AND YOU WILL HAVE VERY GOOD RESULTS, FOR EXAMPLE:
IF YOU HAVE SO3 CYCLE AND YOU DECIDE TO REDUCE THE RAW MIX FINENESS SO YOU WILL HAVE EASY TO BURN RAW MIX SO YOU CAN REDUCE YOUR FUELS, AND THE THERMAL
PROFILE WILL BE CONTROLLED, THEN YOUR BACK END O2% WILL BE INCREASED AND YOU CAN OVERCOME THE SO3 CYCLE . 40
Effect of Oxygen % on Sulphur Volatilization

O2 excess
K2SO4 K2O + SO2 + ½O2

O2 deficiency
K2SO4 K2O + SO2 + ½O2

41
Relation between Oxygen % and SO2 %
Back End SO2 PPM vs. Back End O2 % VS.
Time Hrs
900 5

800 4.5

700 4

% BEO2
3.5
BE SO2 ppm

600
3
500
2.5
400
2
300
1.5
200 1

100 0.5

0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

BE SO2 ppm % BEO2 Time Hrs

42
 Clinker Production – Circulation Phenomena
Effect of Oxygen % and BZ status on Sulphur Volatilization

Sulfur volatility vs. O2 content and temperature Effect of BZ status

43
43
3.10. Solving of Alkalis and Chloride Volatilization ( Effect of By-pass)
Evaporation of chloride is always high and can hardly be significantly reduced due to their extremely high volatilization degree in the burning zone. Measures against chlorides will
therefore not be centered around the reduction of the evaporation. Other ways of reducing the chloride content in the kiln system is therefore necessary.

How to overcome Chlorides:

1-Input from raw materials and other sources
As the evaporation factor of chloride is high, limiting the input is one of the few ways to control the chloride cycle. While it may not be possible to avoid the chloride in the main raw
materials, avoiding a minor component with significant chloride content is often feasible. The natural in-homogeneity of the raw materials can sometimes lead to substantial peaks in the
input of chlorine to the system, which must be avoided. Here the pre-homogenization of the raw materials together with a good knowledge of the quarry deposit can help to avoid such
peaks.

2-Installation of a kiln gas bypass

If the total input of chloride to the SP kiln system exceeds 0.015% Cl on raw meal basis, 0.023 %Cl on clinker basis, the installation of a bypass is normally required and a kiln gas bypass is
most frequently used for the removal of chloride. For SP kilns the rule of thumb applies that the percent bypass should be total input %Cl on raw meal basis times 100.
Example: In raw materials (raw meal basis) = 0.10% Cl
required bypass of kiln gas = 10 %
When is a Bypass Required?
• When the total chloride input (fuel + raw mix), actual or future, is in the range of 250 - 350 g/t clinker a chloride bypass may be necessary to avoid operational issues with build up.
• In plants with higher levels of chloride input, a bypass may also be necessary to avoid excessive chlorine in the clinker.
Problems of Bypass:
a-Dust Handling:
This is a very important topic that we may talk about later, and is it permissible to add it to the cement, and is it useful to wash it off?
b-Impact on Operation:
- Fuel consumption increases:
Precalciner kilns : 10 -14 kJ/kg clinker per 1% bypass
Preheater kilns : 20 - 28 kJ/kg clinker per 1% bypass
- Power consumption increases: 1.5 kWh/t clinker approx.

Solving problems with Alkalis:

Alkali volatility If not covered with sulphur, the volatility of Alkali is very high. In such cases the addition of sulphur to the kiln system in the form of gypsum can be contemplated to
reduce the volatility. As the alkalis are normally combined with either sulphur or chloride they will be out of the system.
44
 Chloride Re-circulation
0.02%
in

Up to 1.5%!!

0.02%
out
45
 Sodium Re-circulation
0.1%
in

0.2%

0.1%
out
46
 Potassium Re-circulation

0.7%
in

2%

0.7%
out47
Typical Inputs of Circulating Elements by the Raw Materials

(loss free basis)

Cl < 0.02 % normal case, no problems
> 0.05 % heavy clogging problems, depending
on the sulfur cycle

SO3 < 0.5 % normal case, no problems

> 1.25 % heavy clogging problems

K 2O < 1.0 % normal case, no problems

> 1.5 % problems with excrustations, depending on
degree of sulfatization
Na2O little volatile, thus no problems

48
 Guide for the size of bypass

Precalciner Kiln:
Chloride Input g/t clinker Bypass size %
<250 Not required
<700 5
<1300 10
<1800 15

Suspension Preheater Kiln:

Chloride Input g/t Bypass size %
clinker
<250 Not required
<1400 5
<2600 10
<3700 15 49
Bypass system

50
 Effect of bypass system
Effect of bypass on the fuel heat consumption

900

Specific heat energy consumption

850

(kcal/kgClinker )
800

750

700

650
0 5 10 15

Bypass rate (%)

Reference basis Rotary kiln with 5-stages and precalciner, 3000t/d, 100% coal

51
3.11. Effect of Alkalis and Sulfates on Quality
As a general rule we want Alkali Sulfates to be inserted between the clinker phases not embedded in the crystal structures of Silicates and Aluminates.

1- Both of Alkalis and Sulfates:

forms a separate liquid to the main oxide flux. Accelerates the formation of nodules at low temperatures but restricts their growth resulting in dustier clinker.
2-Alkalies:
- as alkali sulphates enhance early strength and concrete slump but depress late strengths.
- as alkali in solid solution can enhance the reactivity of belite and C3A.
- can lead to durability problems and ASR( Alkali Silica Reaction) in concrete.
3- Sulfates:
- excess SO3 over alkalis will form Ca langbeinite and free CaSO4, which can result in larger, less reactive alite crystals.
- in clinker limits the gypsum addition in cement mill.
- major influence on formation of lumps in cement.
4- Chloride:
-Can accelerate strengths but can also cause corrosion in steel reinforcing bars.

What will happen if we have excess of Sulfates ( SO3/ALK >1.2)

1- Produce dusty clinker which will increase the power consumption, + 1 % excess SO3 ´ = + 4 to 5 kWh/t.
2-Sulphur begins to be incorporated into the clinker minerals instead, especially belite (C2S). (Belite can contain up to about 2% of SO3 in solid solution).
3-Reduction in alite content of the clinker, since SO3 stabilizes the belite crystal structure hindering the uptake of CaO during clinkerisation and thus retarding the conversion of
belite to alite. (NOTE: This effect is counteracted by the addition of a proportional amount of fluoride).
3-Since belite is stabilized by SO3 it also retards the hydration of belite.

What will happen if we have excess Alkali ( SO3/ALK <0.8)

1-The clinker produced would not have an optimized alkali sulphatisation level. i.e. alkali sulphate levels would not be maximized.
2- The excess of alkalis over sulphur (particularly Na) will promote the formation of the orthorhombic modification of C3A at the expense of the cubic variety. Orthorhombic C3A is
the more reactive of the two (faster hydration and higher water consumption) and could cause problems with setting times and workability of cement. If Na2O and K2O are
equally balanced with sulphur (as alkali sulfates), they are not available for incorporation into C3A.
3- Alkali always works against 28-day strengths no matter what form they are.
+ 0.1 % Na2O equiv. = - 1 Mpa ( Na2O equiv.= Na2O+0.658K2O)
52
Na2O and K2O reduces the 28d-Strengths

Strengths after 28d (MPa) 70.00

65.00

60.00

55.00

50.00

45.00
0.00 0.50 1.00 1.50 2.00

Total alkalis (%)

Influence of Alkalis on Strengths

50
28 Day
40 +0.1% Na2Oeq. -1 N/mm² after 28 Days

30 7 Day

20 3 Day
* For alkaline sulphate

10
0 0.5 1 1.5

Na2O eq. (%)

Saturation of Alkalies by Sulphates

Clinker finer,
poor Grindability
Burnability poor
of Clinker 1%+5 kWh/t
Workability
in Concrete poor S in silicates
Durability poor and
aluminates
Alkali-sulfate
Na and K in Cubic C3A Alkali- Alkali-
orthorhombic sulphate sulfate
C 3A orthorhombic
cubicC3A Cubic C3A
C 3A
Sulphate in Clinker
Increase in Early strength
+0.1% Na2O soluble
+0.5 to 1.5 MPa after 1 day
55
Why is the Alkali Slulfate Saturation important ?

Saturation of Alkalies with Sulphates

Alkalies > Sulphate Sulphate > Alkalies

Burnability, Clinker finer, bad
Workability in the Grindability of clinker
Concrete & Durability 1%  +5 kWh/t
bad

Alkalies = Sulphate
Increase of early strength
+ 0.1% Na2O sol.
to 1.5 MPa more after 1 day
56
Items impacting Grinding Energy ( including alkalis and sulphates)

Average probable impact

INPUT + 0.4% + 10% + 4% + 1% + 1% + 1% + 15µ + 10µ
IMPACT soluble C3 S C 3A MgO Ex.SO 3 / f. CaO d75 Alite d75 Belite
Na 2O eq. tot. alk.

kWh/t for
-3 +4 -0.9 +1.5
250 m2/kg

kWh/t for
300 m2/kg -4 +5 +3

kWh/t for
350 m2/kg -5 -1.2 +6 +3

kWh/t for
400 m2/kg -7 -2.4 +7 +4.5

57
3.12. Effect of Combustion and Flame on Volatilization
Successful operation of a rotary kiln requires an adequate source of heat that will first raise the kiln to the desired operating temperature, and will then maintain this temperature by
compensating for the various heat losses occurring in the kiln system, including the heat required for the process. The required heat is obtained by combustion of the fuel, a chemical
reaction in which carbon, C, hydrogen, H, and sulfur, S, in the fuel combine with oxygen , in the air.
To obtain combustion, two requirements must be fulfilled:
1-sufficient oxygen must be present to mix with the fuel, and
2-a certain temperature must be maintained to ignite the fuel oxygen
Why Combustion is very important:
• Because of its impact over the temperature of the flame and thus the Burning Zone.
• Because of its impact over the volatiles recirculation
• Because of its impact over the refractory life
COMBUSTION DEFINITION:
It is a rapid oxidation of the fuel that releases heat, C + O2 = CO2 + Heat
To achieve this reaction Oxygen is required, this oxygen is supplied by the COMBUSTION AIR
COMBUSTION REQUIREMENTS:
1-How much combustion air is required? Neutral combustion air plus excess air
2- Proper proportioning of fuel and air, Need to have at least the neutral combustion air. But it is not sufficient to maintain a good combustion. Need to have an excess of combustion air,
which is controlled by Oxygen %.
The TOTAL COMBUSTION AIR is made of :
1- The secondary air from the cooler
2- The primary air from the primary air fans (axial + swirl + central) , which is the air injected with the fuel. It is important in controlling the flame shape.
3-Inleakages at the nosering, the cooler throat and at the kiln hood the transport air, when burning solid fuel.
Standard % of each portion of the total combustion air:
Axial ~4%
Swirl ~2%
Transport ~9%
Secondary ~85%
TOTAL COMBUSTION AIR:
is the total air used for the combustion of the fuel. It comprises of primary air plus secondary air from the cooler and any false air at the front-end of the kiln.
TOTAL CONSUMBTION AIR= PRIMARY AIR+SECONDARY AIR+FALSE AIR= STOICHIOMETRIC COMBUSTION AIR+EXCESS AIR
**Low primary air quantity is better , Secondary air increases and Thermal efficiency improved. 58
**False air reduction will result in Secondary air increases and thermal efficiency improved .
Combustion air

Burner Kiln hood

Primary False
air fan Air

Cooler

Secondary
air
59
Flame Characteristics
Affecting factors Affected factors

Burner design Temperature profile

Burner adjustment NOx formation

Excess air Fuel burnout

Flame characteristics

Mixing rate
Clinker quality

Fuel properties Alkali and sulfur cycles

Heat recovery in the heater cooler Coating and rings

60
Schematic -Combustion in a Flame

Radiation
from Recirculation
Shell

Primary Air + Fuel

Secondary
Air
Mixing
Radiation
Hot Secondary Air from
Clinker

Ignition Secondary Air Mixing Last Remaining

Length and Combustion Tar and
Carbon Particles
Burn Out

61
3.13.Effect of Combustion Air
Discussing of combustion and flames and their impact on the production , the volatilization , the quality of clinker, and the lifetime for refractories is very important. Some may ask
what the flame and combustion have to do with all this, and we have explained how the controlled combustion, the O2 % in the kiln, the formation of the flame ( Temp., Strength and
Shortness) have a very big impact on all these parameters, and I would like here to remind you that linking all these factors with each other will be very useful to you in solving any
problems , for example:
If there is uncontrolled combustion and you do not have the O2 % required to complete combustion, and the flame may not be in the required form, then you will find problems in
the operation like volatiles cycle and quality of the clinker.
1- Axial Air:
Minimum flow to cool down the burner pipe.
Increase or decrease the flame temperature which modify the shape of it.
It is responsible to DRIVE the Flame.
High impulsion shortens, stabilizes and compacts the Flame.
Axial Air is responsible for the flame impulse
IMPULSE = Turbulence at burner tip.
The higher is a turbulence, more effective is the mixing of solid fuel / air
2- Swirl Air:
Increase or decrease the mixing of the air and the fuel allowing a higher or lower flame temperature . Sufficient to have a good flame and turbulence at burner tip.
3- Transport Air :
For solid fuel only
Not ratioed to the fuel flow, Must be at the minimum flow, Too low == fuel deposition, Too high == abrasion and wear
4- Inleakages at the Kiln hood:
Real and expensive nuisances, Significant impact on Kiln production, stability of the flame, specific heat consumption, because it changes the flame temperature
5- Secondary Air:
- Heat recuperation, higher temperature, lower Specific Heat Consumption, Flow controlled by the I.D.Fan
- Temperature controlled by the grate speed and Clinker bed depth.
- Kiln hood pressure: Low is better for heat recuperation, Air inleakage can increase with more negative pressure.
- How much Secondary Air is required ? Total combustion air minus primary air
- Strong impact of secondary air temperature on flame temperature
- Impact of secondary air temperature on the Flame Temperature.
Secondary air === Flame
750 C === ~1700 C
850 C === ~1800 C 62
900 C === ~1900 C
Flame adjustment
Axial air

Impulse

Swirl

Flame length

Diameter

Rotational Impulse
air
Swirl

Flame length

Diameter

Impulse

Swirl

Flame length

Diameter
63
Flame formation

64
3.14. Combustion Sensors
1- OXYGENE O2 %:
- This is the most important controlling parameter of the kiln operation.
- In any system, there must be a variable that could be maintained constant.
- In our process ,we take the variable that has the most effect on the process ; this variable is the flame temperature because of its effect on the clinkerisation of the material as well as
on the refractory life.
- We cannot measure the flame temperature ; but we know that the excess of air in the kiln exit gases represents the excess of the total combustion air.
So ,by measuring the % of Oxygen in the kiln exit gases, we can evaluate the amount of such an excess of air .
- According to burning principles, we know that the flame temperature is chiefly depending on the amount of the combustion air.
Flame temperature constant = O2 % constant
To determinate the proper level of O2 % ,two criteria to fix: The Quality of the Clinker, Refractory protection and shell temperature
To control the proper level: Once obtained the optimum level, it fluctuates in a short-term, but on a long-term it is kept constant.

2- CO % :
The CO is a very serious problem in all kilns.
The CO is produced by a poor combustion due to : Poor atomization of the fuel, Low impulse of the flame, Too low level of excess air (O2 %), Wrong position of the burner pipe in the
kiln.
The CO is the stronger generator of SO2 volatilization so the CO % must always be maintained at the minimum (200-300 ppm).

3- SO2 % :
The SO2 is a very good indicator of the combustion state.
It shows the poor combustion some 5 minutes before the CO.
SO2 increases with more reducing combustion or with a very hot burning zone.
It represents the oxidation of sulfur, which comes on all fuel types and mixes.
SO2 response is faster than CO to control the combustion state.

4- NOX :
• The NOX is a very good indicator of the burning zone state:
NOX indicates at any time the burning zone environment temperature and shows a cooling or a warming of the zone some 15 minutes before any other variable.
• The difficulty with the NOX is that we have to interpret its value according to the O2 level; we know that 1 % of O2 is equivalent to ~325 ppm of NOX.
Here is one good reason to well control the O2.
• The NOX very strongly reacts to CO. An extra 200 ppm of CO makes the NOX decrease very fast. 65
• This confirms the efficiency of this variable because the CO also makes the flame temperature decrease very fast.
Clinker Quality & Shell Temperatures drive
conditions of the 3 States

State #2
State #1 Burning
Combustion Zone
BZT
Raw Feed NOx
Analysis Amps
SAT
O2
CO Prep
SO2
FLAME
Ckr
Analysis
Decarbonation. Free Lime
Material Temp. & Density
State #3
Preparation Back End Temp. Microscopy
Clinker
Clinker
Quality
66
TYPICAL NOx vs FREE LIME

NOx ppm LSF 96

3,000
LSF 98
2,500
LSF 100
2,000

1,500

1,000
COMBINABILITY
500 TEMPERATURE

0
0.25 0.5 1.0 1.5 2.0 2.5
% FREE LIME
67
4-Clinker Reactivity and Strength Development

68
 4.1. Effect of Burning and Cooling regimes on Clinker Phases
Increasing clinker C3S (to the detriment of C2S) improves strength at 1, 2, 3 and 7 days. After 28 days, the gain may be less because of the C2S’ contribution
Order of magnitude:
+10% C3S -> +2 to +5 MPa in the short and medium terms.
This is what the customer wants from us, as cement makers, to give him cement that has developed strength that increases with age, of course, in addition to other properties such as
unsoundness, alkali ratio, setting time and so on.
That means talking about the quality of the clinker produced and its ability to give the required properties to the cement produced after grinding with gypsum is the main key
parameter.
The influences on the quality of clinker:
-Correct Raw mix and fuel mix , Preparation and grinding ( Raw mix and fuel mix), Consider minor elements and volatile cycles.
-Burning and cooling conditions in the kiln:
1- Burning regime:
Degree of burning the kiln feed:
The degree of clinker preparation in the kiln greatly affects clinker quality, good quality clinker means:
* Not too much free lime (Too much free lime -> expansion)
* Not too low free lime (Too low free lime -> over burning-> high BZ temp -> damage to bricks)
2- Burning environment:
Oxidizing conditions -Kiln stability-Formation of phases ‘correctly’ Chemical analysis and Bogue calculations are done in the oxide form (i.e.: Fe2O3, SO3 ). If these are in the reduced
form (i.e.: FeO, Fe2S, S), the actual mineralogical content will be drastically different from those calculated by Bogue and the chemist will be unaware.
Very important not to have Reducing conditions !!
3-Cooling rate:
Period between end of burning zone and kiln nose ring, Influences C3A/C4AF and periclase crystal sizes.
Slow cooling :
Depresses strength development, C3A and C4AF produce relatively large crystals, C3S becomes unstable and degrades to C2S + FcaO
Optimum burning and cooling conditions:
Quick rise to maximum temperature
Small crystal sizes
Short burning zone
Maximum reactivity
Flame shape and position correct
Oxidizing conditions/coal ash combination
Quenching in the kiln
69
Crystal structure ‘frozen’ in place
Burning and Cooling of the Clinker

Good quality clinker

Small uniformly sized C3S and C2S Rapidly cooled clinker 70
Slowly cooled clinker C2S forming
from C3S

C4AF

C3 A

71
4.2. Reactions in the kiln system (1)
Zone I:
Evaporation of free water ( Drying) 100 to 400 °C
Water coming from moisture in the material escapes. This reaction requires very little energy because the raw mix has very low moisture.
Zone II:
Dehydration ( Pre-heating)
350°C & 650°C
Clay starts to lose its water of crystallization, 2SiO2.Al2O3.2H2O+ Heat -> 2SiO2.Al2O3 + 2H2O
At 400°C
Magnesium carbonate decomposes into magnesia and carbon dioxide, MgCO3 + heat -> MgO + CO2
At 550°C
CaCO3 starts to decompose at this temperature
Zone III:
Decarbonation ( Calcination)
Is the primary energy intensive reaction of cement kilns. This reaction absorbs around 400 kcal/kg of heat.
At 900°C
This is the zone where CaCO3 decomposes rapidly into CaO and CO2.
Much free lime is produced and starts to react: CaCO3 -> CaO(free lime) + CO2
1st, with SiO2
2CaO + SiO2 -> 2CaO.SiO2 (C2S)
2nd, with Al2O3 and Fe2O3
2CaO + Al2O3 -> 2CaO.Al2O3 (C2A) and 2CaO + Fe2O3 -> 2CaO.Fe2O3 (C2F)
Free CaO combines with SO3 to give anhydrite
CaO + SO3 -> CaSO4
This anhydrite reacts with the alkalis from clay to give alkali sulfates
CaSO4 + Na2O -> CaO + Na2SO4 and CaSO4 + K2O -> CaO + K2SO4 or (3K2SO4.Na2SO)
If The quantity of SO3 is insufficient to combine with the alkalis; these combine then to:
Na2O + C3A -> NaC8A3 and K2O + C2S -> KC23S12
The reactions of Alkali and Sulfates are depending on SO3/ALK as discusses in the Volatilization.
At 850°C
The C2A changes to C12A7 ( intermediate compounds) 72
4.2. Reactions in the kiln system (2)
Zone IV:
Clinkering (burning zone) (A)
At 1200°C
Belite ( C2S) is completely formed, 2CaO + Si2 -> 2CaO.SiO2
C12A7 becomes enriched in lime and changes to C3A then, C2A and C2F form a solid solution of C4AF.
4CaO + Al2O3 + Fe2O3 -> C4AF
Between 1250° and 1300°C
C3A and C4AF liquefy and constitute the flux. This reaction is endothermic.
C2S combines with free CaO to form C3S in the presence of flux.
CaO + C2S -> C3S
Zone IV:
Clinkering (burning zone) (B)
The alkali sulphates decompose, liberating alkalis and SO2
Na2SO4 + heat -> Na2O + SO2 + 1/2 O2
K2SO4 + heat -> K2O + SO2 + 1/2 O2
Anhydrite decomposes into CaO and SO2
CaSO4 + heat -> CaO + SO2 + 1/2 O2
Ferric oxide, in a reducing atmosphere, changes to ferrous oxide.
Fe2O3 -> 2FeO + 1/2 O2
Carbon from the fuel oxidizes to carbon monoxide, then to dioxide.
C + O2 -> CO + 1/2 O2 -> CO2
These reactions are depending on burning zone atmosphere ( oxidizing or reduction) and SO3/ALK .
Zone V:
Cooling
1400°C to 1250°C (rapid)
Clinker phases and liquid phase are affected by rate of cooling
Slow cooling affects clinker phases:
C3A and C4AF produce relatively large crystals
C3S becomes unstable and degrades to C2S + Free CaO 73
Reactions in the kiln system

74
Schematic illustration of raw mix
Prior to heat treatment
50 MICRONS (0.05 mm)

iron oxide SiO2

Fe2O3 limestone
silica
CaCO3 shale/clay
(Al2O3 and SiO2)
Note, for clarity this schematic illustration only shows
relatively large particles. In an actual raw mix a much higher
proportion of finer particles would be present.
75
 Schematic illustration of reactions
Following heat treatment to 1000 deg c
Reaction at point of contact
Reaction between CaO and
between CaO and silica
iron oxide to form C2F 50 MICRONS (0.05 mm)
to form C2S
(ferrite)

Reaction between shale and

Decarbonated limestone (CaO) CaO to form C12A7 and C2S
note cracks/porosity introduced and other intermediate compounds
as a result of ~ 50% loss in mass which are not found in the final clinker.
76
Schematic illustration of reaction
between limestone (lime) particle and
sand (silica) particle at 1300 deg c
pore C2S unreacted silica
C3S
crystallises
from flux

silica
dissolves

lime
dissolves in
flux and moves
to silica

lime 5 MICRONS (0.005 mm) Liquid phase

molten C3A and C4AF
(Molten mixture of shale,
iron oxide and lime)

77
Schematic illustration of reaction
Between limestone (lime) particle and
sand (silica) particle at 1400 deg c
pore space C3S pore Unreacted C2S

Residual free lime 5 MICRONS (0.005 mm)

Molten C3A and C4AF
78
Schematic illustration of clinker at 1400 DEG C
Clinker flux
(Molten C3A and C4AF)
50 microns (0.05 mm)

C2S cluster
C3S Free lime cluster
79
Kiln Reactions ( endothermic and exothermic)

80
Kiln Reactions Mechanism
Kiln Reactions Mechanism
Kiln Reactions Mechanism
Kiln Reactions Mechanism
Kiln Reactions Mechanism
4.3. Clinker Phases Investigation
Clinker Phases are formed inside the kiln, but how actually make sure of its existence and how to calculate it?
The impurities from the raw materials, the kiln instability and the complexity of the cooling step, all these factors make it difficult to obtain a perfect evaluation of the mineralogical
composition of Portland clinker. All the phases are formed in crystalline phases.
Methods for clinker mineral investigation
Needing to know:
1- Identification of the minerals.
2- Estimation of the quantity of each crystal phase present.
3- Determination of the composition of individual crystal of any single phase and hence the composition range of the phases.
4- Determination of the crystal distribution.
Several groups of methods are available for the determination of these properties:
Scanning electron microscope ( SEM), X-ray Fluorescence and X-ray Diffraction ( XRF-XRD) and Wet Analysis techniques
(a) Microscopic investigation:
Qualitative evaluation: raw mix quality, thermal profile in the kiln and overburning conditions, kiln atmosphere and stability, alkali/SO3 saturation, verifying clinker quality.
Quantitative evaluation: crystal sizes of Alite and Belite, clinker phases by manual point counting, (mostly replaced by XRD-Rietveld), it is time consuming and using average sample
Note: Qualitative is what is found and Quantitative is the amount of it.
(b) XRF:
Elements measured: Ca, Mg, Al, Fe, Si, Na, K, S, etc., Out of main elements Bogue calculation for clinker phases: C3S, C2S, C3A, C4AF, Accurate determination of Elements, Calculation
out of the Elements.
(c) XRD:
Relations/ distances between atoms measured and Crystals (Bragg law), Out of diffractogram Rietveld calculation for phases: Alite, Belite, Aluminate, Ferrite, Free lime, Calcite, Quartz,
etc.
Oxides: ( by XRF) CaO -> C , SiO2 -> S, Ale2O3 -> A, Fe2O3 -> F
Clinker Minerals: ( by XRD) C3S -> Alite, C2S -> Belite, C3A -> Aluminate, C4AF-> Ferrite
How do we calculate the phases?
Simplified calculation of clinker minerals according to BOGUE:
% C3S =4,07 x (CaO-CaO free)- (7,60 x SiO2+6,72 x Al2O3+1,43 x Fe2O3)
% C2S =2,87 x SiO2 - 0,754 x C3S
% C3A =2,65 x Al2O3 - 1,69 x Fe2O3
% C4AF =3,04 x Fe2O3
The above models are valid only when AR ( Alumina Ratio A/F<0.64) in other cases they must be further modification. 86
BUT THEY ARE NOT THE REAL PHASES! WHY? WHAT IS THE DIFFERENCE BETWEEN REAL AND CALACULATED PHASES? ARE THERE ANY MODIFIATIONS.
Clinker phases (by Microscopic investigation SEM)

• Alite – C3S
• Belite – C2S
Clinker phases(by Microscopic investigation SEM)

• Aluminate – C3A
• Ferrite – C4AF
Clinker phases(by Microscopic investigation SEM)

Free lime - CaOfr Periclase - MgO

Evaluation of conditions – raw mix quality
(by Microscopic investigation SEM)

CaO

Well distributed clinker – Inhomogeneous clinker – Inhomogeneous clinker –

only small Belite clusters, large Belite cluster -> accumulation of Free Lime
low amount of Free Lime indicates siliceous-rich -> indicates coarse
particles in the raw meal limestone fragments in
raw feed
Evaluation of conditions – temperature
(by Microscopic investigation SEM)

Zoned Alite and large, well

shaped crystal form ->
high temperature

High porosity with Free Lime

and anhedral formed Alit
crystals ->
low temperature of burning

91
 Evaluation of conditions – cooling
(by Microscopic investigation SEM)

Well differentiated matrix,

Belite decomposition ->
slow cooling

Finely differentiated matrix,

round Belite crystals with
multidirectional lamellas ->
quick cooling
Principle XRF and XRD

X-Ray Fluorescence X-Ray Diffraction

93
What is XRD measuring?

Cement
grain

Packed
cement
POWDER Crystal
lattice

Crystal
d2 d1

94
Different crystal systems
cubic hexagonal trigonal tetragonal

rhombic monoclinic triclinic

High symmetric systems have more times the same distance between
crystal layers -> higher measured intensities!!
95
X-Ray Diffractometry

Interaction between X-rays and crystal lattices

Bragg´s Law :

n  2d sin 

d = distance between planes

  wave length of X-ray
  diffraction angle
4.4. Real and Potential Clinker Phases
Bogue calculations are carried out based on loss-free oxides and the following assumptions:
a-There are four major clinker phases.
b. Fe2O3 appears only in C4AF.
c. Al2O3 occurs first in C4AF and then in C3A.
d. CaO that is considered to form C3S and C2S is the amount remaining after apportioning lime to C4AF, C3A, and the unreacted CaO in clinker.
The potential phase composition differs from the actual composition of the clinker, as determined by X-ray diffractometry or optical microscopy, due to the following reasons:
1 . The clinkering reactions seldom reach equilibrium during cooling, which happens to be the basic theoretical assumption in developing the Bogue calculations.
2 . The compositions of the clinker phases differ considerably from those of the pure compounds that are considered in the calculation due to the incorporation of impurities present in
the raw materials.
Correction of SO3:
Bogue considered that all SO3 is combined with CaO ,but it is not correct because SO3 can combine also with Alkali.
SO3 combination
Step #1:
- if K2O/SO3 < 1.176 not all SO3 combined as K2SO4 then SO3 in K2SO4 =0.85 K2O
Step #2:
(Remaining SO3) =SO3-SO3 in K2SO4
- if Na2O/(Remaining SO3 )< 0.775 not all SO3 combined as Na2SO4: SO3 in Na2 SO4 =1.292 Na2O
Step #3:
- CaO combined with excess SO3=0.7 x (SO3 – (SO3 in K2SO4+SO3 in Na2SO4))
Let us now see the difference:
The original C3S=4.07 x (CaO-CaO free)-(7.60 x SiO2+6.72 x Al2O3+1.43 x Fe2O3)
The corrected one: If SO3-(0.85K2O+1.292Na2O) ≤0 the equation will be C3S=4.07 x ((CaO-CaO free)-0.7 x ((SO3 – (SO3 in K2SO4+SO3 in Na2SO4)) - (7.60 x SiO2+6.72 x Al2O3+1.43 x Fe2O3)
The Bogue equations did not take into account the influence of minor elements like Alkalis, MgO, Ti, Mn, Cr, P. .etc.
In reality:
• Alite is not C3S but: ( includes MgO , Fe2O3, and Al2O3 as impurities).
• Belite is not C2S but:( includes MgO , K2O, Na2O, Fe2O3,P2O5, and SO3 as impurities.
• Aluminate is not C3A but:( includes MgO , K2O, Na2O,Fe2O3, TiO2and SiO2 as impurities) in Cubic form. ( includes Na2O ,Fe2O3, and SiO2 as impurities) in Orthorhombic form .
• Ferrite is not C4AF but: phases possible between C2A and C2F ( includes MgO,SiO2 and TiO2 as impurities) .
Summary
1- The equations must be corrected for CaO: if SO3-(0.85K2O+1.292Na2O) ≤0 then, SO3 combined with alkali and CaO.
2- Taking into account the effect of impurities on the activity of the phases. With the introducing of Alternative Fuels ( specially tires and RDF) and Alternative Raw Materials.
These impurities can affect on the reactivity of the phases.
Comparison of the clinker phases
real and potential
C3S C2S
Weight -% Weight -%
25
80

Bogue
75 20 Rietveld
Microscopy

70
15

65
10

60
Bogue
5
Rietveld
55
Microscopy
0
50

C3A C4AF
Weight -%
25 Weight -%
9
23 Bogue
Rietveld 8
21
Microscopy
19
7 Bogue
Rietveld
17 6
Microscopy
15 5

13 4

11
3

9
2
7
1
5
0

Bogue calculations based on XRF

Rietveld estimation based on XRD
98
Microscopy based on SEM
Bogue calculation

In Reality : Alite = C3S + minor elements

ex. solid solutions (3 à 4 %).
Example Alite :
(Ca0.98Mg0.01Al0.067Fe0.00333)3 (Si0.97Al0.03)O5

similar for Belite, Aluminate and Ferrite = impure Phases

99
Typical element composition of clinker phases

• Alite is not C3S but:

[3(Ca0.98 Mg0.01 Al0.067 Fe0.0033)][(Si0.97 Al0.03)] O5

• Belite is not C2S but:

[2(Ca0.975 K0.01 Na0.05 Mg0.01)][(Fe0.02 Al0.06 Si0.9 P0.01 S0.01)] O3.96

• Aluminate is not C3A but:

Cubic : [3(K0.03 Na0.06 Ca2.76 Mg0.08 Ti0.01)][(Fe0.22 Al1.6 Si0.18)] O6
Orthorhombic : [3(Na0.292 Ca2.792)][(Fe0.15 Al1.725 Si0.125)] O6

• Ferrite is not C4AF but:

Ca2 (AlX Fe1-X)2 O5 so phases possible between C2A and C2F.
Ca2Al Fe0.6 Mg0.2 Si0.15 Ti0.05 O5

100
4.5. Clinker Phases Polymorphism
The polymorphism and metallurgical structure of clinker phases are described as follows.
1-Alite C3S:
The pure C3S at temperatures ranging from ambient to about 1100°C has seven polymorphs: M1-M2-M3-T1-T2-T3-R
M is monoclinic form
T is triclinic form
R is rhombohedral
In clinker, alite always crystallises from the melt in a triagonal form. The stabilisation factors decide during the cooling process which modification stable at ambient temperature is
formed. The most common modifications are M1 and M3, and T2 occurs only rarely . The ratio of the nucleation processes and alite crystallisation, and the contents of minor oxides in
the melt are the decisive stabilisation factors. M1 and M3 have good hydraulic properties . M1 is more reactive than M3.
SO3 and MgO are very important to control because of their effect on the viscosity of the liquid phase and the transformation of M1-M3.
2-Belite C2S:
Unlike the alite phase, the properties of belite are more sensitive to different polymorphic modifications. From ambient to 1500°C, this phase may change its polymorphic state. The
high-temperature modifications have high reactivity but their stabilization at ambient temperature is not easy. Industrial clinkers predominantly show the presence of the beta
polymorphic phase, sometimes together with small proportions of the high-temperature forms. The beta form possesses good hydraulic properties, while the gamma form is of poor
hydraulic behavior. One should note that stabilization of the beta phase of belite is quite important for achieving the desired hydraulic properties of cement.
3-Aluminate C3A:
The C3A phase does not have any polymorphic transformation.
Only the alkali elements cause changes in its crystal symmetry to orthorhombic, and monoclinic forms . Pure C3A is cubic in symmetry.
As would be expected from their higher basicity, the alkali-loaded forms of tricalcium aluminate are progressively more reactive with water and because this makes setting of cement
more difficult to control, the production of the orthorhombic and monoclinic forms is avoided in good manufacturing practice. This is usually accomplished by ensuring that there is
sufficient sulfate in the clinker to tie up the alkalis in salt phases.
4-Ferrite C4AF:
This phase in clinker is basically represented by C2 (A, F) in which there is complete miscibility between C2F and hypothetical C2A up to C4AF
The ferrite phase is regarded as having low hydraulic properties.
The C4AF phase has possesses orthorhombic symmetry.
Summary:
1- The presence of impurities in the crystal lattice of the clinker phases is playing an important rule in the stability and reactivity of the phases.
2- The rate of burning and cooling plays an important rule in the stability and reactivity of the phases.
3- If the kiln is under reducing condition , a lot of crystal disorders will be found.
101
Alite Forms

The sequence of Alite transformations

102
 Effect of SO3 and MgO content on Alite forms

The increase of MgO contents in clinker leads to enhanced

nucleation and decelerates the growth of Alite crystals. At
increased MgO levels, Alite forms smaller crystals of
monoclinic M3 modification. On the other hand, increased
SO3 content attenuates the nucleation and accelerate Alite
growth. Alite crystals grow larger, being formed by
monoclinic M1 modification

103
The sequence of Belite transformations

104
Different crystal systems
cubic hexagonal trigonal tetragonal

rhombic monoclinic triclinic

High symmetric systems have more times the same distance between
crystal layers -> higher measured intensities!!
105
4.6. Derivations of some equations and Bogue equations
To understand the SO3 correction:
1- If K2O/SO3<1.176 not all SO3 combined as K2SO4
The value (1.176) came from MW of K2O (94.2)/MW of SO3 (80.06): 94.2/80.06=1.176
2- SO3 in K2SO4=0.85K2O
The value (0.85) came from MW of SO3 (80.06)/MW of K2O (94.2):80.06/94.2=0.85 (Because the reaction is:K2O+SO3=K2SO4)
3- If Na2O/ SO3 remaining < 0.775 not all SO3 combined as Na2SO4
The value ( 0.775) came from MW of Na2O (62)/MW of SO3 (80.06):62/80.06=0.775
SO3 in Na2SO4=1.292Na2O
The value 1.292 came from MW of SO3 (80.06)/MW of Na2O (62):80.06/62=1.292 (Because the reaction is:Na2O+SO3=Na2SO4)
4- CaO=0.7(SO3-(SO3 in K2SO4+SO3 in Na2SO4)
The value 0.7 came from MW of CaO (56)/ MW of SO3 (80.06):56/80.06=0.7 (Because the reaction is:CaO+SO3=CaSO4)
Now let us try to understand the derivation of Bogue equations:
-The MW of the phases:C3S=228.32, C2S=172.24, C3A=270.2, C4AF=485.97, The MW of oxides: CaO=56.08, SiO2=60.08, Al2O3=101.96, Fe2O3=159.69
1- C4AF: MW of Fe2O3=159.69, Fe2O3 in C4AF=159.69/485.97=0.3286. So, C4AF=Fe2O3/0.3286=(1/0.3286)*Fe2O3=3.043*Fe2O
2- C3A:
From Al2O3 which is present in C3Aand C4AF:
Al2O3=(MW of Al2O3/MW of C3A)*C3A+(MW of Al2O3/ MW of C4AF)*C4AF=(101.96/270.2)*C3A+(101.96/485.97)*C4AF=0.3774*C3A+0.2098*C4AF
We have that C4AF=3.043*Fe2O3 then substitute :
Al2O3=0.3774*C3A+0.2098*3.043*Fe2O3=0.3774*C3A+0.638*Fe2O3. So, C3A=(Al2O3-0.638*Fe2O3)/0.3774=(1/0.3774)*Al2O3-(0.638/0.3774)*Fe2O3=2.65*Al2O3-1.69*Fe2O3
3- C2S:
SiO2 which is present in C3S and C2S:
SiO2=(MW of SiO2/MW of C3S)*C3S+(MW of SiO2/ MW of C2S)*C2S=(60.08/228.32)*C3S+(60.08/172.24)*C2S=0.2631*C3S+0.3488C2S
C2S=(SiO2-0.2631C3S)/0.3488=(1/0.3488)*SiO2-(0.2631/0.3488)*C3S=2.867*SiO2-0.754*C3S
4-C3S:
CaO is present in all:
CaO= 3*(MW of CaO/MW of C3S)*C3S+2*(MW of CaO/MW of C2S)*C2S+3*(MW of CaO/MW of C3A)*C3A+4*(MW of CaO/MW of C4AF)*C4AF
=3* (56.08/228.32)*C3S+ 2 *( 56.08/172.24)*C2S+3*(56.08/270.2)*C3A+4*(56.08/485.97)*C4AF=0.7368*C3S+0.6512*C2S+0.6226*C3A+0.4616*C4AF
substitute:
CaO=0.7368*C3S+0.6512*(2.867*SiO2-0.754*C3S) +0.6226*(2.65*Al2O3-1.69*Fe2O3)+0.4616*(3.043*Fe2O3) =0.7368*C3S+1.8667*SiO2-0.4913*C3S+1.649*Al2O3+0.354*Fe2O3
=0.2455*C3S+1.8667*SiO2+1.649*Al2O3+0.354*Fe2O3
C3S=((CaO-(1.8667*SiO2+1.649*Al2O3+0.359*Fe2O3))/0.2455=(1/0.2455)*CaO-((1.8667/0.2455)*SiO2+(1.649/0.2455)*Al2O3+(0.352/0.2455)*Fe2O3
=4.071 *CaO - (7.6*SiO2+6.71*Al2O3 + 1.43*Fe2O3) 106
4.7. Clinker Phases Characteristics
The chemical, physical and cement properties of these compounds.
1-Alite C3S:

Typically 52 to 65% of clinker, Main strength constituent in cement, High initial strength and contribute in final strength, Rapid hydration, Contains impurities: Mg, Al, Fe
Difficult to burn kiln feed if C3S > 65%
Short term Strengths
+ 1% C3S ->0.1 MPa (@ 1 day)
+ 1% C3S -> +0.3 MPa (@ 3 days)
+ 1% C3S -> +0.4 MPa (@ 7 days)
Long Term Strengths
+ 1 % C3S -> + 0.6 MPa (@ 28 days)
this is an average value and can vary on a ratio of 1 to 2 for a given clinker.
Usually :
C2S decreases when C3S increases

2- Belite C2S:

Typically 15 to 25% of clinker, Low early strength but good final strength, Slow hydration, Contain impurities: alkalis, Al, Fe, fluorides, Clinker grindability adversely impacted
by higher C2S

3- Aluminate C3A:

Rapid hydration with heat development, Gypsum added to control rate, Early strength, Typically 3 to 13% of clinker, Important effects on concrete quality,
Plasticity/workability, Resistance to sulfates in soil/water exposure

4- Ferrite C4AF:

Governs the color of cement: higher C4AF = darker cement, No impact on strength, Typically 5 to 15% of clinker
107
Properties of Clinker Phases
Compressive Strength
graph shows phases contribution to strength with time Sequence of Clinker phases
Formation
Compressive Strength Kg/Cm2

CO2 Volatiles Mineral ash

Calcite, C3S
quartz, clays C2S
C3A
CaO C4AF C3A C3S C4AF
C2S

20 min to 3 hr

Time (Days)

108
Alite (C3S) characteristics

Clinker Phases and Strength 109

 4.8. Liquid Phase
Clinker liquid phase or clinker melt is the fraction of the kiln feed that melts between the upper transition and the burning zone. The liquid has a critical role in clinker nodulization
and clinker mineral development . In the absence of liquid, the conversion of C2S and free lime to C3S would be almost impossible in the kiln.

AMOUNT OF LIQUID PHASE

The amount of liquid phase in the burning zone varies between 23 and 30%. Higher values can be damaging to most refractory bricks in the absence of a stable coating. As the brick is
infiltrated and saturated with liquid, its elastic modulus increases and so does its tendency to spall off. Liquid phase calculations can be used to predict where in the kiln the stable
coating will form. The amount of liquid is calculated at 1338 C,1400 C and at 1450 C and the results are compared:
1450 °C: 3.00 A +2.25 F + MgO+ K2O+ Na2O
1400 ° C: 2.92 A +2.2 F + MgO+ K2O+ Na2O
1338 ° C: 8.20 A - 5.22F + MgO+ K2O+ Na2O , when A/F≤ 1.38
1338 ° C: 6.10 F +MgO + K2O +Na2O , when A/F ≥ 1.38
The tendency to coating formation increases with the amount of liquid. However, more coating does not necessarily mean better coating.

IMPORTANCE OF THE LIQUID PHASE

The most important clinker mineral C3S (alite) requires the presence of liquid for its formation.
To understand why alite formation requires liquid phase, one must first understand the alite formation mechanism:
1. C2S and free CaO dissolve in the clinker melt.
2. Calcium ions migrate towards C2S through chemical diffusion.
3. C3S is formed and crystallized out of the liquid.
Without liquid phase the diffusion of Ca ions towards C2S would be extremely slow, and that of C2S almost impossible.
It is important to mention that Na2O and K2O decrease the mobility of Ca ions, whereas MgO and sulphates considerably increase it.

PROPERTIES OF THE LIQUID PHASE

1-VISCOSITY:
MgO, alkali sulphates, fluorides and chlorides reduce liquid phase viscosity. For instance, a regular clinker at 1450 ºC has a viscosity of 0.16 N.s/m2. Adding 2% SO3 to the clinker
reduces that viscosity to 0.05 N.s/m2.
Over-sulfated clinkers are usually dusty as a consequence.
Free alkali and phosphorus increase liquid phase viscosity, but this effect is offset by MgO and SO3.
2-surface tension:
Alkali, MgO and SO3 reduce liquid surface tension.
Sulphur and Potassium have the strongest effects, followed by Sodium and Magnesium. Therefore, MgO, SO3 and K2O, to a certain concentration, are good coating promoters.
110
Unfortunately, the liquid properties that induce C3S formation are detrimental to the refractory lining and to clinker nodulization.
Formation of Liquid Phase

111
Variation in % of Liquid Phase at 1338 C with change in SR and AR at 100% LSF

Effect of minor components on Liquid Phase properties Effect of Liquid Phase

112
Relevance of the Liquid Phase
• Surface tension, or its ability to “wet” the lining:
• Viscosity:
- The surface tension has a direct impact on clinker fineness,
- Decreases with increasing temperature
coating adherence to the lining and clinker quality.
- Depending on composition and minor elements
* Reduced by Na2O,CaO,MgO,Fe2O3,MnO
- High surface tension values favor nodule formation and liquid
* Increased by SiO2,Al2O3
penetration through the pores of the nodules. The resulting
clinker contains less dust and lower free lime content. A liquid
phase with high surface tension has less tendency to adhere to
the brick surface, therefore reducing clinker coatability or
adherence to the lining.
- Affected by alkali ,SO3 and MgO.

The desired liquid phase must have moderate viscosity and surface
tension

113
4.9. Free Lime
For a given total of CaO that should combine, there always is a certain amount that is not combined and left in the clinker. For a given LSF, the % of free lime tells about the level of
the burning. The target free lime is 1-2 % , below 1 % will give less reactive clinker and above 2 % will give expansion problems for cement and concrete.
Factors affecting the Free Lime %
1- Raw Mix Fineness and Raw Mix burnability
a- Effect of Raw Mix Fineness:
The reason for higher fineness in the Raw Mix is local inhomogeneity in the raw mix comes from coarse grains of calcite (rich in CaCO3) or coarse grains of quartz (rich in SiO2).
Clinker with a large belite cluster surrounding a quartz grain, the cluster has not reacted with CaO to form the desired C3S during the clinkerisation, and therefore the unused CaO is
present somewhere in the clinker as free lime. If the original coarse grain had been calcite, a cluster of C3S would have been formed around a grain of free lime. In both cases the
clinker will present a high free lime content. So both coarse quartz and coarse calcite may result in poor burnability, with corresponding high free lime content and too little C3S in the
clinker. The following particle sizes have been found to be critical for the burnability of the mix :
Quartz and silicates: +45 µm
Calcite: +125 µm
An increase in the amount of coarse particles results in the following increases in free lime:
+1% quartz + 45 µm leads to +0.93% free CaO
+1% calcite + 125 µm leads to +0.56% free CaO
Note :(Coarse grains of Quartz is more serious than coarse grains of Calcite).
b- Effects of chemical composition:
LSF and SM increase, Free lime increases. LSF ( CaO/2.8*SiO2+1.18*Al2O3+0.65*Fe2O3), SM ( SiO2/Al2O3+Fe2O3)
After many experiments and burnability tests, they found the following equation:
CaO1400°C =0.33 (LSF - 95) + 2.0 (SM- 2.3) + 0.93 *%Q +45µm + 0.56 *%C+125µm
Chemistry Mineralogy
Q+45µm is quartz grains larger than 45µm, C+125µm is calcite grains larger than 125µm
2- Burning Zone state and Cooling rate:
Good quality clinker means: not too much free lime ( will cause expansion) , not too low free lime ( over burning-high BZ temp-damage to bricks-high heat consumption).
Normal Burning
C2S + Free CaO + (liquid phase) = C3S, Free Lime at 1.0 %, Liter weight at 1200 - 1300 grs, Burning zone short.
Over Burning
Larger Alite crystals, High Liter weight and low F.L, Harder grinding, Lower reactivity, Lower cement strengths.
Under Burning
Very high free lime and low liter weight, Fewer alite crystals (C3S) , Excessive belites crystals (C2S).
• If the cooling rate is slow , the decomposition of C3S will produce free lime.
3- Effect of SO3 Volatility: 114
If the kiln is under SO3 Volatility , the decomposition of CaSO4 will produce free lime in the burning zone.
Coarse grains and free lime

This equation can be generalized to any plant

and the constants can be changed according to the
situation of the raw materials in the plant:
CaO1400oC =0.33 * LSF + 2.5 Ms +K1 * SiO2(45µm) +
K2 * CaCO3 (125µm) - X
K1 and K2 are plant specific constants between 0 and 1
X is a plant specific constant between 30-40

115
Coarse grains and burnability
Chemical changes during burning

Free CaO C3S

CaCO3
C2S

Quartz
C3A
Clays Liquid phase
C4AF

116
Clinker as seen in the Microscope
Porosity
C2S
Porosity

C3S Free CaO

117
Homogeneous Clinker

....insert figure here

118
Raw Mix Fineness and free lime
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120
 Overall free lime

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Heat exchange and free lime

122
Filling degree and free lime

123
5- Cement Hydration and its effect
on Cement and Concrete properties

124
5.1. Cement Hydration Process
The Cement Producers do not sell cement, but they sell quality. they sell what the customer wants from this cement, in terms of its different characteristics such as
strength, unsoundness, setting, workability, and durability etc.

Cement Hydration
The constituents of the cement paste when mixing with water are:
Main Phases: Alite+Belite+Aluminate+Ferrite
Minor Phases: Free lime+Percilase (free MgO) +Gypsum (CaSO4)+Alkali Sulfate
To a minor extent , hydration reactions can also take place before the cement is applied in concrete during the storage of clinker and storage of cement in the silos.
Even this minor surface hydration may cause serious changes of the properties of cement.

Reactions sequence during Hydration

First:
When cement is dispersed in water, and as result of interactions between Gypsum (CaSO4) and the highly reactive compound (C3A), within few minutes the needle-
shaped crystals of Calcium trisulfoaluminat hydrate called(ettringite) first make their appearance also Ca(OH)2 is formed from the hydration of free lime and Calcium
Silicates ( C3S,C2S).
The ettringite covers the Aluminate particles and avoids flash set.
After these first reactions the so called "dormant" period 4-6 h starts.
The "dormant" period is explained by the behavior of C3S which based on the protective layer and the delayed nucleation concept.
The protective layer prevents further hydration then it destroyed with time and the latter regards the retardation in C3S reaction as a cause of a delayed nucleation.
Now the setting is occurred within the first hours which is the stiffening of the paste and it is attributed to the recrystallization of the initially finely divided ettringite
or due to the loss of plasticity after formation of CSH gel from Silicates.
Second:
After about 24h the precipitation of CSH in form of long fibers and Ca(OH)2 takes place on the surface of Silicate phases and the reaction proceed rapidly.
This stage ends with the formation of ettringite formation and development of basic matrix.
Third:
The spaces between solid particles are overbridged and filled with short fibers of CSH phase.
The initial matrix formed by hydrates of Aluminate , Ferrite and Silicates is thus densified and the strength of the cement paste increased.
The Ca(OH)2 formed in large crystals is built into the CSH gel matrix.
At this stage ettringite is converted into monosulfate and the corresponding hydration products are formed from the still not hydrated aluminate and ferrite phases.
As the hydration proceeds the reactions get more diffusion and the overall rate is decreasing.
Hydration of C2S will continue as long as the reactants and space permit it, this can go for years. 125
Time Line of Hydration Process

126
Cement Hydration-Fresh Cement
C2S C3A

Gypsum
Ferrite
C3S

C3S C2S C3A C4AF C-S-H Aluminate Calcium Gypsum

gel hydrate hydroxide

127
Cement Hydration - 3 hours

Calcium
C-S-H hydrate hydroxide
forms on C3S
precipitated

C3S C2S C3A C4AF C-S-H Aluminate Calcium Gypsum

gel hydrate hydroxide

128
Cement Hydration - 28 days
Unreacted
centres of C2S forms
additional
coarse particles
C-S-H hydrate

Porosity
depends on
water:cement Ferrite yields
ratio similar hydrate
to C3A

C3S C2S C3A C4AF C-S-H Aluminate Calcium Gypsum

gel hydrate hydroxide

129
Hydration Process

130
Hydration of C3S + 140 mins

Hydration of C3S + 21 days

131
Hydration of Clinker Minerals Contribution of Clinker Phases
to Strengths Development
Compressive strength (MPa)
80
C 3S
70

60 C 2S
50

40

30

20

10 C 3A
C 4AF
0
7 28 90 180 360 days

132
5.2. Products of Cement Hydration Process
The tricalcium aluminate
Reacts with the gypsum in the presence of water to produce ettringite:
Tricalcium aluminate + gypsum( CaSO4.2H2O) + water = ettringite
(i) C3A + 3CS_H2 + 26H = C6AS_3H32 H is water , CS_H2 is gypsum
Ettringite ( called AFt) consists of long crystals that are only stable in a solution with gypsum. The compound does not contribute to the strength of the cement glue.
Once all the gypsum is used up as per reaction (i), the ettringite becomes unstable and reacts with any remaining tricalcium aluminate to form monosulfate aluminate hydrate( called AFm) crystals:
Tricalcium aluminate + ettringite + lime= monosulfate aluminate hydrate
2C3A + 3 C6AS_3H32 + 22H = 3C4AS_H18,
The monosulfate crystals are only stable in a sulfate deficient solution. In the presence of sulfates, the crystals resort back into ettringite, whose crystals are two-and-a-half times the size
of the monosulfate, this increase in size that causes cracking when cement is subjected to sulfate attack.
The tricalcium silicate (alite)
Is hydrated to produce calcium silicate hydrates ( called Tobermorite gel) , lime ( called Portlandite also) :
Tricalcium silicate + water = calcium silicate hydrate + lime
(ii) 2C3S + 6H = C3S2H3 + 3CH CH is Ca(OH)2 which is lime or Portlandite
The CSH has a short-networked fiber structure which contributes greatly to the initial strength of the cement glue.
The belite (dicalcium silicate)
Also hydrates to form calcium silicate hydrates and heat:
Dicalcium silicates + water = calcium silicate hydrate + lime
C2S + 4H = C3S2H3 + CH
Like in reaction (ii), the calcium silicate hydrates contribute to the strength of the cement paste. This reaction proceeds at a slower rate, meaning that the contribution of C2S to the
strength of the cement paste will be slow initially. This compound is however responsible for the long-term strength of Portland cement concrete.
The ferrite
Undergoes two progressive reactions with the gypsum:
in the first of the reactions, the ettringite reacts with the gypsum and water to form ettringite, lime and alumina hydroxides:
Ferrite + gypsum + water = ettringite + ferric aluminum hydroxide + lime
C4AF + 3CS_H2 + 3H= C6(A,F)S_3H32 + (A,F)H3 + CH
the ferrite further reacts with the ettringite formed above to produce garnets:
Ferrite + ettringite + lime + water = garnets
C4AF + C6(A,F)S_3H32 + 2CH +23H = 3C4(A,F)S_H18 + (A,F)H3
The garnets only take up space and do not in any way contribute to the strength cement.
Hardened paste consists of the following: 133
Ettringite (15 to 20% ) Calcium silicate hydrates, CSH (50 to 60%) Calcium hydroxide (20 to 25%) Voids (5 to 6%)
Hydration of Cement Phases with Time

134
 Cement Hydration Products
Calcium silicate hydrate (Tobermorite): this is the main reaction
product and is the main source of concrete strength. It is often
abbreviated, using cement chemists' notation, to "C-S-H”
Calcium hydroxide: (or Portlandite)- Ca(OH)2, often
abbreviated to 'CH.' CH is formed mainly from alite hydration.
AFm and AFt phases: these are two groups of minerals that
occur in cement, and elsewhere. One of the most common AFm
phases in hydrated cement is monosulfate and by far the most
common AFt phase is ettringite.
The most common AFt and AFm phases in hydrated cement are:
Ettringite: ettringite is present as rod-like crystals in the early
stages of reaction or sometimes as massive growths filling pores
or cracks in mature concrete or mortar. The chemical formula
for ettringite is [Ca3Al(OH)6.12H2O]2.2H2O] or, mixing
notations, C3A.3CaSO4.32H2O.

Monosulfate: monosulfate tends to occur in the later stages of

hydration, a day or two after mixing. The chemical formula for
monosulfate is C3A.CaSO4.12H2O. Note that both ettringite and
monosulfate are compounds of C3A, CaSO4 (anhydrite) and
water, in different proportions
135
C-S-H “needles” Hydration of C3S + 360 days

Hydration of C2S + 3 years

136
C3A Hydration without adding Gypsum ( Flash set)
C3A + Ca(OH)+2 18 H2 O

slows down C4AHn

C3S hydration

“Flash”
set time
aluminate set
short term strength
poor workability 137
C3A Hydration
• No added Gypsum + 10 min, • With Gypsum added + 10 min
Calcium Aluminates Formation

138
Chemical Evolution

water
gypsum
added to mill

C3A

clinker

139
Chemical Evolution
in a few seconds ...
water
gypsum
added to mill
dissolution
Ca2+ SO42-
of the surface of
Ca2+ Al(OH)4-
C3A and gypsum grains
C3A

clinker

140
Chemical Evolution
in a few seconds ...
water
gypsum
added to mill
dissolution
Ca2+ SO42-
of the surface of
C3A and gypsum grains
C3A

clinker formation
“blocking” ettringite
C3A.3CaSO4.32H2O
141
 in a
few + C3A
C3A + H2O

seconds ! CaSO4.2H2O
“blocking” ettringite
C3A.3CaSO4.32H2O

2-3 h
within hours !
ettringite
in long needles

once + remained
all gypsum
has reacted C3A
9-15 h :
C3A.CaSO4.14H2O
hydrated
142
calcium monosulfoaluminate
5.3. Properties of Hydration Products
1. Calcium Silicate Hydrates (C-S-H gel) or Tobermorite gel:

Calcium silicate hydrate (C-S-H gel) is the most important hydration product of Portland cement.
Structure: The hyphen between C-S-H represents the non-defined product of calcium silicate hydrate. It is a poorly crystalline fibrous mass.
C-S-H gel is also called Tobermorite gel as its structure is similar to the naturally occurring mineral Tobermorite.
C-S-H gel is the most important product formed during the hydration reaction as it determines the favorable properties of concrete.
Initially, there was no surely that the product of both C3S and C2S is the same, but later on, it was proved true.
50-60 % of the volume of solids in fully hydrated cement paste comprises C-S-H gel alone.

2. Calcium Hydroxide Ca(OH)2 or Lime or Portlandite:

It constitutes 20 to 25% of the solidified volume of hydrated cement paste.

Structure: Distinct hexagonal prism morphology, stable crystalline.
Calcium hydroxide helps in maintaining a pH value of 13 around the reinforcement, which acts as a passive protective layer preventing the corrosion of reinforcement. This is the
only advantage of Ca(OH)2
It leads to loss of durability of concrete due to the following three reasons:
-Ca(OH)2 is easily soluble in water and gets leached out, making concrete mass porous, resulting in low strength and durability.
-Ca(OH)2 reacts with sulfates present in water or soil and forms CaSO4, which in turn reacts with C3A and forms higher volume products, which produces cracks and leads to
deterioration of concrete. This phenomenon is also called as Sulphate Attack.
-Ca(OH)2 reacts with CO2 present in the atmosphere and forms CaCO3. Initially, the reaction transpires on the surface of concrete but gradually penetrates into the mass. If the
concrete mass is a little porous and reduces the pH value of the passive protective layer, it makes the reinforcement susceptible to corrosion. This type of deterioration is called
carbonation of concrete.
Thus, it can be seen that Ca(OH)2 is mostly undesirable in concrete, but due to its ability to protect the reinforcement, its value can’t be completely undermine.

3. Calcium Aluminate Hydrate and Ferrite hydrate:

The hydrates product of C3A and C4AF may contribute in the early strength if the reaction is rapid.
Ettringite may act negative or positive role , if it will cover the voids ,this we will be positive for the strength gain. If there is Delayed Ettringite Formation ,( DEF phenomenon)
under high temp. curing ( 60-70 C) , there will be crack and deterioration of the concrete.
143
Early hydration of Silicates grains

144
Hydration Process

145
Hydration Process

146
C-S-H and CH formation

147
Hydration Products

148
5.4. Effect of Minor Phases and Gypsum on Hydration Process
1- Free lime and MgO:
The uncombined lime ( free CaO) and Periclase ( MgO), if present in large quantities in cement, may cause expansion due to slow hydration reaction after setting:
CaO + H2O=Ca(OH)2
MgO+H2O=Mg(OH)2
The actual degree of expansion depends on the state and distribution of these oxides in cement, in particular the large crystals of Periclase or hard burnt free lime produce
unsoundness.
2-Sulfates:
As discussed before in the Volatilization session, the sources of Sulfate in clinker are :
Raw materials: pyrites have the high value and sometimes the sulfate is low and gypsum must be added to adjust the SO3/ALK ratio.
Fuels: impact from fuels is often higher than from raw materials
Gas has no sulfates, Coal and Oil have varying amount, Petcoke is in general high, Alternative Fuels: Tires have the highest value
In many cases the sulfates input varies more than alkali input does.
We are talking about Ordinary Portland Cement or CEM I or Type I cements in which the source of SO3 is coming from
Clinker+Gypsum
**What about GYPSUM** ( CaSO4.2H2O)
The gypsum is added to prevent the flash setting-as discussed in hydration- and makes the concrete workable for hours.
The gypsum influences not only the setting as regulator and retarder but also other cement properties such as grindability , sensitivity to storage , volume stability and strength.
Gypsum enhances the workability and fluidity of cement paste by providing lubrication and reducing friction between particles. This results in improved cohesiveness, making the
concrete easier to handle. Presence of gypsum makes the cement easy to grind because of the crystalline water of the gypsum which acts as polars and breaking the interstitial bonds
of the cement phases and enhances the grindability. Its presence in cement has a positive impact on the strength development of concrete over time. It contributes to the formation
of ettringite, a hydrated compound that fills the voids between cement particles, resulting in denser and stronger concrete structures.
Types of Gypsum
Five basic modifications of CaSO4:
CaSO4.2H2O (dihydrate) - CaSO4 ( anhydrite II) - CaSO4.1/2H2O (hemihydrate) - CaSO4 ( anhydrite III) and CaSO4 ( anhydrite I)
The dihydrate and anhydrite II are naturally occurring and they are stable and used in cement.
The metastable semihydrate and anhydrite III are not in nature but they are formed after grinding and storing of cement at elevated temp. by dehydration of gypsum ( false set) , this
is why the temperature in the cement mill is very important.
The anhydrite I is formed in the kiln during the burning.
All the 5 forms are present in cement industry in different stages. 149
Gypsum forms
Designation formula Crystal Density Range of Solubility occurrence
Water g/cm3 stability at 20 oC
% oC
In In cement
nature

Dihydrate CaSO4.2H2O 20 2.32 <40 0.2 Yes Yes

Hemihydrate CaSO4.1/2H2O 6-21 2.7 Metastable 0.95 No Yes
Anhydrite III CaSO4 0 2.5 Metastable 0.95 No Yes
Anhydrite II CaSO4 0 2.98 40-1180 0.2 Yes Yes
Anhydrite I CaSO4 0 ---- >1100 ---- No Clinker

-Use of dihydrate and natural anhydrite II with cement grinding.

-Hemihydrate and anhydrite III are not available in nature but modification occurs during grinding.
-Anhydrite I forms during burning in kiln.
i.e. cement has all forms of gypsum.
Gypsum Forms Transformation

Gypsum (CaSO4.2H2O)
is a chemically stable naturally occurring mineral of moderate solubility. When gypsum is heated however, it
dehydrates and is converted hemihydrate(CaSO4.1/2H2O) and at higher temperatures anhydrite III (CaSO4).
Both these dehydration products are significantly more soluble than gypsum. The dehydration of gypsum occurs at
relatively low temperatures. Such temperatures can occur during the cement grinding process. Strict temperature
controls are therefore exercised during the grinding process. Sustained high temperatures during the grinding of cement
can result in the formation of significant quantities hemihydrate and anhydrite III . These minerals react readily with
water to recrystallize as gypsum. This process is termed a false set, which, contrary to a flash set, is reversible. Extended
or further mixing causes the stiffened cement paste to revert to a plastic state. 151
Why do we need Sulphate in Cement ?

• C3A is a very reactive clinker phase

In the absence of gypsum, the reaction of C3A C3A + CH + 3 H = C4AH4

with water is very rapid. The C3A is converted to
calcium aluminate hydrateC3A (4CaO.Al203.19H).
Which forms interlinking bridges of solid material
between the cement particles. These interlinking
bridges reduce the mobility of the cement Aluminate “FLASH” set,
particles and produce a firm structure, which + C3A
results in setting of the cement mixture. This disturbed C3S set
rapid setting is called a flash set and is + C3S
irreversible. decreased strength

152
Role of Gypsum in Cement Hydration

153
5.5. Effect of Gypsum on Cement Setting
Gypsum is an extremely important part of the cement. It is ,however, often neglected to pay proper attention to it in the production of cement.
The Role of Gypsum in Cement Setting
The Sulfates which came from soluble CaSO4 dissolve and react with C3A to form ettringite, this initial reaction is retarded by cohesive cover around C3A particles by ettringite
and in this way inhibits their further reaction.
Initial Setting Time
The time to which cement can be moulded in any desired shape without losing its strength. Or The time at which cement starts hardens and completely loses its plasticity . Or
The time available for mixing the cement and placing it in position. If delayed further, cement loses its strength.
Final Setting Time
The time at which cement completely loses its plasticity and became hard. Or The time taken by cement to gain its entire strength.
Factors affecting Setting of the cement
The reactivity of the clinker ( C3A content and alkali content) ,The type and amount of Gypsum added-,The dosage of the mineral additives, The cement fineness, Using of
chemical admixtures and Hydration temperature.
In order to obtain normal setting, it is essential to adjust the supply of SOLUBLE SULFATES to the reactivity of the clinker during the first minutes and hours of hydration. If there
is no proper balance between Sulfates and clinker reactivity , abnormal setting can occur:
1- Flash set:
caused by too small amount of easily soluble CaSO4.
Most likely to occur if : High C3A content or reactive C3A (depend on alkali content), Low mill temp, High natural CaSO4 in gypsum, Coarse ground gypsum and Excess of alkali
over sulfate in clinker.
2- False set:
caused by high temp. in the mill and the dehydration of Gypsum to an easily soluble hemihydrate and anhydrite III occurred.
Hemihydrate and anhydrite (III) recrystalize to Gypsum by forming solid framework which affects the stiffening of the cement paste.
This framework is broken down again through reaction with C3A , for this reason the cement paste can regain its previous plasticity by remixing.
Most likely to occur if: Low clinker SO3, High cement SO3, High dihydrate concentration in gypsum, High mill temperature and Low C3A content or less reactive.
Optimum gypsum content:
- Depend on C3A content and Reactivity
- Too much soluble SO3 causes False set and recrytallisation of SO3 then cement loses workability.
- Too little soluble SO3 causes Flash set and C3A reactivity is uncontrolled then cement loses workability.
Optimum level is determined by experiments in lab.
Simply: 154
Cement ( 95% clinker+5% gypsum) and clinker SO3 ( 1.0 %) + gypsum SO3 ( 35 %) then, the SO3 in cement will be ( 0.95 * 1.0 + 0.05 *35 ) = 2.7 %.
 Setting time – C3A & Sulphates

In cement sulphate is necessary to

control the hydration of clinker
mainly for the reaction of C3A

C3A Reactivity:
a) cement fineness
b) C3A level and reactivity
c) Alkali content / solubility

Regular optimisation of sulphate in

cement is necessary !

Syngenite:
Is Potassium Calcium Sulfate CaK2(SO4)2.H2O , a compound
sometimes produced during the hydration and storage by reaction of
Potassium Sulfate and Gypsum causing false set. 155
 Effect of Clinker and Gypsum Reactivity on Setting

The setting of cement is mainly

influenced by the reactivity of the
clinker (i.e. C3A and alkali content)
and by the type and amount of the
calcium sulphate added.

156
Control of C3A Hydration ( CaSO4 Solubility)

• The right amount of Calcium Sulphate is important.

• The solubility “speed” of sulphates is even more important.
• Different types of sulphates have different solubility

Alkali sulphate > Hemihydrate > Anhydrite (III) > Dihydrate (Gypsum) > Anhydrite (II) natural
K2SO4 CaSO4. 0,5H2O CaSO4 CaSO4 . 2 H2O CaSO4
• Soluble SO3 comes from dehydration of dihydrate
CaSO4.2H2O  CaSO4.1/2H2O  CaSO4 ( III )(soluble)

• Process levers:
• Gypsum / Anhydrite ratio
• Mill / Silo temperature
• Alkali Sulphate content of clinker

157
Setting and Hardening of the cement paste
setting
start end
40 25
C3S rate of hydration (%)

(%)
strength / 28 days strength
plastic hardening 20
30 state
15
20
10

10
5

0 0 0
0 2 4 6 8 10 12 14

time (hours) 158

Setting time – Sulphates

good
150
C3A

workability
ettringite gypsum

Ettringite good Plaster

flash set workability false set
bad 0
0 100
hemi-hydrate (%)

159
Factors affecting Setting time

w/c ratio Admixtures

Cement fineness Temperatures

Setting time
C3A Clinker
mineralization

CaO free
C3S

Sulphate content Alkali sulphates

160
Setting vs. Hardening

161
5.6. Dehydration of Gypsum
The controlling of Sulfates in the cement mill and Gypsum addition is very important in Cement Production.
1- Before the cement mill
In order to optimize the rheology of the cement, it is to optimize the quantity of the hemihydrate. It can be done by:
- Selection of CaSO4 addition by ensuring that we add only Gypsum if we are able to master the temperature of the mill.
- Avoid putting hot clinker in the mill to master the mill temperature.
- Avoid weathered clinker

2- Inside the mill

(a) Optimize mill temperature to control the amount of hemihydrate.
Mill Temperature is a function of:
Clinker temperature, Type of mill( open or closed circuit), Mill air flow, separator efficiency, Feed to air ratio.
If the temperature is too low:
Not optimized gypsum phase, Risk of lump formation from hydration.
Actions to adjust the low temperature:
Use fresh clinker if possible, Bring hot gas to the mill, Using dry additives, Reduce the air flow in the mill, Reduce mill load.
If the temperature is too high:
Not optimized gypsum phase, False set, Strength affected, Grindability affected, Hot cement leaving the silo, Risk of lump formation in the silo ( syngenite K2Ca(SO4).H2O formation)
Actions to adjust the too high temperature:
Improve clinker cooling ( cooler efficiency), Use cold clinker if possible, Increase the air flow to the mill, Increase mill loading, Add spray water to inlet and outlet of the mill ( with care
of course).
(b) Optimize air circulation.
(c) Optimize water spray system ( do not prehydrate the cement).

3- After the mill ( storage in the silo)

High cement temperature after the mill will result in dehydration in the silo but free water remains in the silo.
CaSO4.2H2O=CaSO4.1/2H20+1.5H20
this 1.5H2O remains in the silo causing lumps, silo discharge, losing of strength and setting time reduced.
Store below 60°C and reduce the time of storage of the cement in the silo to avoid the dehydration of the gypsum. 162
Dehydration of Gypsum

163
Reasons of lumps formation in cement silo

164
5.7.Effect of Alkalis on Cement and Concrete
Where do Alkalis come from?
- Raw materials: mainly related to Al2O3 and SiO2 (clay minerals and secondary raw materials).
- Fuels: only little impact only from the coal ash.
- Cement additives:
Slag is often contain low alkalis content, Fly ash may contain high alkalis content, Filter dust is varying in content depends on kiln conditions.
Normally we have to avoid alkalis addition.
Types of Alkalis
1- Insoluble:
occurs in clinker structure as free Na2O and K2O in C3A crystal structure.
difficulty in controlling rheology, workability problems, plastic shrinkage, reduced 28d strength
2- Soluble:
are alkalis sulfates
usually improve rheology, increase early strength ( function of C3A content and reactivity), sensitive to lumping and gluing, causes efflorescence, reduced 28d strength
3- Soluble and Insoluble:
reduce 28d strength, maintain a high pH value which is good for reinforcement, favor alkalis aggregate reaction, clinker finer and harder to grind.

Effect on Cement and Concrete properties

1- Strength:
- Alkalis sulfates ( % soluble Na2Oeq) increases the 1-2d strength ( depends on the content and reactivity of C3A).
- Increasing of total alkalis (Na2Oeq) by 0.1% will reduce 28d strength by 1MPa.
2- Efflorescence:
Efflorescence is a crystalline deposit of salts that can form when water is present in or on concrete surfaces. It has a white or greyish tint and consists of salt deposits that remain
on the surface after water evaporates.
-Types of salts :Sodium sulfate-Potassium sulfate-Sodium carbonate-Potassium carbonate
3- Alkalis Aggregate Reaction (AAR) or Alkalis Silica Reaction ( ASR):
The alkali–silica reaction (ASR), more commonly known as concrete cancer, is a deleterious swelling reaction that occurs over time in concrete between the highly alkaline
cement paste and the reactive amorphous (i.e., non-crystalline) silica found in many common aggregates.

Because most of the difficulties and problems come from the high alkalis content - as we discussed - most standards set limits that not to exceed 0.6 %.
Also, the production of low alkalis cements has become an urgent matter, through the expansion of the production of blended cements.
165
Efflorescence

• White layers on surface

• Mainly in young age
• Types:
• Alkalis sulphates
• Alkalis carbonates
• Solution:
• quicker cements, additives, change concrete production
166
Efflorescence

Water transport
Water Evaporation rate is a
liquid transport function of = f (T, wind,
- gas relative Humidity)
Salt transport

Speed of water
transport
Zone of evaporation

“Efflorescence”

Water transport liquid When liquid transport reaches

the surface of the concrete
efflorescence may occur

Salt transport • Alkali –Sulphates

•Alkali carbonates

167
Alkali Silica Reaction ASR or Alkali Aggregate Reaction AAR

AAR: Chemical reaction within concrete between:

aggregate - sensitive versus alkalis

+ alkalis hydroxides - cement, admixtures)
+ water (humid conditions)

time, concrete type

alkali silicate gel aggregate type,
temperature,.....
swelling due to moisture cracking
absorption

168
Concrete Cracks caused by AAR

AAR “macrostructure”:

Cracks, through the whole

concrete structure

169
AAR mechanism

170
AAR - most affected constructions
 Foundations
 Concrete roads
 Bridges
 Railway sleepers
 Walls
 Pipes
“Constructions exposed
to humidity”

Repair:
Only in limited cases possible
demolition
Possibilities to lower the Alkali Content
Dilution in cement Removal during Low alkali Raw Mix
clinker burning
 CEM II/III cements 1. Alkali Bypass:  Selective mining

 expensive, possible  Use of alternative raw

BUT materials
for all preheater kilns
 Lower early strength  Strong depending on
2. Separation filter
dust present quarry / Raw
 High sensitivity for Mix situation
curing after moulding
 only limited decrease
depends on alkali
concentration in dust

 General: problem
dust management

172
5.8. Heat of Hydration
Heat of Hydration
The hydration reaction is an exothermic process, that means during the reaction of cement with water heat is liberated. The quantity of liberated heat is quite appreciable (typically
380 J/g for OPC at 28 days) and can lead to a significant temperature rise in mass concrete construction, where the heat is not allowed to escape . During cooling of the hardened
concrete, thermal gradients may develop and give problems with crack formation. That is the reason why special low heat cements have to be used for mass concrete applications.
The main measure to control the heat of hydration of Portland cement is the adjustment of clinker composition. The clinker minerals contributing most to the heat of hydration are
C3S and C3A , so that it is necessary to limit these compounds to reduce heat development during hydration. On the other hand, it is also possible to keep the heat liberation low by
not grinding the cement too fine.
The low heat cements used for mass concrete - type II and IV ASTM - with low heat of hydration of about 250 to 300 J/g after 28 days contain less C3S and C3A and are fairly coarse.
The rapid hardening cement - type III ASTM - with increased heat of hydration of about 420 J/g after 28 days is usually richer in C3S and C3A and of higher fineness, compared with
the ordinary Portland cement - type I ASTM-.
A very effective means to reduce the amount and rate of heat of hydration of portland cement is to use additives like slag ( blended cements).

Acceleration and Retardation of cement hydration

The process of hydration can be accelerated or retarded by different factors
Use of accelerators and retarders:
The most efficient accelerator is calcium chloride (CaCl2), but the problem with this product is the corrosion of the steel reinforcement.
It is believed that CaCl2 is acting like a catalysator.
Retarders for cement hydration are for instance phosphates, zincates and carbohydrates (including sugar). The retarding action is simply explained by the formation of a
monomolecular protective film around the cement particles which slows down their reaction with water.
Hydration temperature:
The rate of hydration is strongly influenced by the temperature. Temperature increases, rate increases.
The effect of temperature on cement hydration is of particular importance in extreme climates and for steam curing.
Cement fineness:
The higher the fineness of the cement, the more extended is the zone of reaction. This leads of course to a higher rate of hydration.
Cement composition:
The activity of the clinker used in the cement affects considerably the rate of hydration.
A high rate of hydration can be expected of clinkers rich in C3A and C3S and with a high alkali content.
173
Heat of Hydration
500 J/g
C-S-H
C3S + H2O

H2O 850 J/g calcium

C3A + +
sulfoaluminate
CaSO4.2H2O

260 J/g
C2S + H2O C-S-H

450 J/g Calcium

C4AF + +
H2O
sulfo(iron,aluminate)
CaSO4.2H2O 174
Heat of Hydration (a)

Heat evolution

time
1h 24 h
(calorimetry curve on cement paste)
175
Heat of Hydration (b)

Heat evolution

- High C3S CSH

- non-blocking ettringite

Blocking ettringite

Acceleration
C3S CSH

1h time
24 h
(calorimetry curve on cement paste)
176
Heat of Hydration (c)

Heat evolution

- High C3S CSH

- non-blocking ettringite
ettringite

Blocking ettringite
monosulfoaluminate

Acceleration
C3S CSH

time
1h 24 h
(calorimetry curve on cement paste)
177
Heat of Hydration (d)

Heat evolution

- High C3S CSH

- non-blocking ettringite
ettringite

Blocking ettringite
setting monosulfoaluminate
zone
Acceleration
C3S CSH

1h 24 h time
(calorimetry curve on cement paste)
178
Rate of Heat of Hydration Evolution

179
Hydration and heat generation in concrete

180
Effect of heat generated from cement paste on concrete

181
 6. Alternative Raw Materials( AFR)
and Supplementary Cementitious Materials(SCMs)

182
 6.1. Slag as AFR and SCMs
The different types of cement and the additives used, whether to improve properties or try to reduce costs and reduced emissions will be discussed in the following chapter.

Using of Alternative Raw Materials (AFR) , Alternative Fuel (AF) or Supplementary Cementitious Materials ( SCMs) in the production of the
different types of cement becomes now un urgent matter.
Depending on their composition and characteristics they supplement different natural raw mix components and additives in the final product. As a result, they help conserve natural
raw material resources on one side and recycle the polluting industrial wastes on the other.
From the perspectives of both energy conservation and pollution abatement, the use of alternative fuels and (AF) raw materials (AFR) has emerged as an important operational
strategy in the cement industry.

The most important and famous AF and AFR which is *SLAG*

(1) Generation of SLAG:

In the Iron and Steel production, limestone is added to remove the impurities from the Iron Ore.
During the process of reducing iron ore, it is necessary to remove the silica, alumina (Al2O3), and other non-ferrous components contained in iron ore. The added limestone fuses
with these components and lowers their melting point, making it easier to separate them from the iron and recover them. This recovered substance is slag.
(2) Classification:
Iron and steel slag can be broadly classified into blast furnace slag that is generated when iron ore is melted and reduced in a blast furnace, and steelmaking slag that is generated
during the steelmaking processes used to modify the components of iron.
Blast furnace slag
is a combination of silica and other non-ferrous components of iron ore, ash from coke used as a reducing material, and limestone auxiliary material.
Because its specific gravity is less than that of pig iron, during the heating process the molten slag rises above the pig iron allowing it to be easily separated and recovered.
Steelmaking slag
is generated by the process that turns pig iron produced by a blast furnace into tough and highly workable steel. Converter slag is the oxidized material that is generated when lime
and other auxiliary materials are added and oxygen is blown onto the pig iron in order to remove carbon, phosphorous, sulfur, and other components from the pig iron and refine it
to produce strong steel. The other type of steelmaking slag, electric arc furnace slag, is generated when iron scrap is melted and refined.

183
Slag Production

184
Slag Production Process

185
Extraction of molten Slag from Blast Furnace

186
Generation of Slag

187
6.2. Classification of Slag and its Applications
1- Types of Slag
The iron and steel slag that is generated as a byproduct of iron and steel manufacturing processes can be broadly categorized into blast furnace slag and steelmaking slag.
(A) -Blast furnace slag
Blast furnace slag is recovered by melting separation from blast furnaces that produce molten pig iron. It consists of non-ferrous components contained in the iron ore together with
limestone as an auxiliary materials and ash from coke.
When it is ejected from a blast furnace, the slag is molten at a temperature of approximately 1,500℃. Depending on the cooling method used, it is classified either as Air-Cooled Slag or
Granulated Slag.
Air-cooled slag (ACS)
The molten slag flows into a cooling yard, where it is cooled slowly by natural cooling and by spraying with water. This results in a crystalline, rock-like air-cooled slag.
Granulated slag (GGBFS)
The molten slag is cooled rapidly by jets of pressurized water, resulting in a vitreous, granulated slag.
(B) Steelmaking slag
This slag is a byproduct from steelmaking processes in which the components of pig iron and steel-scrap are modified. Steelmaking slag consists of converter slag and electric arc slag.
Converter slag
In the same way as air-cooled blast furnace slag, converter slag is cooled slowly by natural cooling and water spray in a cooling yard.
Electric arc furnace slag
Is generated when iron scrap is melted and refined. It consists of oxidizing slag that is generated during oxidation refining, and reducing slag that is generated during reduction refining.

2-Characteristics and application of Iron and Steel Slag

As a result of growing environmental awareness, iron and steel slag is highly regarded as a recycled material that can reduce impacts on the environment due to its resource-conservation
and energy-saving effects.
Air-cooled blast furnace slag
Because of its large load-bearing capacity, it is used in road base coarse material in the same way as gravel. There is no risk of alkali-aggregate reaction, and this slag contains no clay or
organic impurities. As a result, it is also used as a concrete aggregate in the same way as natural aggregate.
May be used as alternative raw materials in cement production and additive to the finished product under certain conditions.
Granulated blast furnace slag
This slag has a hydraulic property and there is no risk of alkali-aggregate reaction. Because of the powerful latent hydraulic property that results from fine grinding and glass content, this
slag is used in products such as Portland blast furnace slag cement.
The advantages of this blast furnace slag cement, such as increasing strength over long periods of time, low heating speed when reacting with water, and high chemical durability, are put
to effective use in a broad range of fields including in the construction of ports and harbors. 188
Classification of Slag

189
Characteristics of Slag

190
Blast furnace slag

Air-cooled slag
Granulated slag

191
Blast furnace slag

• by-product from pig iron production

 forms in blast furnace from fusion of lime-
stone flux with ash from coke and siliceous/
aluminous residue that remains after reduction and separation of iron from
iron ore
 less dense blast furnace slag floats on top of the molten pig iron
 both products are periodically tapped at the bottom of the blast furnace
 latent hydraulic material
 it is NOT: steel slag or slag from other (non-ferrous) metallurgical process

• rapid cooling/quenching necessary for hydraulic reactivity

 minimize crystallisation and get amorphous (glassy) slags

192
Steelmaking slag
Steelmaking slag:
Because of its hydraulic property and the large bearing
capacity it can provide, steelmaking slag is used as a road
base course material. With high particle density and
hardness, this slag has superior wear resistance and for this
reason is used as an aggregate for asphalt concrete. In
addition, due to its high angle of shearing resistance, high
particle density, and large weight per unit volume, it is also
used as a material for civil engineering works and as a ground
improvement material (i.e., material for sand compaction
piles)

Converter

193
Electric arc furnace Steelmaking slag (converter slag)
Primary characteristics and applications of iron and steel slag
Characteristics Applications
Hydraulic property Road base course material
No alkali-aggregate
Coarse aggregate for concrete
reaction
Cement clinker raw material
Low Na2O and K2O
(replacement for clay)
Air-cooled
slag Thermal insulation and
sound absorption
Raw material for rock wool
effects when made into
a fiber
Fertilizer component
Calcium silicate fertilizer
(CaO, SiO2)
Raw material for Portland blast
Strong latent hydraulic furnace slag cement
property when finely
Blending material for Portland cement
ground
Blast Concrete admixtures
furnace slag
Raw material for cement clinker
Low Na2O and K2O
(replacement for clay)
Latent hydraulic Material for civil engineering works,
property ground improvement material (Backfill
material, earth cover material,
Granulated
Lightweight, large angle embankment material, road subgrade
slag
of internal friction, large improvement material, sand
water permeability compaction material, ground drainage
layers, etc.)
Does not contain
chlorides.
Fine aggregate for concrete
No alkali-aggregate
reaction

Fertilizer component Calcium silicate fertilizer

(CaO, SiO2) Soil improvement
Hard, wear-resistant Aggregate for asphalt concrete
Hydraulic property Base course material
Material for civil engineering works,
Converter Large angle of internal
ground improvement material
Steelmaking slag, electric friction
(Material for sand compaction piles)
slag arc furnace
slag FeO, CaO,
Raw material for cement clinker
SiO2 components
Fertilizer components
194
Fertilizer and soil improvement
(CaO, SiO2, MgO, FeO)
Slag Applications

195
6.3. Air Cooled Slag Utilization in Cement Production
ACS contains CaO, SiO2, Al2O3, Fe2O3 and MgO as major components. Also contains SO3, Na2O, K2O and TiO2 as minors.
The more important property of ACS is that it is free from Cl % and CO2 % (its LOI is zero or minus or very low).
Its chemical and physical properties are somewhat similar to those of clinker and cement, so it can be used in the production of clinker and cement.
There is a very important thing that must be taken into consideration before making the decision to use ACS in the
cement industry:
a-Comprehensive survey must be conducted of the types of this slag in iron factories, as there are many types and different sizes, as some of it is crushed into different sizes, and
some is fine and does not need crushing.
b-Practical and laboratory experiments must be carried out to know all the effects and to ensure proper and smooth operation.
The utilization process
1- Using of ACS as secondary raw material or Supplementary Cementitious Materials (SCMs) in the raw mix
From the analysis of ACS, we can notice that there are some types rich in Al2O3 which can be used for replacing some of clay in the Raw Mix. Other types rich in CaO which can
replace some of Lime in the Raw Mix. Other types rich in SiO2 which can replace some of Sand or Marl in the Raw Mix.
Under certain conditions in the processing of Iron production, there are some types of ACS which contain considerable amount of Fe2O3 and it can replace Iron Ore in the Raw Mix.
ACS addition can be done through the pile or a separate hopper.

2- Using of ACS as an additive material in the finished product

As we discussed, ACS has components such as clinker and has cementitious properties, even if they are very weak compared to its fellow GGBFS, which has very strong cementitiuos
properties. It is possible to be an additive with gypsum and clinker, and this is of course after reviewing the specifications of each country and after doing trials as well.

Advantages and Disadvantages of Using ACS in Cement Industry

1- Advantages:
-Reducing of CO2 emission from the Cement Industry.
-Reducing of the cost of the Cement because ACS is cheaper than most of Cement raw materials.
-Consuming the large amount of ACS.
-Reducing the Heat Consumption because the ACS is already burnt material so it will enhance the burning conditions and act as fluxing agent material in the Kiln.
2- Disadvantages:
-ACS is hard to grind, so the wearing of the mill body and diaphragm must be monitored.
-Using of ACS in the Cement Mill as additive material may affect the early strength and Setting time of the cement produced which can be overcomed by producing more fine
cement and using suitable grinding aid. 196
Analysis of Air Cooled Slag (ACS)

The percentage of Fe2O3 is varied from process to

another, sometimes reached to 20-30%

197
Types of Air Cooled Slag (ACS)

198
ACS addition in Cement process

ACS addition

ACS addition

ACS addition

199
ACS as Cement Raw Material

200
6.4. GGBFS (Ground Granulated Blast Furnace Slag)
The following topics will be discussed
1- What is GGBFS?
2- How is GGBFS produced?
3- What are the chemical and physical properties of GGBFS?
4- Production of Slag Cement and the types of it.
5- Hydration of Slag Cement.
6- Importance of Blended Cement.

What is GGBFS?
It is obtained by quenching molten iron slag (a by-product of iron and steel-making) from a blast furnace in water or steam, to produce a glassy, granular product that is then dried
and ground into a fine powder.
Ground granulated blast furnace slag is a latent hydraulic binder forming calcium silicate hydrates (C-S-H) after contact with water. It is a strength-enhancing compound improving
the durability of concrete.
Its main advantage is its slow release of hydration heat, allowing limitation of the temperature increase in massive concrete components and structures during cement setting and
concrete curing, we will discuss it in details later.
How is GGBFS produced?
In the case of pig iron production, the flux consists mostly of a mixture of limestone or in some cases dolomite. In the blast furnace the slag floats on top of the iron and is
decanted for separation. Slow cooling of slag melts results in an unreactive crystalline material consisting of an assemblage of Ca-Al-Mg silicates. To obtain a good slag reactivity or
hydraulicity, the slag melt needs to be rapidly cooled or quenched below 800 °C in order to prevent the crystallization of minerals. In order to cool and fragment the slag, a
granulation process can be applied in which molten slag is subjected to jet streams of water or air under pressure.
Alternatively, in the pelletization process, the liquid slag is partially cooled with water and subsequently projected into the air by a rotating drum. In order to obtain a suitable
reactivity, the obtained fragments are ground to reach the same fineness as Portland cement.
Chemical Composition
Silicate and aluminate impurities from the ore and coke are combined in the blast furnace with a flux which lowers the viscosity of the slag.
The main components of blast furnace slag are: CaO (35-45%), SiO2 (30-40%), Al2O3 (8-25%), and MgO (1-18%).
In general increasing the CaO content of the slag results in raised slag basicity and an increase in compressive strength. The glass content of slags suitable for blending with
Portland cement typically varies between 90 and 100% and depends on the cooling method and the temperature at which cooling is initiated.
201
GGBFS (Ground Granulated Blast Furnace Slag)

Samples of "ground granulated blast furnace slag" (left) and "granulated blast furnace slag" (right)
GGBFS Shapes and Colors
Process Operation of GGBFS
Sources of GGBFS
Comparison between Chemical Composition of GGBFS and Portland Cement

Mineral GGBFS Portland Cement

CaO 35-45% 55-66%
SiO2 30-40% 20-24%
Al2O3 8-25% 0-8%
MgO 1-18% 5%
Comparison between GGBFS , Pozzolana and Fly Ash
Although GGBFS , Pozzolana and Fly Ash have very different properties in many respects, they have one thing in
common: they consist essentially of the same major chemical elements as PC clinker: SiO2 - Al2O3- CaO.

Chemical Composition of Hydraulic Additions GGBFS , Pozzolana and Fly Ash

Natural and/or
GGBFS Class F Fly Ash
Elements Artificial Pozzolan

SiO2 30 - 40 50 - 75 40 - 65
15 - 40
Al2O3 (TiO2) 8 - 25 15 - 25
1 - 10
CaO 35 - 45 1 - 15
3 - 17
Fe2O3 0.5 - 1.5 3 - 10

MgO 1 - 18 <5 -3
0.3 - 3
SO3 1.5 - 6 0.1 - 1.5
2-3
K2O 0 - 0.5 0.5 - 4
Ternary System Si , Ca and Al
6.5. Properties of GGBFS
GGBFS has great importance currently in terms of the production of blended cement ( Slag Cement) or as additives in Concrete which reduce emissions from these
industries and reduces energy as well. And reduction of the cost in general at the end.

Chemical Properties

High CaO content is beneficial to the development of strengths. However, the CaO/SiO2 ratio can only be increased to a limited degree because increasing CaO content
results in an increasing of viscosity necessitating higher operating temperature, which in turn affects costs. At constant basicity, the higher Al2O3 content has a favorable
effect on the strength development. Fe2O3 and MnO and S ( sulfides) generally have an adverse effect on strength development. MgO is not present in form of periclase,
and therefore does not affect the soundness of the hardened concrete. MgO content up to 20% are permissible in slag.
The increase of SiO2 content reduces grindability, and the presence of metallic iron increases the milling time.

Mineralogical Properties

The chemical composition of GGBFS is not significant enough to predict their behaviour. Much more important than chemistry, is the mineralogy of GGBFS, and principally
the proportion between the crystalline and the glassy phase. A good GGBFS shall contain at least 2/3 by mass of glassy GGBFS, according to EN standard.
The mineralogical properties can be determined by:
¨ Microscopy
¨ X-ray diffraction (XRD)
¨ Differential thermal analysis
Common crystalline constituents of GGBFS are merwinite and melilite. Other minor components like, belite, monticellite, rankinite, wollastonite and forsterite.
The most common mineral is melilite, a name applied to any of a series of solid solutions from akermanite, which is represented by (2CaO . MgO . 2SiO2), to gehlenite
(2CaO . Al2O3 . SiO2).
In GGBFS of low lime and high alumina content, the mineral anorthite (CaO . Al2O3 . 2SiO2) may appear. In GGBFS with a high lime content, the wollastonite (CS) may be
formed.
You can see that most of the minerals are Clacium Silicates like what we have in the clinker except C3S and C3A.
I asked you to think about it, why we have not C3S ( alite) and C3A in GGBFS while we have C2S ( belite) ?

GGBFS Reactivity

Many researchers have attempted to define the hydraulicity of GGBFS in terms of chemical formulae based on the observed effects of the various oxides on the
compressive strengths of slag cements. The usefulness of calculated empirical formulae is questionable and the only fixed line guide is the strength development in cement.
Various specifications have paid attention to the activity of GGBFS and the extent to which it can be used in the cement. 209
Summary of the reactivity indices for GGBFS

Numerous indices have been

developed to predict and
specify the reactivity of
GGBFS.
While such indices may be
convenient for quality
control of GGBFS from one
source, they are not
satisfactory for a general
prediction of strength of
various GGBFS in cement,
because there is no linear
relationship between
strength and oxide contents
in GGBFS over a large
composition range.
Commonly occurring Minerals in GGBFS

Mineral Formula Analysis (% by mass)

SiO2 Al2O3 CaO MgO

Gehlenite 2CaO . Al2O3. SiO2 21.9 37.2 40.9

Akermanite 2CaO . MgO . 2SiO2 44.1 41.1 14.8
Wollastonite CaO . SiO2 51.7 48.3
C2S ( Belite) 2CaO . SiO2 34.9 65.1
Rankinite 3CaO 2SiO2 41.7 38.3
Merwinite 3CaO . MgO2SiO2
Anorthite CaO . Al2O3 . 2SiO2 43.2 36.6 20.2
Monticellite CaO . MgO . SiO2 38.4 35.8 25.8
Spinel MgO . Al2O3
Composition of GBFS in the ternary diagram CaO-SiO2 –Al2 O3 with 10% MgO
Factors affecting the reactivity of GGBFS
 Fineness
Increased surface area leads to better strength development and
more water requirement; however, the fineness of slag is limited
from practical aspects, such as economic and performance
considerations, setting time and shrinkage.

 Glass content
During the quenching process, the liquid slag forms glassy and
crystalline contents. Practical glass content of slag depends on
the cooling rate, in general, rapid rate results in high glass
content. The main difference between glass content and crystal
content of slag is that the former part has a latent hydraulic
property that makes the glass content of slag a very important
factor affecting the engineering performance of slag cement

 Chemical composition
The chemical composition of slag is mainly the four components,
namely, MgO, Al2O3, SiO2, and CaO. From a metallurgical
standpoint, slag can be sorted as either basic or acidic, and the
more basic of slag, the greater its hydraulic activity in the
presence of alkaline activators, the hydraulic values of slag
increase with the increasing CaO/SiO2 ratio up to a limiting
value.
Noting that CaO and MgO are basic oxide while SiO2 is acidic.
Al2O3 and Fe2O3 are amphoteric.
6.6. Standards and Specifications of GGBFS
First, let us answer the question, which is why there are no C3S and C3A and there is C2S in GGBFS?
We have learned that the composition of the GGBFS is a bit similar of the clinker, but CaO % in GGBFS is about 35-45 % while in clinker is about 55-66 %
meaning that it is almost doubled in clinker.
For SiO2 % in GGBFS is about 30-40 % while in clinker is about 20-24 % meaning that it is almost doubled in GGBFS.
Based on this, the reaction that takes place between CaO and SiO2 , the entire amount of CaO is consumed in the production of calcium silicate compounds,
which contain a relatively low percentage of calcium, such as CS and C2S , and there is no additional CaO for production of C3S or C3A.

GGBFS Reactivity

GGBFS has a high silica content, so it can be considered as more acidic medium rather than alkaline. If activated by OH ions, it displays hydraulic activity
(cementitious properties).
In practice, the activation is realized by addition of lime, Portland cement clinker (OH) or any alkaline salts.
Due to its latent hydraulic properties, GGBFS starts to hydrate when in contact with water. However, this reaction diminishes with time. Only in presence of an
activator the GGBFS hydration continues.
The most common activator of GGBFS in concrete is Portland cement. Here the GGBFS activation is alkaline due to the liberation of calcium hydroxide and
alkalis during Portland clinker hydration.
Apart from that, GGBFS can also be activated by other compounds such as alkali and alkali earth hydroxides, sulfates, chlorides, nitrates, carbonates, and
silicates. Compared to OPC the hydration rate of GGBFS is slower. This is reflected by a later initial setting time and lower early strength with increasing GGBFS
content . However, late strength development of concrete with GGBFS composites mostly exceeds that of OPC concrete.
ASTM C989 classifies GGBS into three grades according to its performance in the slag activity test. The three grades are:
1. Grade 80
2. Grade 100, and
3. Grade 120
GGBFS activity is evaluated by determining the compressive strength of Portland cement mortar and the corresponding mortars made with the same mass of a
blend that is 50% GGBFS and 50% Portland cement by mass. GGBFS activity is determined by the following formula,
GGBFS activity index, % = (SP/P) x 100
Where,
SP = average compressive strength of GGBFS-Cement reference mortar cubes designated age.
P = average compressive strength of reference cement mortar cubes at designated age.
Grade 80 min 75 % at 28-d
Grade 100 min 95 % at 28-d
Grade 120 min 115 % at 28-d
BS EN 15167-1 does not classify GGBFS into different grades or classes but requires the GGBFS activity index at 7 days and at 28 days shall not be 214less than
45% and 70% respectively.
Some Standards for GGBFS and its use in Cement and Concrete

BS 6699 ASTM C595

GGBFS for Use with Portland Cement Standard Specification for Blended Hydraulic Cements

BS EN 15167-1 ASTM C989

GGBFS for use in concrete, mortar and grout Definitions, Standard Specification for Slag Cement for Use in
specifications and conformity criteria Concrete and Mortars
ASTM grades and Reactivity Index for GGBFS
Brief of EN 15167
1-Glassy content ≥ 66.7% by mass
2- (CaO+MgO+SiO2) ≥ 66.7% by mass
3. (CaO+MgO)/(SiO2) > 1.0 by mass

4. Chemical requirements:

5. Physical requirements (not less than 275 m2/g)

6. Requirements when blended with cements (in 50-50 ratio)

- initial setting time (i.e. not more than twice the setting time of the reference cement)
- strength activity index (>45% at 7 days and >70% at 28 days,)
Parameters which influence on the properties of GGBFS
6.7. Blended Cement and GGBFS in Concrete
The principal reason for the production of blended cements is economic and environmental, although in most cases blended cements perform better than
Portland cement. Blended cements allow an economy of fuel and an increase of cement production due to the lower clinker/cement factor.

Technical advantages, such as:

improved durability (beneficial for service life of concrete structures), reduced heat of hydration (beneficial for casting of thick sections), reduced alkali level of
the blend (to minimize the risk of alkali-silica reaction) , improved characteristics of fresh concrete.
Possible disadvantages, such as:
slower rates of strength gain at early ages (and at lower temperatures, longer setting time, higher sensitivity to poor curing.
The disadvantages are largely overcome by the advantages gained in the overall performance.
Production of blended cements, then, has effect on the:
*reduction and optimization of production costs by:
· improved clinker factor, saving on thermal and electrical costs, increased cement output,
*activities related to environment protection and preservation by:
· conservation of natural fuels and mineral resources, use of by-products as mineral components, reduction of CO2 and heat emission,
*differentiation of products and applications by:
· opportunity to produce tailored products, improvement of cement properties for special applications,

Impact of GGBFS on Fresh Concrete Properties

1-Workability and Superplasticizer Demand
Using GGBFS in concrete generally improves workability. Thus, with increasing content of GGBFS the dosage of superplasticizer or the paste content can be
reduced, compared to a mix with Portland cement.
2-Segregation and Bleeding
Coupled with the effect of workability improvement by GGBFS is an increased tendency to bleeding and segregation. To adjust the concrete design the
superplasticizer dosages and/or the water added should be reduced to achieve the target workability.
3-Setting Time
An increase in setting time can be expected when GGBFS is used as a replacement. The degree to which the time of setting is affected is dependent on:
The proportion of GGBFS in the mix, The initial temperature of concrete and curing, w/c ratio of the mix, Type of admixture used and its dosage, Type of cement
used (OPC/SRC)
SRC has low C3A content in comparison with OPC and hence higher setting time. So a blend of GGBS and SRC coupled with the in-built retarding effect of
admixture often results in a longer setting time of concrete mixes.
219
EN 197-1 Cement Types
EN 197-1 Cement Types Classifications

In the EN standard EN 197-1 the cement types are defined by two basic criteria: proportion of components and strength
levels.
There is a matrix of five compositional classes of cements (CEM I, II, III, IV, and V) and three strength categories (32.5,
42.5, and 52.5 Mpa ) .
CEM I is Portland cement consisting of greater than 95% clinker;
CEMII is a blended Portland cement in which the designated types of additives can be added in the range of 6–35%;
CEM III is a blast furnace slag cement containing 36–95% slag;
CEM IV is a pozzolan cement containing 11–55% pozzolanic material,
and CEM V is a composite cement containing 36–80% slag, pozzolan, or fly ash.
The strength classification defines three levels:
32.5 having 28-day compressive strength of 32.5–52.5 MPa, 42.5 having 42.5–62.5 MPa, and 52.5 having strength greater
than 52.5 MPa.
The compositional classes have subclasses, depending on the level of clinker content, such as “A” (high), “B” (medium),
and “C” (low).
There is also a suffix to the strength parameter indicating high early strength shown by “R” and normal early strength,
shown by “N,” based on two-day compressive strength.
EN 197-1 DESIGNATION

Composite cement EN 197 -1 CEM V/A (S-V) 32.5N

Cement type
18-30% slag
Strength class
18-30% siliceous fly ash
ASTM C-150 for Cement Types
Hydraulic cements for general construction purposes are specified in the USA in three standards: ASTM C 150, ASTM C 595, and ASTM C 1157.
There are eight types of Portland cements, specified in ASTM C 150:
1. type I: normal
2. type IA: normal, air-entraining
3. type II: moderate sulfate resistance
4. type IIA: moderate sulfate resistance, air-entraining
5. type III: high early strength
6. type IIIA: high early strength, air-entraining
7. type IV: low heat of hydration
8. type V: high sulfate resistance
The above cements are distinguished by properties such as mechanical strength, sulfate resistance, and heat of hydration, which are achieved by manipulating the chemical
and phase composition of the products at the time of manufacture. The first three types have air-entraining varieties, which are produced by intergrinding small quantities
of airentraining chemicals. The air entraining varieties are important for making concrete resistant to freezing and thawing. There is also an alternative way to produce such
concrete by using air-entraining admixtures in the concrete mixes, instead of using air-entraining varieties of cement.
ASTM C 595 specifies the following five types of blended cements:
i. type IS: Portland blast-furnace slag cement
ii. type IP or P: Portland pozzolan cement
iii. type I(PM): Pozzolan-modified Portland cement
iv. type S: slag cement
v. type I (SM): slag-modified Portland cement
The modified varieties of blended cements are those in which the slag or pozzolan quantity is less than their respective threshold requirements,i.e., 15% and 25% for IP and
IS types, respectively. In this standard specification, as in ASTM C 150, there is provision for further categorizing the blended cements in terms of their sulfate resistance and
airentraining properties. An interesting development in specifying cements is the adoption of “performance specification” in place of “prescriptive specification,” which
means that cements can be classified in terms of their physical properties and environmental exposure conditions without any restrictions on prescribing the ingredients
and other chemical characteristics. ASTM 1157 is the prevailing performance specification and has provisions for six types:
a. type GU: general use
b. type HE: high early strength
c. type MS: moderate sulfate resistance
d. type HS: high sulfate resistance
e. type MH: moderate heat of hydration
f. type LH: low heat of hydration
For application purposes both the prescriptive and performance standards can be used as they have their prescribed conditions of field applications.
ASTM C-150 for Cement Types
ASTM C-150 for Cement Types
ASTM C-150 for Cement Types
ASTM C-150 for Cement Types
ASTM C-150 for Cement Types
Benefits of Blended Cement
Blended Cement
Advantages of GGBFS in Concrete
Advantages of GGBFS in Concrete
Effect of GGBFS % in Concrete color
6.8. GGBFS Concrete
CO2 Footprint
Using GGBFS as secondary main constituent, either in cement or in concrete production reduces the carbon footprint of total cementitious materials.
The CO2 footprint of the cementitious materials can be reduced to less than 30% of that of CEM I, due to the high replacement levels of GGBFS.
Portland cement and traditional concrete are environmentally hazardous materials for the following reasons:
1. Raw materials for cement (limestone and others) are mined from quarries, which deplete our natural resources and upsetting ecosystem.
2. Cement production consumes extremely intensive energy (from fossil fuel)
3. Releases high quantity of CO2 making it the third-ranking producer of CO2 emission.
4. Aggregate materials (sand and stone) for concrete are mined from quarries, which deplete our natural resources and upsetting ecosystem.
While GGBFS is one of the ‘greenest’ of construction materials. Its only raw material is a very specific slag that is a by-product from the blast-furnaces manufacturing iron. Manufacture of
GGBFS utilises all of the slag and produces no significant waste stream.
Further ‘green’ benefits are that manufacture of GGBS does not require the quarrying of virgin materials, and if the slag was not used as cement it might have to be disposed.

Effect of GGBFS on Development of Concrete Strength

With the same cementitious material content (the total weight of Portland cement CEM I plus GGBFS), similar 28-day strengths to Portland cement CEM I will normally be achieved when
using up to 50% GGBFS.
At higher GGBFS percentages the cementitious content will need to be increased to achieve equivalent 28-day strength. The rate of reaction and strength development of GGBFS concrete is
slower than equivalent concrete made with Portland cement CEM I but continues at a significant rate for much longer (data indicates continued development after many years).
Impact of GGBFS on Heat of Hydration
By replacing part of the hydraulic, rapidly hydrating OPC by the latent hydraulic, slower reacting GGBFS, the heat production rate and total heat of hydration is reduced. This is especially
beneficial for mass concrete to avoid thermal shrinkage cracking.
Sulfate resistance
GGBFS in concrete improves the sulfate resistance of concrete ( no C3A in GGBFS).
Alkali-Silica Reaction (ASR)
GGBFS is known to reduce the potential expansion of concrete due to alkali-silica reaction ( low alkali content in GGBFS).
Chloride resistance
Chloride ingress into concrete can be notably diminished by the addition of GGBFS.
This is due to the reduced capillary porosity and the increased chloride binding capacity of GGBFS concrete.
Colour
The concrete mix with GGBFS will produce a lighter color in concrete after curing.
234
CO2 emission of GGBFS
CO2 Footprint of GGBFS
CO2 e2 (without transport of
Content of the addition constituents to the concrete
plant)
Combination (CEMI + GGBFS)

CO2 e2 /t (addition content

wt.% low–high)

735–617
CEM IIB-S 21–35 (GGBFS)

608–363
CEM III A 36–65 (GGBFS)

354–236
CEM III B 66–80 (GGBFS)
Strength development of GGBFS Concrete
Comparison between OPC and Slag Cement Strength

Age (days)
 Strength development of different GGBFS %in Concrete
7 days 28 days

Relative strength 70 % GGBFS 70 % GGBFS

development of concrete
with different GGBFS % 50 % GGBFS 50 % GGBFS

addition
30 % GGBFS 30 % GGBFS
At 7 Days
• CEM I 100%
CEM I CEM I
• 30% GGBS 70%
• 50% GGBS 50% 0% 20% 40% 60% 80% 100% 120% 0% 20% 40% 60% 80% 100% 120%
• 70% GGBS 35%
At 28 Days
• CEM I 100% 56 days
• 30% GGBS 105%
• 50% GGBS 100% 70 % GGBFS

• 70% GGBS 80%

At 56 Days 50 % GGBFS

• CEM I PC 100%
• 30% GGBS 105% 30 % GGBFS

• 50% GGBS 110%

• 70% GGBS 100% CEM I

94% 96% 98% 100% 102% 104% 106% 108% 110% 112%
Chloride and Salt Attack of GGBFS Concrete
Steel embedded in concrete is normally protected
against corrosion by the high alkalinity created inside
concrete by hydrated cement.

In such conditions, a passive layer forms on the

surface of the steel and rusting is inhibited. However,
if significant amounts of chloride are able to penetrate
the concrete this protection can be destroyed and the
embedded steel will rust and corrode.

Because of its finer pore structure, GGBS concrete is

substantially more resistant to chloride diffusion than
Portland cement concrete.

For reinforced concrete structures exposed to

chlorides, the use of GGBS will give enhanced
durability and a longer useful life. Generally the
higher the proportion of GGBS, the greater will be the
resistance to chloride penetration.
Heat of Hydration of GGBFS Concrete
Color of GGBFS Concrete
 PH value with and without GGBFS
PH Value Of Concrete With
GGBS
PH value of GGBS and OPC is around 9.7
and 12.8, respectively. Hence, many are
apprehensive that pH value of pore
solution particularly with high
percentages of GGBS, may fall below
10.0, thereby exposing the reinforcement
to corrosion; fortunately, such an
apprehension is found to be untrue.
Laboratory experiments were conducted
and it was observed that concrete even
with 70% GGBS and after a period of 1
year had pH values higher than 12.1

PH value of pore solution in concrete is

generally in the region of 12-14. Steel will
not be generally corroded until the PH drops
below 10.
Comparison of different SCMs on Concrete and Environment
6.9. Pozzolana
The blended cement is a binder that contains - in addition to Portland cement clinker and calcium sulfate - one or more of the following materials:
a latent hydraulic material (GGBFS)
a pozzolanic component (natural pozzolana, fly ash, silica fume, burnt clay...etc)
a filler (usually limestone).
Latent hydraulic materials have a natural hydraulic potential (i.e. they can develop silicate hydrates by hydration reactions), but require an activator such as:
Lime or Portland cement clinker or Gypsum or Chemical activator in order to accelerate the reaction with water. GGBFS is the most typical latent hydraulic
material.

Pozzolanic Materials:
Pozzolanic materials are natural or industrially activated products. Pozzolanas are siliceous or siliceous and aluminous materials which in themselves
possess little or no cementitious properties. When finely ground, they react in the presence of water at ambient temperatures with dissolved calcium
hydroxide Ca(OH)2 from lime or Portland cement clinker to form strength developing calcium silicate and calcium aluminate compounds. Natural Pozzolanas
are mostly of volcanic origin and they can be found in various parts of earth.

Classification of Pozzolanas
Natural Pozzolanas
Artificial Pozzolanas

1- The natural Pozzolanas

are mainly of volcanic or metamorphic origin or of other highly siliceous materials such as diatomaceous earth.
Typical examples of Natural Pozzolanas are: Volcanic Tuffs and pumicites , Diatomaceous earth, Opaline cherts and shales, Tuffs, phonolites, zeolites, etc.

2- The Artificial Pozzolanas

- Activated Natural Materials: Clacinated Clays, Calcinated Volcanic Rocks, Metakaolinite, Calcinated Shales
- Activated Industrial By-products: Pulverized Ashes of Lignitic or Anthracitic Coal, Bottom Ash, Industrial SiO2 rich residue ( Silica Fume), Calcinated
Red Muds, Calcinated Wastes, Pulverized Clay Bricks or Tiles, Rice Husk ash
The artificial Pozzolanas are produced by means of thermal treatment from non-pozzolanic material (e.g. marl, shale) or from material with very low pozzolanic
properties (e.g. phonolite). When exposed to a rise of temperature, depending on the nature of the raw material (150°C to about 1500°C), they are activated
(crystalline structure is modified and glass if formed) and therefore develop pozzolanic properties.
245
Classification of Pozzolana
Natural Pozzolana
Volcanic eruption products
«Volcanic rocks come from the fast solidification of a
silicate-rich magma at the surface of the earth»

Scoria Pumice phonolite

Magma Tuff glassy volcanic rock
vesicular lava ashes & rocks
 Zeolites as Pozzolanic Material

Zeolites are porous minerals with high absorbency and ion-

exchange capacity. Their molecular structure is a dense
network of AlO4 and SiO4 that generates cavities where water
and other polar molecules or ions are inserted/exchanged

Due to economic, environmental and technical benefits, one

of the most widespread applications of natural zeolites is to
be found in the cement and concrete industry. Application of
natural zeolite in the manufacture of pozzolanic cements
began from the first decades of the 20th century and shows a
growing trend in recent decades. Use of natural zeolite as a
supplementary cementitious material in the production of
cement, mortar and concrete has been investigated in many
studies. Generally, it is shown that the use of natural zeolite
leads to the improvement of mechanical strength and
durability properties of cement and concrete composites
Artificial Pozzolana
Fly ash

by-product of thermal
power plant
 typically from
combustion of
pulverized coal
 Pozzolanic reactivity
& water demand
reduction

Useable as
cementitious additive
Artificial Pozzolana
Silica fume
by-product from electric arc furnaces
used in the production of ferrosilicon
and silicon metals & alloys
 extremely fine amorphous SiO2 (> 150.000
cm²/g)
 Pozzolanic reactivity & pore filling effect
 also known as Microsilica, Silica dust,
Condensed SF, Volatilized silica

SF precipitation
Fineness of Cementitious
0,001 0,01 0,1 particle size in mm

Cement
Fine cement 20 µm

Fly ash
10 µm

Silica fume
1 µm
Artificial Pozzolana
Metakaolin

Metakaolin is a high-quality pozzolanic material. Metakaolin is

one of the most widely used mineral admixtures these days. It
helps concrete obtain both higher performance and economy.
Unlike others, it is neither the by-product of an industrial process
nor entirely a natural product. It is specially produced from high
quality Kaolin.
Metakaolin is produced by the calcinations of pure or refined Kaolin Clay
kaolinite clay at a temperature between 650℃ to 850℃. Once
the burning process gets completed it is properly grinded to
achieve desired fineness to improve various strengths and
property parameters concrete.
Kaolin clay is the raw material for the Metakaolin. Kaolinite clay
is a mineral which is fine and white in colour and it is used in the
manufacturing of porcelain. Kaolinite clay is also known as china
clay or kaolin clay.
Activated Pozzolana

Dried activated pozzolan, agglomeration of activated

pozzolan particles are visible in the container
SiO2-CaO-Al2O3 ternary system
6.10 Pozzolana Reaction and Reactivity
Reactivity of Pozzolana

The reactivity of a pozzolan depends on its chemical and mineralogical composition, the type and proportion of its active phases, the particle’s specific
surface area, water content, curing time and temperature . It is widely accepted that an increase of specific area and/or decrease in particle size will expose a
greater surface to chemical reaction enhancing reactivity. It is also widely accepted that amorphous structures are more reactive than crystalline ones.
Glassy pozzolans with a limited amount of non-reactive, crystalline minerals are considered to be very active, while, on the contrary, weak pozzolans contain
little glass and considerable amounts of crystalline minerals.

Pozzolana Reaction
Pozzolana is siliceous or aluminous material ( higher amount of Silica & Alumina and lesser amount of Iron Oxide, Calcium Oxide, Magnesium Oxide, alkalies)
that doesn’t possess cementitious properties on itself.
But in its finely ground form, it reacts with Ca(OH)2 (lime or Portlandite) in the presence of moisture to form a compound having cementitious properties.
The hydration process of PPC ( Pozzolana Portland Cement) can be given as,
Hydration of cement clinker,
C3S + H → C-S- H + CH (fast)
Hydration of pozzolanic content/ Pozzolanic reaction,
Pozzolan + CH + H → C-S- H (slow)
As we know from above the pozzolanic reaction is a reaction between pozzolanic material and Ca (OH)2 ( CH or Lime or Portlandite).
Also, Many pozzolans may also contain Aluminate, or Al(OH)4−, that will react with calcium hydroxide and water to form calcium aluminate hydrates such as
C4AH13, C3AH6 or hydrogarnet. AFm phases and AFt or ettringite phases can form.
Pozzolanic reaction is a long term reaction, which involves dissolved SiO2, water and CaO or Ca(OH)2 or other pozzolans to form a strong cementation matrix.
Sufficient amount of free calcium ion and a high pH of 12 and above is needed to initiate and maintain the pozzolanic reaction.
This is because at a pH of around 12, the solubility of SiO2 and Al2O3 is high enough to support the pozzolanic reaction.

The major advantage of using PPC over OPC comes from 3 features of this slow conversion of calcium hydroxide into C-S-H gel by reaction with the
pozzolana:
1. As the pozzolanic reaction is slow, the rate of heat generation and strength development of PPC is also slow.
2. This reaction consumes the calcium hydroxide (lime) produced during the hydration of cement clinker content instead of producing it.
This is important for the durability of concrete structures in an acidic environment. ( to overcome sulfate and salts attack).
3. The reaction product from hydration is efficient in filling up capillary spaces. This improves the strength and permeability of concrete. 257
Characteristics of pozzolans and pozzolanic reaction
Mechanism of the pozzolanic reaction
Pozzolanic Reactions
Pozzolanic reactions occur over long
time scales (months to years). The
main mechanism involves the
transportation of calcium hydroxide to
combine with the aluminate and/or
silicate clay minerals .
The high surface area aluminate and
silicate minerals are pozzolan phases,
which in the presence of water and an
alkali (e.g., calcium) produce
cementitious materials, comprising
calcium silicates and aluminate
hydrates .
Any dissolved Ca2+ ions then react
with any dissolved SiO2 and Al2O3
located on clay particles to produce
hydrated gels of C-S-H and C-A-H,
 Mechanism of the strength development caused by pozzolanic reaction products

Pozzolans are primarily siliceous in

nature and contribute to the densification
of the microstructure of concrete by
reacting with water and hydrated cement
paste to form additional strength-bearing
phases . According to ASTM C618 , the
sum of SiO2, Al2O3, and Fe2O3 shall be
70% for the for a raw pozzolan, and 50%
for Class F and C fly ashes, to be
considered as pozzolan. Pozzolans
stabilize portlandite (Ca (OH)2), which is
produced during cement hydration
reactions, to form calcium silicate
hydrates (C–S–H), calcium aluminate
hydrates (C–A–H), or calcium
aluminosilicate hydrates (C–A–S–H).
Pozzolanic reactivity can be directly
measured based on Ca (OH)2 reduction
and the formation of hydrated phases
Hydraulic and pozzolanic reactivity
6.11. Properties of Portland Pozzolana Cement PPC
Properties of Pozzolana Cement and Concrete containing Pozzolana
Heat of hydration decreases, The rate of clinker hydration increases. Paste porosity increases and Permeability decreases in early age due to the slow hydration
of Pozzolana but improved in later age.
Both Ca(OH)2 and Ca/Si ratio in C-S-H decrease and the C-S-H content increases.
Early strength decreases while ultimate strength is often found to exceed that of the reference portland cement.
If cements contain small amounts of very active pozzolana (silica fume, for example), both early and ultimate strengths may be higher than those of the
substituted cement.
The low basicity and permeability resulting from the presence of pozzolana increase the concrete's resistance to lime leaching, sulphate and sea water attacks,
and chloride penetration. Pozzolana containing cements can help avoid expansion induced by alkali-silica reaction.

Comparison of Ca(OH)2 Content Produced in Hydrated PPC and OPC

An investigation was conducted, old hydrated OPC paste and similarly hydrated PPC paste containing 30% pozzolana. It was found:
Calcium hydroxide content in hydrated OPC paste – 20%
Calcium hydroxide content in hydrated PPC paste – 8.4%
Some reduction of calcium hydroxide content in PPC paste may be attributed to dilution and leaching. Even then, the amount of calcium hydroxide should have
been around 14%.
The fact that only 8.4% calcium hydroxide content remained suggests that 5.6% of calcium hydroxide was converted by pozzolanic reaction in PPC.

Advantages of Portland Pozzolana Cement

1- It is an eco-friendly cement as the material used in the manufacture are made of natural recycled waste.
2-Pozzolanic material used in PPC is cheaper compared to OPC clinker, making it more economical.
3-The rate of hydration in Portland pozzolana cement is lower in comparison. Which means that it produces less heat of hydration.
4-PPC has improved permeability due to soluble calcium hydroxide converting to insoluble cementitious products.
5- It is sulphate resistant.
6-The concrete and mortar prepared with PPC are workable and plastic.
7-PPC has better resistance to expansion.
8- Long term compressive strength of PPC is higher than OPC.
9-PPC has improved durability due to improving permeability and lower calcium hydroxide content.
Disadvantages of Portland Pozzolana Cement
1-Early days compressive strength is quite low.
2- It has a longer curing period due to the moisture requirement for pozzolanic activity.
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3-The resulting cement might be inconsistent in quality.
4-Due to the reduction in alkalinity, the reduction in resistance to the corrosion of steel is seen.
Comparing OPC (Ordinary Portland Cement) and PPC (Portland Pozzolana Cement)
Description Ordinary Portland Cement (OPC) Portland Pozzolana Cement (PPC)
1 Composition Comprises mainly clinker, gypsum, and Contains clinker, gypsum, and pozzolanic
minor additives. The clinker is the primary materials like fly ash, volcanic ash, or silica
binding agent. fume, which enhance its properties.
2 Setting Time Generally has a faster setting time, making it Typically exhibits a slower setting time due
suitable for projects where quick setting and to the presence of pozzolanic materials. This
early strength are critical. can be advantageous for long-term strength
development.
3 Heat of Hydration Generate greater heat during the hydration Has a slower hydration process and
process of concrete. generates less heat during the hydration of
concrete.
4 Strength Development Known for achieving higher early strength, While it may have slower initial strength
making it suitable for applications where development, PPC often exhibits higher
quick strength gain is crucial. ultimate strength over the long term.
5 Durability May have lower resistance to certain Enhanced durability due to the pozzolanic
aggressive chemical environments. materials, reducing permeability and
improving resistance to chemical attacks.
6 Colour Typically has a darker gray colour. Tends to be slightly lighter in colour due to
the inclusion of pozzolanic materials.
7 Application Commonly used in general construction Widely used in projects where long-term
where quick setting and early strength are durability and sustainability are priorities,
critical, such as residential buildings and such as bridges, dams, and other
pavements. infrastructure projects.
8 Workability The workability is less compared with PPC The addition of pozzolanic materials
cement. improves the workability of cement, making
it easier to handle and install.
9 Cost Often more costlier Comparatively cheaper
10 Use in Mass Concrete Suitable for mass concrete applications. Preferred for mass concrete due to its lower
heat of hydration and reduced risk of
thermal cracking.
11 Leaching More susceptible to leaching of calcium Reduced leaching due to the pozzolanic
hydroxide. reaction that binds calcium hydroxide.
12 Corrosion Resistance: May offer lower corrosion resistance, Improved corrosion resistance due to the
especially in aggressive environments. presence of pozzolanic materials.
Comparing of color of OPC (Ordinary Portland
Cement) and PPC (Portland Pozzolana Cement)

OPC PPC
Reduction of Ca(OH)2 by Pozzolana

All the advantages of PPC are

mainly due to the slow conversion
of Ca(OH)2 in the hydrated cement
paste into cementitious product

Typical reduction of Ca(OH)2

 Applications of Portland Pozzolana Cement PPC.

•If you want to do footing concreting in soil that

has aggressive chemicals instead of OPC, we
can go for Portland Pozzolana Cement since it
provides better impermeability characteristics.
•For mass concreting works, it is advisable to
use PPC since it has lower Heat of hydration.
•If you need more time in concreting works like
column starter works or finishing works, It is
advisable to use PPC cement since it sets slower
than OPC and buys us some extra time.
•If you need to do concreting in hot weather
conditions, it is advisable to use OPC because
PPC requires a moist environment and longer
curing time to reap its benefits, as it is not
possible in hot climatic conditions we can go
for OPC. (If Suitable curing arrangements can be
made, then PPC is also a viable choice)
7. Alternative Fuels

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7. Alternative Fuels in Cement Production
Cement is considered one of the most important building materials around the world.. Cement production is an energy-intensive process
consuming thermal energy of the order of 3.3 GJ/ tonne of clinker produced, which accounts for 30 – 40 percent of production costs .
Worldwide, coal is the predominant fuel burned in cement kilns. Cement production consumes approximately 120 kg of coal per tonne of
cement.

The cement manufacturing industry is also under increasing pressure to reduce emissions. Cement manufacturing releases a lot of
emissions such as carbon dioxide (CO2) and nitrogen oxide (NOx). It is estimated that 5 percent of global carbon dioxide emissions
originate from cement production. The use of alternative fuels in cement manufacturing, therefore do not only afford considerable
energy cost reduction, but they also have significant ecological benefits of conserving non-renewable resources, the reduction of waste
disposal requirements and reduction of emissions. Use of low-grade alternative fuels in some kiln systems reduces NOx emissions due to
reburn reactions. There is an increased net global reduction in CO2 emissions when waste is combusted in the cement kiln systems as
opposed to dedicated incinerators

Benefits of using alternative fuels in cement production

Cement producers worldwide are striving to lower their production costs. One effective method of achieving this end
is the use of alternative fuels. Use of low-grade alternative fuels such as waste coal, tyres, sewage sludge, and
biomass fuels (such as wood products, agricultural wastes, etc.) in precalciners is a viable option because
combustion in a precalciner vessel takes place at a lower temperature. In precalciners where kiln exhaust gases pass
through, the NOx emissions are much reduced due to reburn reactions. There is an increased net global reduction in
CO2 emissions when waste is combusted in the cement kiln systems as opposed to dedicated incinerators, resulting
in reduction in the CO2 penalties. Since alternative fuels are often deemed cheaper than conventional fossil fuels, the
possibility of a competitive edge is generated.
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Types of Conventional and Alternative Fuels
Types of Alternative Fuels
Category Fuels
Gaseous fuels
Refinery waste gas, landfill gas,
pyrolysis gas, natural gas

Liquid fuels Tar, chemical wastes, distillation

residues, waste solvents, used oils,
wax suspensions, petrochemical
waste, asphalt slurry, paint waste, oil
sludge

Solid fuels Petroleum coke (petcoke), paper

waste, rubber residues, pulp sludge,
sewage sludge, used tyres, battery
cases, plastics residues, wood waste,
domestic refuse, rice husks, refuse
derived fuel, nut shells, oil-bearing
soils, diapers, etc.
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Types of Alternative Fuels

Rice husks

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Types of Alternative Fuels
Feeding of Alternative Fuels in the Kiln
Analysis of different Fuels

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Feeding of Tires to the Kiln
Processing of Alternative Fuels

Input Output
•Household •Plastics
waste •Textiles
•Industrial waste •Paper
•Bulky waste •PVC
•Production •Ferrous and non-
residues ferrous fraction

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7.1. Refused Derived Fuel (RDF) as an example for AF

Definitions: RDF
The definition of "waste fuels” or "Refuse Derived
Fuels” (RDF)

Therefore, after adequate and extensive (pre-

)treatment in different processing plants and
applying strictly defined quality assurance
measures, various non-hazardous and/or
hazardous waste materials from households,
commerce and industry can be used as RDF in co-
incineration plants (i.e. cement industry etc.):
sewage sludge, waste wood, high calorific fractions
from mechanical-physical (MPT) or mechanical-
biological treatment (MBT) plants, calorific fractions
of household and commercial wastes, shredder light
fractions (e.g., from old vehicles and waste electric
and electronic equipment (WEEE)), scrap tyres,
waste oil and used solvents, etc.
 RDF Meaning
Refuse Derived Fuel(RDF) is the generic
name for alternative fuels obtained from
recycling. Almost any organic material is
suitable as fuel: cellulose, rubber, plastic,
leather, its substitutes, etc.
By using professional machinery, it is
possible to make MSW to solid fuel pellets,
briquettes or pellets, but RDF can also be
sold in bulk in a shredded state. Recycled
fuel is in demand at metallurgical and cement
plants, thermal power plants and boiler
houses.

What is refuse derive fuel? Refuse-derived

fuels (RDF) or secondary fuels (SRF) are
fuels obtained from waste. This can be solid,
liquid or gaseous waste, which is processed
to different degrees of depth for the respective
purpose. The waste usually catagorized as
household waste, industrial waste, and
production waste
Importance of RDF
The importance of refuse-derived fuels RDF in the cement
industry
RDFs refuse derived fuel has taken on an increasingly
important role in the renewable energy industry. But what
are RDFs and what are they for? They are mainly fuels
produced from non-hazardous waste for energy recovery
through co-processing that serve as a supplement to
fossil fuels.
RDF is obtained from waste and raw materials
composed of waste, which are then treated,
subsequently used as alternative fuels and used by
different industries, such as the cement industry.
The relevance of alternative fuels in the cement industry
The cement industry has been working on the use
of RDF fuels derived from waste for energy
recovery and to avoid as much as possible dependence
on fossil fuels, which in the long run are more harmful to
the environment and the ozone layer. .
RDF is the most efficient, economical and sustainable
solution for harnessing the energy and raw materials
contained in waste, which can be properly treated and
used as fuel for production in the cement industry.
RDF sorting and shredding
Refuse Derived Fuel (RDF)
RDF stands for Refuse-Derived-Fuel, a fuel produced by sorting and shredding
combustible materials contained in municipal solid waste (MSW) and industrial
waste. Compared to fossil fuels, RDF is more affordable, abundant, and
environmentally friendly.
Sorting
The diversification of waste stream and the control of the supply chain are the
most important tools to guarantee the constancy in supply in terms of quantity
and quality.
In the transfer station, the raw MSW and industrial waste are segregated in
order to purify combustible fraction from the organic fraction and inert;
consequently, the material is transported to the shredding station.
The role of transfer stations is vital to assure high quality of the RDF and the
most competitive price; as the higher is the purity of the combustible fraction the
lower is the cost of transportation.

Shredding
Once the waste is segregated, the combustible fraction is transported in the
final shredding station which is equipment by other sorting equipment such as
disc screen (to remove any residual fraction and dust), wind sifter (to remove
inserts) and finally, it is fed in a secondary shredder with a production of 3000
ton of high quality RDF, with a size up to 50 mm.
References
1- 17. H. F. W. Taylor, Cement Chemistry, Academic Press, London (1990).
2 - A. K. Chatterjee, Chemistry and engineering of the production process – incremental advances and lack of
breakthroughs, Cement & Concrete Research, Vol. 41, Issue 7, July 201

3 - LEA‘S CHEMISTRY OF CEMENT AND CONCRETE

FOURTH EDITION EDITED BY PETER C. HEWLETT
4 - Concrete technology and practice M.H TAYLOR 1977
5 - HOLDERBANK CEMENT COURSE “Material Science”
6 - BLUE CIRCLE CEMENT COURSE
7 - LAFARGE CEMENT TRAINING COURSE VADE-MECUM
8 - Training Course: Kiln Process and Operation “ FLS”
Raw Material Characteristics (Including Burnability and Volatile Matter)
9 – (10 Golden Rules for Clinker Burning)

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