RECAP AGGREGATES

MWASHA
Aggregates gradation
PORTLAND CEMENT
COEM 6013
NOVEMBER 2021
ABRAHAM MWASHA
 PORTLAND CEMENTS AND
CEMENT REPLACEMENT
MATERIALS
• PC and PCC
• WHY Portland cement is  the earth’s most used
material and possible most valuable construction
material
• Cement Production
• Hydration
• Types of Portland cement
• Other cements
• Changes in cements
 PC and PCC
• PC- Portland Cement is the largest
manufactured product on Earth by mass. 
• Combined with water and mineral
aggregates it forms cement-based materials
(e.g. PCC- Portland Cement Concrete). 
• PCC is the second most used substance in
the world after water
Production of the construction
materials
 WHY Portland cement is  the earth’s
most used material . 
• The processes of nuclear fusion in stars and in planet formation have
yielded the 8 elements — oxygen, silicon, aluminium, iron, calcium,
sodium, potassium and magnesium — that make up more than 98% of
the earth’s crust . 
• Minerals containing other elements are not available in the quantities
needed to supply the global demand for cementitious materials. 
• Phosphorus and Germanium are important examples; as
elements  essential for life and also chemically suitable for use in
hydraulic cements. 
• Global reserves of phosphorus ores are barely sufficient for its primary
use as a component of fertilisers. So, any significant diversion of
phosphorus into the construction sector would present an enormous
problem for the sustainability of modern agriculture
• Germanium for producing electronic components
 WHY Portland cement is  the
earth’s most used material 
C

Composition of PC and the Universe elements​

The Limitations of Earth
Chemistry
WHY Portland cement is  the
earth’s most used material . 
 An alternative construction
material instead of cement?
Not Easy for example wood and steel or plastics?
1. The annual usage of wood is much above the replanting
level, and it is not possible to get wood in some places such
as Africa and China.
2. Production of steel, it is costly and again the production of
steel also gives CO2 emission.
3. Plastics such as PVC has higher energy consumption and
CO2 gas emission and require fossil fuel
4. Production of cement is not that energy intensive compared
with other materials.
Production energy of important
construction materials
 WHY Portland cement is  the
earth’s most used material . 

Cements have the following advantages:

• Economy of scale of production and optimised
processing, affecting both cost and energy
requirements
• Widespread availability of raw materials
• Ease of use enabled by workability time before
setting
• Confidence in long term durability based on wide-
ranging and prolonged usage
 WHY Portland cement is 
the earth’s most used material .

CEMENT CARBON
CYCLE 
 SUMMARY:
WHY Portland cement is 
the earth’s most used material
• Amount of wood, steel, asphalt, and brick — are very small in
comparison to concrete.
• These materials generally have a higher environmental footprint than
cementitious materials.
• The production of these materials could not be sufficiently increased
to replace concrete to any significant extent.
• The current production cost of cement is relatively low; a tonne of
bulk cement in Europe and North America typically costs USD $100–
120, and less than $50 in China.
• The low cost and high volume means that it is essentially a local
material produced close to the site where it is used, as the cost of
overland transportation
 Cements
• Safety
• Cement Production
• Stages of production and hydration
• Types of Portland cement
• Other cements
• Changes in cements
 The process requires:
Extensive energy ≈ 3 to 6
million Btu (3.2 to 6.3 GJ)

Large quantities of raw

materials ≈ 1.7 tons (chiefly
limestone) per ton of clinker
produced

The process is also

accompanied by significant
Greenhouse Gas emissions,
particularly CO2, but also
NOx, SOx and other
particulates

Figure 1: Process flow diagram for the cement manufacturing process, showing energy and
heat inputs and particulate and gas emissions (Huntzinger and Eatmon 2009)
 RAW MATERIALS FOR
PRODUCING PC
PC- Portland Cement is manufactured by crushing, milling and
proportioning the following materials:
• Lime or calcium oxide, CaO: from limestone, chalk,
shells, shale or calcareous rock
• Silica, SiO2: from sand, old bottles, clay or argillaceous
rock
• Alumina, Al2O3: from bauxite, recycled aluminum, clay
• Iron, Fe2O3: from from clay, iron ore, scrap iron and fly
ash
• Gypsum, CaSO4.2H20: found together with limestone
According Sidney Mindess & J. Francis Young (1981): Concrete, Prentice-Hall, Inc., Englewood Cliffs, NJ, pp. 671 .
 CEMENT PRODUCTION
Cement Composition
CaCO3 (limestone)
2SiO •Al O (clay, shale)
2 23
Fe2O3 (iron oxide)
SiO (silica sand)
2

Finished interground 4CaO•Al O •Fe O

Clay mineralogy
 Kaolinite
The reasons for selecting kaolin for
manufacturing PC are:
• A good source of alumina and silica.
• Kaolin is thermally activated when
heated to 650-850°C for 1-2 h.
• The composition of kaolin is similar to
that of cement, which finesses it and
makes it consistent with cement.
 Cements
• What PC and PCC Portland Cements Concrete
• WHY Portland cement is  the earth’s most
used material
• Cement Production
• Cement hydration theory
• Types of Portland cement
• Other cements
• Changes in cements
• Safety
 Cement
production
 Cements
• Safety
• Cement Production
• Stages of production and hydration
• Types of Portland cement
• Other cements
• Changes in cements
Cement Manufacture
Schematic diagram of rotary kiln.
 design features of cement kiln

http://www.rotarykilnfactory.com/cement-kiln/
accessed 2021
CLINKER
Laboratory
Ball mill
 The stages of cement production
and hydration
1. Component Elements - These are in the raw materials.
2. Component oxides - These are produced in the kiln.
3 . Cement compounds - These are formed from the oxides.
4. Portland cements - The properties of these are determined by the
compounds.
5. Hydration products - Produced when the cements react with water.
Cement hydration theory
6. Types of Portland cement
7. Other cements
8. Changes in cements
9. Safety
Component Oxides of Cement
Name Abbreviation Chemical
Lime C CaO
Silica S SiO2
Alumina A Al2O3
Iron F Fe2O3
Water H H2O
Sulphuric Anhydride S SO3
Magnesia M MgO
Soda N Na2O
Potassa K K2O
 HOW MUCH ENERGY
REQUIRED
The production of 1 tonne of cement produced = 1
tonne CO2 released.

Limestone + Silica (1450°C) =

Portland cement + carbon dioxide

5CaCO3 + 2SiO2 (3CaO.SiO2) (2CaO.SiO2) + 5CO2

 The Four Major Cement
Compounds
• Tricalcium Silicate C3S
• Dicalcium Silicate C2S
• Tricalcium Aluminate C3A
• Tetracalcium Aluminoferrite C4AF
Clinker compound Chemical CO2
emissions (kg/tonne)
• Alite (C3S) [typically, >60% of Portland
cement clinker] 579
• Belite (C2S) 512
• Tricalcium Aluminate (C3A) 489
• Tetracalcium Alumino-Ferrite (C4AF,
“Ferrite”) 362
 Other Clinker compound Chemical
CO2 emissions (kg/tonne)
• Quicklime (CaO) 786
• Wollastonite (CS) [a major component in
Solidia clinkers] 379
• Ye’elimite (C4A3$) [made with CaSO4 as
sulphur source] 216
• Periclase (MgO) [made from magnesium
carbonate] 1100
• Periclase (MgO) [made from basic magnesium
silicate rocks] 0
 The stages of cement production
and hydration
1. Component Elements - These are in the raw
materials.
2. Component oxides - These are produced in the
kiln.
3. Cement compounds - These are formed from the
oxides.
4. Portland cements - The properties of these are
determined by the compounds.
5. Hydration products - Produced when the
cements react with water.
 Properties of the Compounds
• C3S: Rapid strength gain gives early strength (e.g. 7
days)
• C2S: Slow strength gain. This gives long term strength.
• C3A: Quick setting. The gypsum (calcium sulphate) is
added to control this otherwise flash set would occur.
C3A reacts with sulphate resulting in sulphate attack on
the concrete. It also reacts with chlorides to form
chloroaluminates and protect the steel against corrosion.
• C4AF: Little contribution to setting or strength.
Responsible for the grey colour of cement.
 calcium aluminoferrite (C4AF)
• The calcium aluminoferrite (C4AF) forms a
continuous phase around the other mineral
crystallites, as the iron containing species
act as a fluxing agent in the rotary kiln
during cement production and are the last to
solidify around the others. 
SHOWS A TYPICAL CEMENT
GRAIN.
 The stages of cement production
and hydration
1. Component Elements - These are in the raw materials.
2. Component oxides - These are produced in the kiln.
3 . Cement compounds - These are formed from the oxides.
4. Portland cements - The properties of these are
determined by the compounds.
5. Hydration products - Produced when the cements react
with water.
8. Types of Portland cement
7. Other cements
8. Changes in cements
9. Safety
 Hydration of the Compounds
Compound + Water = Cement glue + Calcite

C3S
C2S
C3A + H2O = CSH + Ca(OH)2
C4AF
 Hydration of the Compounds
Compound Time to 80% Heat of
Hydration days Hydration J/g
C3S 10 502
C2S 100 251
C3A 6 837
C4AF 50 419
HYDRATION OF CEMENT
COMPONENTS
 Aluminate hydration
• The ferrite undergoes two progressive reactions with
the gypsum:
1. Ferrite + gypsum + water = ettringite + ferric
aluminum hydroxide + lime
• C4AF + 3CSH2 + 3H = C6(A,F)S3H32 + (A,F)H3 + CH
• C4AF + C-S-H + H= C-A/F-S-H +AFH +CH
2. Ferrite + ettringite + lime + water = hydrogarnets+
ferric aluminum hydroxide
• C4AF + C6(A,F)S3H32 + 2CH +23H = 3C4(A,F) SH18 +
(A,F)H3
• C4AF +C-AF-S-H +CH +H = C-AF-S-H +AFH
 Aluminate hydration
• Tricalcium aluminate reacts with the gypsum in the
presence of water to produce ettringite and heat:
C3A + 3CSH2 + 26H  = C6AS3H32,   h = 207 cal/g
C2A +3CSH +26H =C-A-S-H
• Ettringite 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.
 

https://civildigital.com/wp-content/uploads/2019/07/Ettringite-Crystals-Source-YouTube-American-Concrete-Institute.jpg ACCESSED 3032

 HYDRATION OF ALITE
•  The tricalcium silicate (alite)
• Tricalcium silicate + water = calcium silicate
hydrate + lime + heat
• 2C3S + 6H = C3S2H3 + 3CH, H = 120 cal/g
• C3S + H = C-S-H + CH
• The CSH has a short-networked fiber structure
which contributes greatly to the initial strength of
the cement glue.
Scanning electron microscopy of Calcium Silicate
Hydrate (C-S-H)
 HYDRATION OF BELITE
• The belite (dicalcium silicate) also hydrates to form
calcium silicate hydrates and heat:
C2S + 4H =  C3S2H3 + CH  H = 62 cal/g
C2S +H = C-S-H + CH
• Like in reaction ALITE, the calcium silicate
hydrates contribute to the strength of the cement
paste. This reaction generates less heat and
proceeds at a slower rate, meaning that the
contribution of C2S to the strength of the cement
paste will be slow initially.
Microstructure of the cement products

C-S-H CH
 Summary
Chemicals of the hydrated PC
Chemical reactions during hydration

1. Tricalcium aluminate + gypsum + water  ettringite + heat

C3A + 3CSH2 + 26H  C6AS3H32,  H = 207 cal/g

2. Tricalcium silicate + water  calcium silicate hydrate + lime +

heat
2C3S + 6H  C3S2H3 + 3CH,  H = 120 cal/g

3. Tricalcium aluminate + ettringite + water  monosulfate

aluminate hydrate
2C3A + 3 C6AS3H32 + 22H  3C4ASH18,

4. Dicalcium silicates + water  calcium silicate hydrate + lime

C2S + 4H  C3S2H3 + CH,  H = 62 cal/g

5. Ferrite + gypsum + water  ettringite + ferric aluminum

hydroxide + lime
C4AF + 3CSH2 + 3H  C6(A,F)S3H32 + (A,F)H3 + CH
HYDRATION THEORY
HYDRATION THEORY
•  
 Heat of hydration of cement in
concrete
• When Cement in concrete is mix with water heat is evolved
due to the breaking and making of chemical bond during
hydration process this is known as heat of hydration it is
actually exodothermic process.
• Heat of hydration of cement generally divided into five
stage
• 1) pre – induction ( zone 1)
• 2) dormant induction (zone 2)
• 3) acceleration (zone 3)
• 4) deacceleration (zone 4)
• 5) steady stage ( zone 5)
HYDRATION THEORY

Dr. Kimberly Kurtis

School of Civil Engineering
https://www.researchgate.net/figure/Graph-of-hydration-stages-and-schematic-representation-of-anhydrous-cement-particle-At_fig2_42251882
 HYDRATION PHASES
Phase 1: Initial Mixing Reaction

• The aluminate (C3A) reacts with H2O

(Calcium and sulfate ions) to form ettringite
(aluminate hydrate).
 HYDRATION PHASES
Phase 2 Dormancy
• A surface coating of the cement particles. This coating
keeps increases, but also slows down the reaction
(hydration) as the access to H2O isn’t as good as when the
concrete was mixed. The amount of hydrated concrete
keeps increasing on a steady level while the surface of the
concrete keeps fluid.
• This phase is good for transporting and pouring the
concrete, as the concrete stays on a fluid level.
• This phase ends with an initial set of the concrete.
 HYDRATION PHASES
• Phase 3: Strength Acceleration
• A heat increase happens due to the reaction between
calcium silicate (C3S and C2S) which creates the
silicate hydrate CSH The creation of CSH also has a
major impact on the concrete strength during this
phase.
• The concrete temperature during this phase can
increase rapidly to reach internal temperatures like
70-80C (in some cases even higher). It is normally
not recommended to exceed temperatures at around
70C.
 HYDRATION PHASES
• Phase 4: Speed reduction
• A maximum temperature has now been
reached and the availability of free particles is
now reduced and therefore slows down the
temperature increase.
• This phase often ends with the desired strength
and the formwork around the concrete can
now be removed.
• Monitoring of concrete maturity and
temperature and therefore enable the user with
the exact time where this is possible.
 HYDRATION PHASES
• Phase 5: Steady Development / Post Formwork
• The hydration process is now slowed down and will
continue slowly to finish the remaining available
cement and water particles.
• The formwork is now often removed and the
hydration process and reach final strengths (can
take weeks or months even years).
 HYDRATION OF CEMENT
• Watch this video and try to answer these questions
• https://www.youtube.com/watch?v=Bolb7Hr81z4&t=1023s accessed 2021
 The hardened cement paste

Hardened paste consists of the following:

Ettringite                                      - 15 to 20%
Calcium silicate hydrates, CSH     - 50 to 60%
Calcium hydroxide (CH lime         - 20 to 25%
Voids     - 5 to 6%
(In the form of capillary voids and entrapped and
entrained air)
Strength development of cement
compounds (Neville, 1997)
 Cements
• Safety
• Cement Production
• Stages of production and hydration
• Types of Portland cement
• Other cements
• Changes in cements
 Cement from TCL
TCL primary activity is the manufacture of
• Portland Pozzolan Cement,

• Ordinary Portland Cement, as well as

• Class G High Sulphate Resistant (HSR) Oil

well Cement
 Types of Portland Cement
• According to ASTM C 150, Standard Specification for
Portland Cement, recognizes eight types of portland
cement:

• Type I and Type IA*

General purpose cements suitable for all uses where the
special properties of other types are not required.
• Type II and Type IIA*
Type II cements contain no more than 8% tricalcium
aluminate (C3A) for moderate sulfate resistance. Some Type
II cements meet the moderate heat of hydration option of
ASTM C 150.
 Types of cement
• Type III and Type IIIA*
Chemically and physically similar to Type I cements except
they are ground finer to produce higher early strengths.
• Type IV
Used in massive concrete structures where the rate and
amount of heat generated from hydration must be
minimized. It develops strength slower than other cement
types.
• Type V
Contains no more than 5% C3A for high sulfate resistance.
*Air-entraining cements
 HEAT OF HYDRATION

watch this video: https://

www.youtube.com/watch?v=hl0SwEz71u8 accessed 2021
 Sulphate Resisting
Cement(SRPC)
Sulphate attack (from sulphates in the ground,
the sea etc) is due primarily to the effect of
Sulphates on C3A. Sulphate resisting portland
cement thus has low C3A (maximum 3.5%).
SRPC offers poor protection against
chlorides. Note that GGBS may be used for
sulphate resistance
Find from the literature why?
 Rapid Hardening Cement(RHPC)
This has a fineness of not less than 350 m 2/kg
(compared with 275 m2/kg for OPC) and a
high C3S content.
It has a strength approximately 50% higher
than OPC at 3 days but similar long term
strength. Heat evolution rates are high.
 Rapid
Hardening
 White Cement
This has a low C4AF content to give white
content for architectural purposes.
GGBS gives a reasonably white concrete.
 Typical compositions
CompoundOPC SRPC RHPC LHPC White Cement
C3S% 55 43 60 30 51
C2S% 16 36 11 46 26
C3A% 11 3 12 5 11
C4AF% 9 12 8 13 1
Free CaO% 0.8 0.4 1.3 0.3 0.2
 
 Cements
• Safety
• Cement Production
• Stages of production and hydration
• Types of Portland cement
• Other cements
• Changes in cements
 High Alumina Cement, HAC
• Also known as Fondue cement or HAC
• Highly sulphate resisting and has a high
early strength. Around 24 hours
• Unfortunately after some years in a warm
moist environment the strength is partially
lost. This "conversion" process is due to a
crystalline transformation of one of the
hydrates and is irreversible.
HAC
 Expansive Cements
These cements promote a reaction similar to
sulphate attack and expand with considerable
force after setting. They may be used for
demolition. For expansion with less pressure
(for void filling) use aluminium or zinc
additives
 Cements
• Safety
• Cement Production
• Stages of production and hydration
• Types of Portland cement
• Other cements
• Changes in cements
 Changes in UK Cement
Year 1910 1960 1980
C3S% 25 47 53
C2S% 45 25
Changes in cement
2.2 CEMENTS AND CEMENT
REPLACEMENT MATERIALS

• 2.2.1 Cements
• 2.2.2 Cement replacement materials
• EN197
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
Cement  and cement replacement
materials
 Cement Replacements
These are materials which are used as a
replacement for part of the cement in order to
reduce cost or improve properties. Not all of
the cement in concrete is replaced.
e.g. a mix containing 300 kg/m3 of cement
could be modified to contain 200 kg/m3 of
PCC and 130 kg/m3 of GGBS.
 Cement replacements
Cement replacement can be:
•  1) Fully hydraulic: will undergo hydration on its
own and gain strength.
• 2) Latent hydraulic: will exhibit hydraulic
properties only in the presence of hydration
products of Portland cement  
• 3) Filler: material chemically inert but has a
catalytic effect on the hydration of other materials or
can have a physical effect on the fresh properties of
the concrete.
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
 GGBS (GROUND GRANULATED
BLASTFURNACE SLAG)
• Slag is derived from the production of iron in
blastfurnaces.
• The slag contains all of the compounds which would affect
the purity of the iron.
• The slag is a hot liquid and may be cooled in air, by
mixing with water (foaming) or with high pressure water
jets at high water/slag ratios (granulation).
• Only granulation produces non-crystalline slag and only
this slag exhibits hydraulic properties and is therefore
suitable for use with cement.
• The other types of slag are used as aggregate.
• The granulated slag is ground before use.
• Slag sets in the presence of water and lime. The lime is
produced by the hydration of OPC and acts as a catalyst -
it is not depleted.
 The major use of GGBS
The major use of GGBS is in ready-mixed concrete,
benefits including:
• Workability - making placing and compaction
easier.
• Lower early-age temperature rise, reducing the
risk of thermal cracking in large pours.
• Elimination of the risk of damaging internal
reactions such as ASR .
• High resistance to chloride ingress, High
resistance to attack by sulphate and other
chemicals.
Blastfurnace
Slag
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
 PFA (PULVERISED FUEL ASH)
• PFA is the ash from the burning of pulverized coal
in power stations.
• About 20% of the PFA fused into large particles
and drops out of the flue gases to form furnace
bottom ash.
• The remaining 80% (fly ash) is extracted with
electrostatic precipitators and the material for use
with cement is obtained from this.
• PFA is a pozzolanic material. These materials
react with lime to form hydrates.
PFA Production
 The products produced are:
• Pulverised fuel ash (PFA)
• or fly ash, as it is known in many countries and in
concrete
– Dry material mainly for use in concrete.
• Transported in cement tankers
– Conditioned material for use mainly for fill and
grouting applications
• Water is added to produce an earth dry material that
can be transported in sheeted tipping vehicles.
Readily available in large quantities
– Lagoon ash also for use for fill and grouting
applications
• Material is mixed with copious amounts of water
and sluiced to lagoons
Hydration of PFA …
PFA reacts with the lime produced
by the hydration of cement to give more
hydration products - reducing the voids
and lowering the permeability.
 Strength gain properties of pfa

When cured at 20C PFA concrete gains more strength after 28 days compared to PC (CEM I) concrete.
 Barriers to the use of PFA…
• The classification the PFA/fly ash that it is a
waste!
– A long and complex story
– The Environment Agency and SEPA believe PFA is a
waste
– The UKQAA/Power Industry believe that fresh PFA is
NOT a waste!
– Discussions have been ongoing for years
• EU Thematic Strategy may resolve;
• PFA/fly ash would be classified as a by-product
• WRAP style protocols may be part of a solution
• Issues should be clear by spring 2007?
 Emissions to the environment:
• CIA/DETR project showed that using 30% PFA
for equal 28 day strength in a concrete mix that:
– Greenhouse gas emissions are reduced by 17%
– Acidification reduced by 15%.
– Winter smog reduced by 15%.
– Eutrophication reduced by 13% .
– Primary energy requirements reduced by 14%.
NB” Eutrophication the process by which a body of water becomes rich in dissolved nutrients from
fertilizers or sewage, thereby encouraging the growth and decomposition of oxygen-depleting plant life
and resulting in harm to other organisms
 Reduced impacts using additions:
• Current savings due to the use of cementitious
additions (PFA and GGBS)
– Primary aggregate consumption in cement manufacture
reduced by 12%.
– 1,200,000 tonnes of CO2 emission saved.
– 1.94 million megawatt hours of energy saved.
– 6,000 tonnes of SO4 equivalent saved.
– Overall reduction of environmental impact 9% due to
utilising PFA.
• These figures are increasing every day that passes
• As more cement companies, concrete producers, road
makers, etc see the environmental benefits of PFA/fly
ash
 PFA/fly ash utilisation on increase
despite EA and waste issue …
Tonnage and Utilisation of UK PFA
UKQAA Annual PFA Statistics
8,000,000 70%

7,000,000
60%

6,000,000
50%

5,000,000
40%

% Utilised
Tonnes

4,000,000

30%
3,000,000

20%
2,000,000
Tonnes utilised
Total of PFA in tonnes 10%
1,000,000 % utilised

0 0%
1999 2000 2001 2002 2003 2004
Year
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
 PFA in concretes - summary
• PFA is a pozzolana
– This means a material that reacts with lime to form
silicate hydrates - these hydrates give concrete strength
and durability.
– Pozzolanas were used by the Romans to build many
buildings, for example the Pantheon.
– Classified/processed PFA reduces the water content of a
concrete - reducing permeability.
– PFA improves the sulphate resistance and reduces the
risk of alkali silica reaction
– It reduces the heat of hydration compared to Portland
Cement
 The effect of using up the lime in
the chemical reaction
• The maximum percentage of PFA is limited to about
40%. After this there is no lime left.
• Lime is a weak component of hydrated cement and also
eventually dissolves in water. Removing it therefore
theoretically increases strength and durability.
• Lime provides the hydroxyl ions that conduct electricity
in concrete. Removing the lime therefore increases the
resistivity and reduces corrosion.
• Lime is responsible for a lot of the alkalinity of
concrete. Removing it therefore theoretically makes the
concrete more susceptible to loss of alkalinity (e.g.
carbonation) causing corrosion.
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical CompositionsAdvantages and
Disadvantages
• Pre-Blended cements
 CSF (Condensed Silica Fume)
• This is a highly reactive pozzolan is also known as
microsilica and is derived from the production of
silicon steel.
• The production process is highly energy intensive
and is carried out in countries like Sweden where
hydropower is available.
• The high reactivity can be used to obtain very high
strengths but means that great care must be taken
with curing etc.
• Various problems have been reported with this
material.
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
 Natural Pozzolans
• These are mined in many parts of the world
but not in the UK and they are not available
here. In general they are less reactive than
PFA but make an excellent cheap cement
replacement material.
 Pozzolanic reaction
• The Pozzolanic reaction occurs between
amorphous siliceous materials (namely, pozzolan
and pozzolana, a finely divided volcanic ash, rich
in Obsidian,
• Pozzolanic reaction is acid-base reaction
between calcium hydroxide (Portlandite), or
(Ca(OH)2), and silicic acid (H4SiO4)

• Ca(OH)2 + H4SiO4 —> Ca2+ + H2SiO42- + 2 H2O

—> CaH2SiO4 · 2 H2O
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
 Typical Compositions
OPC PFA GGBS CSF
C% 64.1 2.5 40 -
S% 20.0 50 35 98
A% 6.0 27 10 -
F% 3.0 10 0.5 .2
% 2.0 0.8 - .45
M% 2 1.5 8.7 .26
N% .2 1.2 .37 -
K% .5 3.5 .5 .45 
 Ternary Diagram
SiO2

CSF
Natural
Glass
Pozzolana
PFA
GGBS

OPC
Lime HAC
CaO Al2O3
MgO Fe2O3
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
Advantages and disadvantages of
cement replacement materials (1)
• Low early strength (except CSF)
• Reduce cost of raw materials (assuming CSF is
used to save cement)
• Increase cost of production and possibility of
errors in mix proportions.
• May improve durability
• Require better curing and therefore increase cost
of placing. GGBS can cause bleeding but PFA
generally improves cohesion.
Advantages and disadvantages of
cement replacement materials (2)
• PFA and CSF produce a darker colour mix. GGBS
gives an almost white colour (it may be a bit blue
or green initially but this soon fades !)
• GGBS, PFA and CSF are all industrial by-products
which could be environmentally damaging if not
mixed into concrete (substantial amounts of PFA
have to be disposed of each year).
• Using replacement materials in concrete saves the
energy required to make cement.
 Cement Replacements
• Introduction
• Ground Granulated Blastfurnace Slag
• Pulverised Fuel Ash
• The Effect of Pozzolanic Materials
• Condensed Silica Fume
• Natural Pozzolans
• Chemical Compositions
• Advantages and Disadvantages
• Pre-Blended cements
2.2 CEMENTS AND CEMENT
REPLACEMENT MATERIALS

• 2.2.1 Cements
• 2.2.2 Cement replacement materials
• EN197-1
 BS EN197-1
Cement types
• I Portland
• II With PFA (up to 35%), CSF or limestone
• III with GGBS
• IV with PFA (up to 55%)
• V composite cement.
note that these new "cement types" do not coincide
with the American (ASTM) cement types which
have been used in many parts of the world for many
years.
 Typical example of a cement to
the new standard
Portland-slag cement
BS EN 197-CEM II/A-S 42.5N
• This is a type II cement.
• A indicates a high clinker content (C would be
low).
• The S indicates a slag content, V would indicate
PFA and D silica fume.
• 42.5 is the strength.
• N indicates normal setting, R would indicate
rapid hardening.
 BS EN197-1
• New "Portland limestone cement" up to 20%
limestone flour (finely ground calcium
carbonate). Good water retention and workability.
• Up to 5% "minor additional constituents" now
permitted except in SRPC.
• Up to 1% additives permitted.
• "Ordinary Portland Cement" is now called
"Portland Cement".
• "Rapid Hardening Portland Cement" is now the
"R" subclassification of "Portland Cement"
 Typical example of a cement to
the new standard
Portland-slag cement
BS EN 197-CEM II/A-S 42.5N
• This is a type II cement.
• A indicates a high clinker content (C would be
low).
• The S indicates a slag content, V would indicate
PFA and D silica fume.
• 42.5 is the strength.
• N indicates normal setting, R would indicate
rapid hardening.
 Chrome sensitisation
• : Hexavalent chromium in wet cement
may cause allergies in some people.
• The cumulative effect of daily exposure
may take months or years to cause a
reaction and results in what is termed
‘chrome sensitisation’.
• It is estimated that some 5 to 15% of
workers coming into contact with cement
suffer from what is termed Allergic
Contact Dermatitis.
 SAFETY HAZARDS
• High Alkalinity. It has been reported that
an operative who fell into a pour and
soaked his clothes in cement subsequently
had to have his leg amputated due to skin
damage.
• Chrome content is toxic for long-term
exposure.
• Dust hazard