CE 772 Pavement Materials

Module 7: Cementitious Materials

Dr. Solomon Debbarma Email: sdebbarma@iitb.ac.in Phone: 8837237899 (M); 7131 (O)
 Referred Books

• Concrete Microstructure, Properties and Materials by Mehta and Monteiro

• Properties of Concrete by A.M. Neville,
• Concrete Technology, M.S. Shetty
• Integrated Materials and Construction Practices for Concrete Pavement: A State-
of-the-Practice Manual, FHWA HIF - 07 – 004,
https://intrans.iastate.edu/app/uploads/2019/05/IMCP_manual.pdf
 Materials for Concrete Structures

Coarse Aggregates Fine Aggregates Cement Water

Chemical Accelerators Plasticizers Retarders Air entraining

Admixtures

Mineral
Common Terminology
 Challenge
Coarse Aggregate Fine Aggregate

Already selected in the previous module

Cement Type???

Technical parameters Economic & Environmental parameters

• Strength (compressive or flexural) • Economical
• Early age strength • Less green house gas emissions
• Less shrinkage • Higher storage life
• Marine water Resistance
• Durability….
 Interesting Facts about Cement

• Current consumption of concrete is more than 30 billion tons every year

• Second highest used material after water
• Why concrete?

➢ Can be molded into any shape and size

➢ Water resistant

➢ Cheapest and most readily available material

• Cost of 1 kg of concrete?

• 1 m3 = 6000 Rs
• Density of concrete = 2400 kg/m3
• 2400 kg/m3 = 6000 Rs
• 1 kg = 2.50 Rs • Much Cheaper than 300 ml water
 Common Terminology

• Cement is the glue that binds concrete together, and its chemical composition
influences concrete behavior
• Hydraulic cement is a material that sets and hardens when it comes in contact with
water through a chemical reaction called hydration, and is capable of doing so under
water (ASTM C 125-03) i.e. cements that only hardens by reacting with water but also
form a water-resistant product are called Hydraulic Cements. Whereas, nonhydraulic
cements are the cements that hydrates but the final product is not water-resistant

• Hydraulic cements include Portland cement and blended cements

• The inventor of the first Portland cement thought its color was similar to that of rock
found near Portland, England; thus, the name

• Pozzolan: Material that reacts with cement & water to improve its microstructure

• Supplementary cementitious materials: cements and pozzolans other than Portland

cement
 Cement Production
• What do we need from cement ?
• Binding Strength: Cement react with water (hydration process) to produce Calcium Silicate
Hydrate (C-S-H) gel that provides strength.

C-S-H

calcareous Siliceous Mixing Water

materials Materials

• Clay apart from silica could

contains alumina (Al2O3) and iron
oxide (Fe2O3) and alkalies (Na2O
• Limestone (CaCO3) • Clay is used for silica and K2O)
Mostly Used • Alumina and Iron oxide helps in
Why clay is preferred?
• Chalk reducing the fusion temperature i.e.
• Sea-Shells • Quartz (which are highly siliceous) are formation of calcium silicates at
difficult to grind lower temp. Fluxing Agents
• Clay is available in finely grounded • If not present in clay, intentionally
state; saves energy could be added (Bauxite & Iron
• It also contains Al & Fe oxides which ore)
lowers fusion temperature • Alkalies are not desirable since
leads to alkali-silica reaction
 Cement Production
• Stages
Step 1: Mining of Aggregates:
• Limestone & Clay (silty clay, Zafarana clay, and Kaolin.)

Step 2: Crushing, stacking, and reclaiming of raw

materials
• Aggregates are crushed by crushers (jaw & then
impact) to reduce size less than 50 mm
Step 3: Raw meal drying, grinding, and homogenization
• The raw mix, limestone, clay and additives (iron &
bauxite ore) are fed from their bins to raw mills for
drying and fine grinding
• Materials are blended in powdered form (size < 75
µm)
Step 4: Clinkerization
• Blended materials are heated together in a rotatory
kiln (temperature above 1400° C); clinkers of size
~25 mm are formed
Step 5:Cement grinding and storage
• Clinker and 5% gypsum (to avoid flash set) are
extracted from their respective hoppers and fed to
the cement mills which reduces the cement clinkers
sizes between 10-15 µm.
 Cement Production

Two Process are used: DRY & WET Production. In wet production grinding and homogenization of
the raw mix is carried out in the form of slurry (30-40% water). Modern cement plants favors the
dry process, which is more energy efficient because water in the slurry must be evaporated before
clinkering.
02-02-2023 10
 Process Map for a Typical Cement Plant in India – Ordinary
Portland Cement (OPC)

Major raw materials: Limestone, Coal, Pet coke, Lignite, Clay

Other significant inputs: Electricity (from the grid), Alternative fuels, Gypsum,
Water, Plant and equipment
Important sub-processes: Limestone extraction, Raw meal preparation,
Clinkerization, Blending, Packing and dispatch,
Power generation
Products: Bulk cement, Cement bags, Clinker
 Cement Production

Virtual tour of cement plant

http://www.cement.org
Mindess & Young, 1981
 Cement Production
• Chemical Reactions in Rotary Kiln
Limestone CaO + CO2

Clay SiO2 + Al2O3 + Fe2O3

Gypsum CaSO4· 2H2O

• Main Compounds: Bogue’s Compounds • Abbreviation

3Cao. SiO2 Tri-Calcium Silicate C3S

Limestone + Clay 2Cao. SiO2 Di-Calcium Silicate C2S

3Cao. Al2O3 Di-Calcium Aluminate C3A

4CaO. Al2O3. Fe2O3 Tetra-Calcium Aluminoferrite C4AF

Proportion Significance
C3S Since due to impurity Al, Fe, S (gypsum) in ~55-60% Early Age Strength
production, these compounds are impure and
C2S ~15-20% Later Age Strength
hence known as alite (C3S) & belite (C2S)
C3A Aluminate ~5-10% Setting Time
C4AF Ferrite ~5-8% Color
CSH2 Gypsum (S = sulphate) ~2-6% C3A retardation
 Cement Composition of Cement

Chemical formula Notation Name Typical

weight %
CaO C Lime, calcium oxide 60-67
SiO2 S Silica, silicon dioxide 17-25
H2O H Water --
Al2O3 A Alumina, aluminum oxide 3-8
Fe2O3 F Iron or ferric oxide 1-6
MgO M Magnesia, magnesium oxide 1-4
K2O, Na2O K, N Alkalis, Potassium & sodium oxides 0.5-1.2
SO3 S Sulphur trioxide 2-3.5
CO2 C Carbon dioxide --

• This (MgO)is due to impurtity in limestone. This is not good for

concrete since leads to expansive reaction & breaking of concrete. Shall
< 5%
• From Clay, may lead to alkali silica reaction;
• Na2O + 0.658K2O should not exceed 0.60%
02-02-2023 M. Santhanam and G. Sivakumar 14
 Cement Production
• IS 8112 for OPC 43 grade requirement

• Insoluble residue: is a measure of adulteration of cement largely arising from impurities in

gypsum; determined by treating with HCl

• Loss on ignition: extent of carbonation and hydration of free lime and free magnesia due to
exposure of cement to atmosphere
 Cement Production
• How to perform the chemical composition of cement? X-Ray Fluorescence (XRF)

Pellets XRF Machine Output

• How to estimate the compounds proportion for a particular grade of cement? X-Ray Defraction
(XRD)/Rietveld Analysis
 Cement Production
• How to estimate the compounds proportion without having XRD machine?

• Bogue equations could be used:

%C3S = 4.071C – 7.600S – 6.718A – 1.430F – 2.85S

%C2S = 2.867S – 0.7544C3S

%C3A = 2.650A – 1.692F

%C4AF = 3.043F

C= CaO S = Sio2 A = Al2O3 F = Fe2O3 S = SO3

Home activity: The chemical analysis of a clinker was: O = {C, S, A, F, S } = {64.80, 21.08, 5.25, 2.71,
2.88} %. Using the above analysis, calculate the amounts of the four main clinker minerals (C3S, C2S,
C3A & C4AF)

Check it with the literature value in the previous slides…

 Cement Hydration
• Anhydrous (substance that contains no water) cement does not bind aggregates. It
requires water for achieving adhesive property. The chemical reaction that take
place between cement and water is referred as hydration of cement.

• Cement compounds + water = Hydrated products + heat

❑ Hydration Mechanisms: a) Through Solution b) Direct Contact/solid state/topochemical

a) Through Solution: In this, cement compounds (C2S,C3S

etc) dissolves in water to produce a supersaturated
solution followed by precipitation of hydrated products

b) Direct Attack: In this, reaction takes place directly at

the surface of anhydrous cement compounds without the
compounds going into the solution

Through solution mechanism is dominant in the early

stages of cement hydration. At later stage, when the ionic
mobility in the solution becomes restricted, the hydration
of residual cement particles may occur by direct attack
reactions
 Hydrated Products

Hydration of Aluminate to Ettringite (AFt): This reaction is immediate and leads to flash set of cement.
Unless this is lowered down by some method, its not possible to use cement. This is done by adding gypsum.
C3A + 3CSH2 + 26H = C6AS3H32, Δ H = 207 cal/g or -1672 J/g

• The tricalcium aluminate reacts with the gypsum in the presence of water to produce calcium aluminate
tri sulphate hydrate i.e. ettringite (AFt)
• Large amount of heat is generated due to this reaction
• The compound does not contribute to the strength of the cement glue
• Ettringite consists of long crystals that are only stable in a solution with gypsum

Hydration of Ettringite to Monosulphate (AFm):

• This happens in cement having C3A more than 5% only

• Since more gypsum cannot be added (5-6%; expansive reaction), after depletion of gypsum, the
aluminate concentration goes up due to renewed hydration of C3A and C4AF. At this stage, ettringite
becomes unstable and is gradually converted into mono-suplhate.
• Calcium monosulphate is not good for concrete as is an expansive reaction

C6AS3H32 + 2C3A + 4H → 3C4ASH12

Overall reaction:
C3A + CSH2 + 10H → C4ASH12 (ΔH = -1144 J/g)
 Hydrated Products
Hydration of Ferrite:
• From hydration point of view, it is convenient to discuss the hydration reaction of C3A and C4AF together since both
results in formation of products similar in structure
• Depending on sulfate concentration: C4AF forms C6AFS3H32 (similar to ettringite but different chemical
composition) or C4AFSH18 (similar to calcium monosulphate)
• The reactivity of C4AF is slower than C3A
Then why to take risk and add Al & Fe in cement? They act as fluxing agent
Hydration of Calcium Silicates

Calcium silicates (C3S + C2S) + water → C-S-H + Ca(OH)2

provides strength • Does not contribute to strength

• Leads to durability issues in
sulphate environment
• However, being alkaline maintain
pH value around 13: good for
reinforced concrete (protective
layer)

02-02-2023 20
 Hydrated Products
Hydration of Calcium Silicates
2C3S + 6H → C3S2H3 + 3CH (ΔH = -500 J/g)
Moderate reaction rate, gives high strength and heat liberation

2C2S + 4H → C3S2H3 + CH (ΔH = -260 J/g)

Slow reaction rate, gives low initial but high later strength, and low heat liberation

C3S produces round 61% CSH & 39% CH C2S produces round 82% CSH & 18% CH

C3S requires 24% water for complete hydration & C2S requires only 21%

What do you think, which is better?

Obliviously cement rich in C2S will give higher ultimate strength with lesser heat and lower
quantity of CH (more durable)
However, we need higher strength at initial days. Fine particles of C3S in presence of gypsum
starts to hydrate within an hour of addition of water
What to do now???
Addition of SCM will reduce CH content and increases the CSH product along with higher initial
strength
02-02-2023 21