Ecole centrale Nantes

2023-2024

Cement chemistry and hydration

Prof. A. Loukili – Dr. S. Boudache

 What are we talking about??

Cement
Concrete is the most commonly
used material in the world Consumption in France:

about 1 m3/pers./year About 20 Million Tons/year ,

1 0,8 kg/pers./day!
m
Concrete: a composite material

Concrete/Mortar
 Concrete: a composite material
Aggregates

Béton/Mortier
Concrete/Mortar

 0<D<125 mm
 Ranked by size
 Naturals or recycled
 Silicious or carbonated
 Concrete: a composite material
Aggregates

Cement Béton/Mortier
Concrete/Mortar
 Concrete: a composite material
Aggregates

Cement Béton/Mortier
Concrete/Mortar Water

 Hydration: crucial step that will fix many of the

concrete/mortar properties
 Water is rich in minerals
 Concrete: a composite material
Aggregates

Cement Béton/Mortier
Concrete/Mortar Water

Fibers...

Admixtures

 To improve the use of the material

 Concrete: a composite material
Granular
Aggregates skeleton

Cement Béton/Mortier
Concrete/Mortar Water

Fibers...

Admixtures
 Concrete: a composite material
Granular
Aggregates skeleton

Cement Béton/Mortier
Concrete/Mortar Water

Fibers...

Admixtures

Paste
 History of cement

- The cementitious properties of lime in mortars and concrete have been

known since early historic times : Egyptians, Greeks and Romans used
lime and pozzolanic binders (volcanic earths)

- Lime mortars continued to be used in the middle Ages.

-1818, Louis Vicat invented the cement

•1824, Joseph Aspdin from Leeds city - England, produced a powder made
from the calcined mixture of limestone and clay and he deposited a
patent

•He called it "Portland Cement", because when it hardened it produced a

material similar to stones from the quarries near Portland Island in UK.
 I- Cement production
Raw materials

Limestone
(75%) MIX AND Storage
Grinding HOMOGENIZATION

Clay 25% COOLING - Tremping KILN

1450°C

CLINKER
• Limestone fillers
Gypsum • Fly ash
< 4% Grinding • Slags
• Pozzolan
Setting CEMENT • Silica fume
regulator
F < 100 mm

Artificial Portland Cement

Production steps of Portland cement
 Production steps of Portland cement

CaCO3 + Al2SiO4

CaSO4,2H2O
C3S, C2S, C3A, C4AF
 Définition of cement
 Production
1. Grinding and homogenization of "raw materials" (mixture of 80%
limestone and 20% clay)

2. Furning à 1450°C
 Dehydration (loss H2O)
 Decarbonation (CaCO3  CaO + CO2)
 Formation of solid materials by chemical reactions
 Cement and environment

o CO2 EMISSIONS accompanying the production of cement:

o CO2 from decarbonation reaction:

o CaCO3 (Limestone)  CaO + CO2 (g)

o thermal CO2 from combustion during firing

• 1 t of cement = 0.87 t of CO2

•CO2(cement industry)  5 % du CO2(Global Industry)
 Définition and properties of cement

“A cement is a binder, a substance that sets and hardens and can bind
other materials together.

It principal constituents for constructional purpose are compounds of

Ca (calcareous) and Al + Si (argillaceous)”

The cement have property of setting and hardening under water, by

virtue of certain chemical reactions and is called : hydraulic cement
 Diagramme de phases

Hydraulic binder:
At least 50 % of the lime is combined with silica or alumina
Pozzolanic binder:
Lime must be provided by other constituents to ensure hydraulicity
 Chemical composition of cement
Potland cement (CEM I)
Cementitious
o Powder Notation
Oxide Average mass Content

Calcareous rocks CaO C 62-67%

SiO2
S 19-25%

Al2O3
A 2-9%

Fe2O3 F 1-5%

Clays SO3 1-3%

MgO 0-3%

K2O 0.6%
( H = H2O) Alcalins
Na2O 0.2%
 Phases of cement
Four main phases:

 Alite (tricalcium silicate) : C3S - 3 CaO, SiO2

 Belite (bicalcium silicate) : C2S – 2 CaO, SiO2

 Aluminate (tricalcium aluminate) : C3A – 3 CaO, Al2O3

 Ferrite (Tetracalcium alumino-ferrite) :

C4AF - 4 CaO, Al2O3, Fe2O3

 Bogue formula
Bogue formula are used to calculate the approximative
proportions of the four main mineral phases of a Portland
cement

C3S = 4.0710x CaO – 7.6024xSiO2 – 1.4297xFe2O3 –

6.7187xAl2O3

C2S = 8.6024xSiO2+1.0785xFe2O3+5.0683xAl2O3-
3.071xCaO

C3A = 2.6504xAl2O3 – 1.6920xFe2O3

C4AF = 3.0432xFe2O3
Cements classification

o Types of cement according to standard EN 197

95-100 % clinker
65-94 % clinker
5-64 % clinker
45-89 % clinker
20-64 % clinker
 II- Hydration of cement
- Definition : Reaction between water and cement
- The hydration reactions are very complex

- Cement hydration is exothermic

- The reaction liberates heat because of the reaction between
aluminates and sulfates
- Consequences of hydration
1/ Setting: fluid state  solid state
2/ Hardening: development of mechanical strength
 A- Hydration of C3S and C2S
2 C3S + 6 H => C3S2H3 + 3 CH
2 C2S + 4 H => C3S2H3 + CH

Major contribution to mechanical behaviour

 portlandite Ca(OH)2 / C-H

 25-27% of hardened cement paste
 major part in durability.
 Stoichiometry of CSH
xCa2+(aq) + 2(x-1)OH-(aq) + H2SiO42-(aq) → (CaO)x(SiO2)(H2O)y(s)
 SEM observations

Amorphous
Structure depends on C/S ratio
May include aluminates (CASH)
 Portlandite

C3S + (y + 3 – x )H → CxSHy + (3- x)CH

C2S + (y’ + 2 – x’ )H → Cx’SHy’ + (2- x’)CH

 Stable at pH ≥ 12
 Competition between precipitation of CSH and CH
 If [H2SiO42-(aq)] is high, CSH will precipitate preferantially
 B. Hydration of C3A
 In the absence of gypsum, fast setting of cement:
2 C3A + 21 H => C4AH13+ C2AH8
 In the presence of gypsum
C3A + 3CSH2 + 26 H => C3A 3CS 32H

Formation of:
 Hydrated calcium trisulfoaluminates - Ettringite
 Crystal needles

When gypsum is totally dissolved:

 Dissolution of ettringite
 Formation of monosulfoaluminate with excess of C3A

* Same process for C4AF, with a slower kinetic

 B. Hydration of C3A
Ca3Al2O6 + 6H2O → 3Ca2+ + 2Al3+ +12OH-

CaSO4,xH2O → Ca2+ +SO42- + xH2O

6Ca2+ + 2Al3+ + 12 OH- + 3SO42- + 26H2O → Ca6Al2(SO4)3(OH)12,26H2O

Stability depends strongly on

pH and T°
25°C : 10,43 < pH < 12,52
50°C : 10,52 < pH < 12,41
85°C : 10,87 < pH < 12,25
 B. Hydratation of C3A
Stability depends strongly on pH and T°
25°C : 10.43 < pH < 12.52
50°C : 10.52 < pH < 12.41
85°C : 10.87 < pH < 12.25
 General principal of hydration

Cement = hydraulic binder: reaction with water creates a

strong connection (hydrates) between cement grains

2. Introduction of water 3. Dormant period

1. Grains of
and mixing: (Induction period) -
anhydrous
Formation of hydrates Hydratation continues
cement
crystals aound the cement slowly
grains. (The batching of the concrete
Initial dissolution must be done during this
period)
 General principal of hydration

4. Initial setting 5. Final setting

Hydration accelerates,
bridges of hydrates begin to
connect the grains of
cement
Beginning of
Acceleration Period
All cement grains are linked.
The Continuation of
hydration leads to
hardening.
End of Acceleration
Period

Initial setting: Birth of elastic modulus

Hardening: solid + and + resistant
 General principal of hydration

Initial dissolution
Ettringite Formation

Induction Period Acceleration Period Deceleration Period Slower Reactions

Increase in Rapid formation of Slower reaction
[Ca2+] CSH and CH diffusion through
hydrates layers
 Porosity
Cement paste = porous environment

 Capillary porosity: spaces between cement grains that are not filled
with hydrates (µm)

 Hydrates porosity (nm)

Porosity depends on:

 w/c
 Type of CSH
 Mineral additions

Porosity is one of the most important parameters. It controls the

diffusion of alien species within the cementitious material.
Diffusion depends on pores size and interconnection
 Pore solution
 It contains alcaline ions (basic pH) and calcium ions

 Ionic concentration in the pore depends on the age of the material

and the nature of the cement

 The composition is affected by the environment of the material

 It has a big influence on the chemical equilibria and the migration of

chemical species

Ionic strength Composition Redox pH

Electrostatic Competition Reducing or Activity of
interactions between ions oxydizing protons
solution
Physical consequences of cement hydration

The hydration reaction is done

with a volume decrease
= Le Chatelier Contraction
Or Chemical shrinkage (CS)

CS refers to the reduction in absolute volume of

solids and liquids in paste resulting from cement
hydration.
Physical consequences of cement hydration

Volume of the solid increases

but
Total volume decreases
 Autogenous shrinkage
(Self dessiccation)

AS is the macroscopic volume reduction of cement paste caused by cement hydration.

Relation between autogenous shrinkage
and chemical shrinkage

The macroscopic volume reduction of AS is much less

than the absolute volume reduction of CS because of the rigidity of
the hardened paste structure.
 Summary
Porosity
(water and air !)
Anydrous
cement Gas phase due to chemical
shrinkage
hydrates
Water
Initial state Grain of anhydrous
cement and water

Cement paste

 The hydration of cement ends when :

• all the water is consumed
or
• all cement is hydrated
Volume balance of hydration according to
Powers model
 Powers model for cement hydration
Powers Model : The Cement hydration is completed for W/C = 0.42
Phases distribution after complete hydration (infinite time) without external
water supply

Optimum at w/c = 0.42