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Cement Hydration

(CE 3420 – Concrete Technology)

Radhakrishna G. Pillai
Building Technology & Construction Management (BTCM) Division
Department of Civil Engineering
Indian Institute of Technology Madras, Chennai, India

Courtesy: Prof. Ravindra Gettu


RECAP of previous section

• Hydraulic and non-hydraulic cement


• Clinker formation in rotary kiln
• Cement composition
• Notations in cement chemistry
• Calculation of the compound composition
• Soundness and fineness tests
C3S (alite) and C2S (belite) crystals

Light, angular  Alite (C3S) Alite (C3S) crystals in portland


Darker, rounded crystals  Belite (C2S) clinker
[Magnification 400X] [Magnification 3000X]

PCA: Kosmatka (2005)


Portland Cement Composition

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 ore (hematite), 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 --
3CaO·SiO2 C3S Tricalcium silicate, Alite 45-60
2CaO·SiO2 C2S Dicalcium silicate, Belite 15-30
3CaO·Al2O3 C3A Tricalcium Aluminate 6-12
4CaO·Al2O3·Fe2O3 C4AF Tetracalcium Aluminoferrite 6-8
CaSO4·2H2O CSH2 Gypsum, Calcium sulphate dihydrate 3-4

M. Santhanam
Two mechanisms of hydration

1. Through-solution hydration (TSH)


– Dissolution of anhydrous compounds
– Formation of highly insoluble hydrates in solution
– Precipitation of hydrates from the supersaturated solution

2. Topochemical or solid-state hydration (SSH)


– Reaction at the surface of anhydrous cement compounds

• Initially TSH and then SSH

Mehta and Monteiro


• Videos on cement hydration (ACBM-NSF, Univ. of Illinois, USA)
http://www.youtube.com/watch?v=VLzoD-g_o5g&feature=related
Peculiarity of the cement hydration process

• Simultaneous reactions between anhydrous compounds


and water
• Hydration rate varies from one reaction to the other
– Ratealuminates > Ratesilicates

• Aluminates  Stiffening/Setting
• Silicates  Hardening/Strength development
Hydration reactions (Oxide notation)

2 (3CaO•SiO2) + 11 H2O = 3CaO•2SiO2•8H2O + 3 (CaO•H2O)


Tricalcium silicate Water Calcium silicate Calcium hydroxide (CH)
hydrate (C-S-H)
2 (2CaO•SiO2) + 9 H2O = 3CaO•2SiO2•8H2O + CaO•H2O
Dicalcium silicate Water Calcium silicate Calcium hydroxide (CH)
hydrate (C-S-H)
3CaO•Al2O3 + 3 (CaO•SO3•2H2O) + 26 H2O = 6CaO•Al2O3•3SO3•32H2O
Tricalcium aluminate Gypsum Water Ettringite (AFt)

2 (3CaO•Al2O3) + 6CaO•Al2O3•3SO3•32H2O + 4 H2O = 3 (4CaO•Al2O3•SO3•12H2O)


Tricalcium aluminate Ettringite Water Calcium monosulfoaluminate

3CaO•Al2O3 + CaO•H2O + 12 H2O = 4CaO•Al2O3•13H2O


Tricalcium aluminate Calcium hydroxide Water Tetracalcium aluminate hydrate
4CaO• Al2O3•Fe2O3 + 10 H2O + 2 (CaO•H2O) = 6CaO•Al2O3•Fe2O3•12H2O
Tetracalcium Water Calcium hydroxide Calcium aluminoferrite
aluminoferrite hydrate

PCA: Kosmatka (2005)


Relative reactivity of cement compounds (typical)

The curve
labeled “overall”
with no marker
has a
composition of
55% C3S,
18% C2S,
10% C3A, and
8% C4AF

Fig. 2-29, Kosmatka (2005), PCA; Tennis and Jennings 2000


Hydration process (until about 14 days)

Mehta and Monteiro


Formation of calcium sulphoaluminates

• Ettringite (AFt) formation:


C3A  3CSH 2  26H  C6 AS3H32 (H  -1672 J/g)
– Fast reaction, low strength and very high heat liberation
• Monosulfoaluminate (AFm) formation:
C6 AS3H32  2C3A  4H  3C4 ASH12
– After the depletion of sulfates and increase in aluminate
ions, AFt reacts further to become AFm
• Overall reaction:
C3A  CSH 2  10H  C 4 ASH12 (H  - 1144 J/g)
OR
2C3A  C6 AS3H 32  22H  3C 4 ASH18
Taylor
Microstructure of calcium sulfoaluminates

• AFt (first): Prismatic needles


• AFm (later): Plane hexagonal crystals
– low surface area ≈ 2 m2/g
Why AFt first and AFm second?
• Volume ≈15-20%

Ettringite Monosulfoaluminate

Mehta and Monteiro; Mindess and Young


Formation of calcium aluminohydrate

C4 AF  2 CH
  14 H
  C4 (A, F)H13  (A, F)H3
 calcium water
  
tetracalci um hydroxide tetracalci um aluminate ferric -aluminum
alumino ferrite hydrate hydroxide

• C4AF may also react with gypsum, as C3A does,


but it is much less reactive.

Young et al., 1998


Formation of calcium silicate hydrate (C-S-H) and
calcium hydroxide (CH)
2C3S  6H
 C 3S2 H 3   
3CH
 
    calcium hydroxide
tricalcium silicate water

H  500 J / g
C-S- H

  
   
2C3S  11H  C3S2 H8  3CH 
• Moderate reaction rate
• High strength
• High heat liberation

Young et al., 1998


Formation of calcium silicate hydrate (C-S-H) and
calcium hydroxide (CH)
2C S  4H
 C 3S2 H 3   
3CH
 2
    calcium hydroxide
dicalciumsilicate water

H  250 J / g
C-S- H

  
   
2C 2S  9H  C3S2 H8  CH 
• Slow reaction rate
• Low initial but high later strength
• Low heat liberation

• Overall reaction: C3S + C2S + water → C-S-H + CH

Mehta and Monteiro; Mindess et al.


Microstructure of C-S-H gel

• C/S ratio of 1.5 to 2 ( C3S2 H3 )


• High surface area (≈ 100-700 m2/g)
• High covalent/ionic and Van der Waals forces
• Volume ≈ 50-65%

Taylor; Mehta and Monteiro


Schematic representation of the
features of C-S-H gel

Young et al., 1998


Microstructure of calcium hydroxide or
portlandite

• Large hexagonal crystals


• Low surface area (0.5 m2/g)
• Low Van der Waals forces
• Volume – 20-25%

Mehta and Monteiro


Microstructure of hydration products

Dicalcium silicate hydrate Tricalcium silicate hydrate Hydrated normal cement

• Fibrous nature of the calcium silicate hydrates


• Broken fragments of angular calcium hydroxide crystallites
• The aggregation of fibers and the adhesion of the hydration particles
is responsible for the strength development
Brunauer 1962 and Copeland and Schulz 1962
Microstructure of hydrated cement paste

C-S-H:
Agglomerations of C-S-H
particles of 1-100 nm.

H:
Hexagonal crystals of
calcium hydroxide,
monosulfoaluminate and
calcium aluminohydrate of
about 1 μm.

C:
Capillary pores and voids of
10 nm to 1 μm.

Mehta and Monteiro


Morphology of hydration products in 7 days

Large crystals of
calcium hydroxide

Platelets of
monosulfoaluminate

Cement particle
coated with C-S-H,
which is surrounded
by ettringite needles

Young et al., 1998


Dimensional range of solids and pores in
hydrated cement paste
• 1 to 107 nanometers OR 10-6 to 10 millimeters

Mehta and Monteiro


Influence of aluminate/sulphate ratio in the
solution on the setting characteristics
Pure C3A is
cubic

Impure C3A is
orthorhombic
with a lot of
holes in the
crystal structure.
The reactivity
depends on the
amount of holes.
Monosulfoaluminate is
formed before ettringite

Discuss rigidity
and plasticity for
Cases IV and V?

Mehta and Monteiro


Rate of heat evolution during hydration

Stage I: Rapid evolution of heat, lasts about 15 minutes (C3A and some C3S reaction).
Stage II: Dormant period, lasts until initial set occurs in 2 to 4 hours
Stage III: Rapid reaction of C3S during the acceleration period, with the peak being reached
at about 8-10 hours, much after final set at 4-8 hours and hardening has begun
Stage IV: Rate of reaction slows down until steady state is reached in 12-24 hours
Stage V: Steady state

Mindess & Young


Amount of hydration products formed

PCA, Young et al.


Relative volumes of pores, cement compounds,
and hydration products

(8%)

(10%)

(18%)

(55%)

NOTE: “AFt and AFm” includes ettringite (AFt) and calcium


monosulfoaluminate (AFm) and other hydrated calcium aluminate compounds.
PCA: Tennis and Jennings 2000
Evolution and volumes of hydration products

PCA: Kosmatka (2005)


Gel and pore volumes as a function of the degree
of hydration (α) and water-cement ratio (w/c)

w/c = 0.6 w/c ≈ 0.42 w/c = 0.3


empty pores
1

capillary pores capillary pores


capillary pores
gel pores gel pores
relative volume

gel pores

hydration products
hydration products (gel)
hydration products (gel)
(gel)

unhydrated cement unhydrated cement unhydrated cement


0

α  α  α 

≈ 0.5 to 10 nm  Gel pores are intrinsic part of C-S-H gel

≈10 to 10,000 nm  Capillary pores are water-filled space


between the partially hydrated cement grains
Calculating the gel and pore volumes

For constant w/c = 0.5

For degree of hydration α,


Non-evaporable water, wne = 0.24α g/g of original cement
Gel water wgel = 0.18α g/g of original cement
Hydrated product (cement gel) volume, Vhp = 0.68α cm3/g of original cement
Gel porosity = 0.26 (i.e., approximately one-fourth of C-S-H gel is pore volume)

Mindess and Young


Calculating the gel and pore volumes

For degree of hydration, a = 1

To completely form the hydration products, the minimum w/c required = 0.42α (i.e., complete
hydration cannot occur if w/c < 0.42).
For durable concrete, it is recommended to keep it ≈ 0.35 and use chemical admixtures to
improve workability etc.
Mindess and Young
Evolution and distribution of pores in hydrated
cement paste with different pozzolan contents
• Determined using mercury intrusion porosimetry
• Same w/c

Mehta and Monteiro


Physical Properties of Cement
In general, 1 cm3 of cement will occupy ≈2.1 cm3
• Colour: Dark gray of space when fully hydrated  almost double
the original volume.
• Specific gravity: 3.15
• Specific surface area: 300 – 500 m2/kg
• Grain size distributions of some cements
– Obtained by laser granulometry using a suspension of cement in ethanol

NOTE: Spinor E12 is a


special (micro-) cement for
grouts. La Malle cement is a
blended cement with 8% of
silica fume.

de Larrard
Influence of Specific Surface Area (SSA) on
Cement Properties
• Clinker mixed with 5% gypsum was ground to four
different fineness using a ball-mill.
Compressive strength of
Specific Setting time of cement Water requirement roller compacted
surface (hour:minute) of cement paste for concrete (MPa)
area normal consistency
(m2/kg) Initial Final (%) 7 90 180
28 day
setting setting day day day

258 2:28 3:15 23.8 5.7 10.4 22.9 26.4

289 2:37 3:25 23.9 5.6 10.0 20.7 26.4

325 1:43 2:20 24.0 5.7 11.4 22.1 26.8

360 1:33 2:22 24.1 5.7 11.4 21.8 25.6

Yuebo et al. 2010


Physical aspects of setting and hardening
processes
• Stiffening - Loss of consistency by the plastic cement paste
– Free water  plasticity
– Loss in free water due to the adsorption by the C-S-H and AFt and
evaporation
• Setting - Solidification of the plastic cement paste
– Initial set: Beginning of the solidification (unworkable)
– Final set: Complete solidification
• Hardening - Strength gain with time
– Higher C3S and C3A content  Higher early strength
– Higher proportion of C2S
• Slow hardening  Lower early strength and higher final strength
• Lower rate of heat of hydration
– Fineness also influences the strength development and heat evolution
Indian Standard (BIS) Cements

• Ordinary Portland Cement


– IS:269-1989 (classified as 33, 43 and 53 grade; the grade implies the
strength achieved by the cement mortar at 28 days)
• Portland Cement, Low Heat
– IS:12600-1989
• Rapid Hardening Portland Cement
– IS:8041-1978
• Portland-Pozzolana Cement
– IS:1489-1976
• Portland-Slag Cement
– IS 455-1976
European Standard (CEM) Cements: According to
ENV 197-1
• Permitted constituents
– Clinker, Ground granulated blast furnace slag (GGBS), Pozzolans, Fly Ash,
Burnt shale, Limestone, Silica fume, filler, calcium sulfate and additives
• Cement types
– I: 95-100% clinker
– II/A: 80-94% clinker (further classes depending on other constituents)
– II/B: 65-79% clinker (further classes depending on other constituents)
– III: Blast furnace cement (5-64% clinker; III/A, III/B, III/C)
– IV: Pozzolanic cement (45-89% clinker; IV/A, IV/B)
– V: Composite cement (20-64% clinker; V/A, V/B)
• Strength classes: 32.5, 32.5 R, 42.5, 42.5 R, 52.5 & 52.5 R (R: for higher
early strength)
– For example, Portland fly ash cement CEM II/B-V 42.5 R can have 65-79% clinker,
21-35% fly ash (V) and 0-5% filler. Also, calcium sulfate and additive may be present
but not included in 100%. It should have an early 2-day strength ≥ 20 MPa, and a
standard 28-day strength ≥ 42.5 MPa & ≤ 62.5 MPa.

Ravindra Gettu
American Standard (ASTM) Cements: According
to ASTM C 150
• Type I: General purpose
• Type II: Moderate sulphate resistance and moderate heat of hydration
– Lower C3S and C3A
• Type III: High early strength
– Higher C3S, and a higher fineness
• Type IV: Low heat of hydration
– Lower C3S (lower than Type II) and C3A
• Type V: High sulphate resistance
– Lower C3A
• Type IA, IIA and IIIA are Air-entrained cements
• Blended cements (ASTM C 595)
– Portland Blast-Furnace Slag Cement: Type IS (slag content of 25-70%)
– Portland-pozzolan cement: Type IP (pozzolan content of 15-40%)
Initial and Final setting times
Special Cements

• High alumina or calcium aluminate cement


• Expansive cements


Rapid setting and hardening cements
Oil-well cements Uses?
• Sulphate-resisting cement
• White cement
High Alumina Cement or Calcium aluminate
cement
• Contains about 40% of alumina and 40% of lime.
• Raw materials are limestone and bauxite.
• During the manufacture, the materials are completely fused in the kiln
(so, called ciment fondu, in french).
• Main cementitious compounds are CA and C12A7.
• Hydration results in C-A-H.
• Has good resistance to sulfate attack
(due to the absence of CH).
• 80% of its strength is developed in
24 hours.
• Some hydrates are unstable and
undergo a change in the crystalline
form with time. This conversion takes
place in the presence of water, resulting
results in considerable loss in strength.
Neville; Taylor; Mindess and Young; Mehta and Monteiro
Expansive cements (Type K, M, S)

• Expand during early hydration after setting


• Shrinkage-compensating cement
– Unrestraint expansive cement paste  cracking
– Restrained expansive paste  prestress (0.1 to 0.7 MPa)
• Self-stressing cement
– Prestress (~ 7MPa)
• Basic mechanism - Formation of AFt
• Type K, M, and S cements
– Source of aluminate ions for ettringite formation
Type K : C 4 A 3 S  8CS  6CH  90H  3C6 AS3H 32
Type M : CA  3CS  2CH  30H  C6 AS3H 32
Type S : C3A  3CS  32H  C6 AS3H 32
Rapid setting and rapid hardening cements

• Uses - Emergency repairs of leaks, shotcreting, etc.


• Setting time
– As low as 10 minutes by mixing portland cement and
plaster of paris (CaSO4.1/2 H2O) or calcium aluminate
cement
– Setting and hardening based on ettringite formation and
continued hardening based on C-S-H
• Regulated-set cement (Jet cement)
– Setting time: 2 to 5 minutes
Oil-well cements

• Need: Long setting time and quick hardening after that


• High water-cement ratio mortar is pumped to
– Depth : > 6100m
– Temperature and pressure > 204oC and 140 MPa
• API recommendations:
– Low C3A, coarse ground portland cement and some of the following
• Retarders
• Accelerators
• Lightweight or heavyweight additives
• Friction reducers
• Low water-loss additives

– Mainly based on C2S


• API RP-10B for testing
– Thickening time is important as opposed to setting time
Sulphate resisting cement

• Sulphates from soil and water


• Low C3A content (< 8%)
• Sulphates reacts with hydrated C3A
– AFt formation

Type V Cement Type V Cement


W/C-ratio = 0.65; 12 years W/C-ratio = 0.39; 16 years

Stark 2002
White cement

• Less iron content


– Typically less than 0.5% Fe2O3
– Iron-free clay and carbonates as raw materials
– Ball-mills with ceramic liners and balls for grinding the
raw mix
– Clean fuel (oil or gas) for clinker production
– higher fineness increases brightness of the colour
• Coloring pigments

ASTM Headquarters in West Conshohocken, Pennsylvania


Indian Cement Industry

• Large plants
– Capacity > 0.2 Mn. T. p.a. (Million Tonnes per annum)
Parameter 2005-2006 2008-2009
Companies 52 46
Cement plants 130 148
Installed capacity (Mn. T.) 160 219
Production (Mn. T.) 142 182
Plants with more than Mn. T. capacity 76 95
Manpower 1,35,000 1,40,000
Turnover (Mn. $) 9,700 18,500
• About 365 Miniplants
– Capacity ≈ 46 Mn. T. p.a.
– Production ≈ 6 Mn. T. p. a
• World production in 2008: 2840 Million Tonnes

www.cmaindia.org/industry.html
References

• Concrete, S. Mindess, J.F. Young, & D. Darwin, 2nd Edition, Prentice-Hall,


Englewood Cliffs, New Jersey, USA, 1981
• Concrete: Microstructure, Properties and Materials, P.K. Mehta & P.J.M.
Monteiro, 3rd Edition, Tata McGraw Hill Education Pvt. Ltd., New Delhi
• High-Performance Concrete, P.-C. Aïtcin, E&FN Spon, London, 1998
• The Science and Technology of Civil Engineering Materials, J.F. Young, S.
Mindess, R.J. Gray and A. Bentur, Prentice Hall, Upper Saddle River, New
Jersey, USA, 1998
• Cement Chemistry, H.F.W. Taylor, Thomas Telford Publ., London, 1997
• Euro-Cements, Eds. R.K. Dhir & M.R. Jones, E&FN Spon, London, 1994
• Properties of Concrete, A.M. Neville, Pearson Education, Delhi, 2004
• Concrete Mixture Proportioning, F. de Larrard, E&FN Spon, London, 1999
• Portland Cement Association, USA, web site:
http://www.cement.org/basics/concretebasics_classroom.asp
• Cement Manufacturers’ Association (India), web site:
http://www.cmaindia.org/index.html
• Cai Yuebo, Shi Quan, Ding Jian-tong, Gong Ying and Chen Bo, Indian Concrete
Journal, 2010