CVL141 Civil Engineering Materials: Shashank Bishnoi

CVL141
Civil Engineering Materials

Chapter 3
Shashank Bishnoi
Production and hydration of
cement
Illustrations in this section from Portland Cement Association

and various other authors
2
S. Bishnoi, IIT Delhi
Outline
 Production of cement
 Composition of cement
 Hydration of cement phases
 Microstructural development
3
Cements
 In construction, cements are usually fne
powders (~100nm to 300μm) that
harden on reacting with water
From PCA
4
Cement
 There are many types of cements, e.g.:

 Portland cements,
 Calcium aluminate cements (High alumina
cements),
 Calcium sulpho-aluminate cements
 Blended cements, etc.
5
Portland cement
 The most commonly used cement is
Ordinary Portland Cement or simply
OPC
 OPC is so called as it bears similarity to
the Portland Stone found in England
 Joseph Aspdin, a British brick-layer got
a patent to Portland cements in 1824
6
Minerals in Portland cement
S N a
M g rest K rest
K M g
N a
C a
F e
O
A l O
C a
S i
S i
F e A l
Earth's crust Typical cement
Slide from K.L. Scrivener

7
Primary components of OPC
 Calcium
 Silica
 Iron
 Aluminium
 Sulfate
8
Quarries and transportation
Limestone quarry and trucking rocks to the crusher
9
Modern dry process manufacture
From PCA
10
Blending of raw materials
From PCA
11
Burning in kiln
From PCA
12
Rotary kiln
13
Inside a kiln
14
Grinding and packing
From PCA
15
Typical reactions in the kiln
 Limestone
 Production of CaO + CO2
 Clay
 Production of SiO2 + Al2O3 + Fe2O3
16
Production of clinker
 Up to 700°C
 Raw materials are in powder form
 No interaction between particles
 Water is lost and clay recrystallises
 700°C to 900°C
 Particles are still solid
 Free lime increases
 C2S starts to form
 1150°C to 1200°C
 Particles start to stick from reactions
 Small Belite crystals form
From PCA
17
Production of clinker
 1200°C to 1350°C
 Agglomeration of particles
 Liquid phase is formed
 Free lime and Belite react to form Alite
 1350°C to 1450°C
 Belite crystals reduce in number and
increase in size
 Alite cyrstals grow in size and number
 Clinker nodules form with sufcient liquid
 Cooling
 C3A and C4AF crystallise
From PCA
18
Grinding
 The clinker is then ground
 Gypsum is mixed with clinker during
grinding to regulate time of set and
expansion properties of cements
From PCA
19
Cement chemistry notations
 CaO – C
 SiO2 – S
 Al2O3 – A
 Fe2O3 – F
 SO3 – S
 H2O – H
20
Main phases in OPC
 3CaO.SiO2 – Alite – C3S
 2CaO.SiO2 – Belite – C2S
 3CaO.Al2O3 – Aluminate – C3A
 4CaO.Al2O3.Fe2O3 – Ferrite - C4AF
21
Example oxide contents
Kocaba 2009
22
Determination of phase content
 Oxide analysis from X-Ray forescence
 Phases from Bogue equations
 C3S = 4.071C – 7.6S – 6.718A – 1.43F -
2.53S
 C2S = 2.687S - 0.7544C3S
 C3A = 2.65A – 1.692F
 C4AF = 3.043F
 Loss on ignition for total moisture and
CO2 in cement
23
Example: Bogue of Indian cements
Cem 1 Cem 2 Cem 3 Cem 4
SiO2 % 21.59 20.68 21.36 21.71
Al2O3 % 5.59 5.13 5.38 4.65
Fe2O3 % 3.75 4.11 4.18 4.47
CaO % 62.62 63.09 61.88 62.22
MgO % 1.29 1.24 1.05 1.15
K2O % 0.42 0.43 0.32 0.32
Na2O % 0.19 0.15 0.19 0.05
SO3 % 2.37 2.24 2.33 2.46
TiO2 % 0.42 0.4 0.45 0.26
Mn2O3 % 0.11 0.07 0.08 0.18
P2O5 % 0.1 0.25 0.15 0.28
Cr2O3 % 0.00 0.01 0.01 <detection limit
ZrO2 % 0.00 <detection limit <detection limit <detection limit
SrO % 0.16 0.13 0.07 0.05
PAF % 1.21 1.91 2.80 1.24
Total % 99.83 99.82 100.24 99.04
C3S 41 53 41 44
C2S 31 19 30 29
C3A 8 7 7 5
C4AF 11 13 13 14
24
Indian standards on cements
 IS269: 33 Grade OPC
 IS1489: Portland-Pozzolana cement
 IS455: Portland Slag cement
 IS8043: Hydrophobic cement
 IS12600: Low-heat cement
 IS12330: Sulphate resisting cement
 IS6452: High alumina cement
 IS6909: Supersulphated cement
25
ASTM C150 classifcation of OPC
 Type I: General purpose
 Type II: Moderate sulfate resistance
(aluminate < 8%)
 Type III: High early strength
 Type IV: Low heat of hydration (low
alite, high belite)
 Type V: High sulfate resistance
(aluminate < 5%)
26
Hydration of cement phases
27
Stages in cement hydration
From Bishnoi 2008

28
Hydration of Aluminate
 Hydration is the reaction of water with
the phases in OPC
 C3A + 6H → C3AH6
 C3A + 3CSH2 + 26H → C6AS3H32
 2C3A + C6AS3H32 + 4H → 3C4ASH12
29
Setting
Mehta and Monteiro

30
Hydration of Ferrite
 Hydration of ferrite is similar to that of
aluminate
 C4AF + 10H → C3AH6 + CH + FH3
 C4AF + 3CSH2 + 30H → C6AS3H32 + CH

+ FH3
 2C4AF + C6AS3H32 + 12H → 3C4ASH12 +

2CH + 2FH3
31
Hydration of Slilicates
 Silicates are the largest phases in OPC
 C3S + 5.3H → C1.7-S-H4 + 1.3CH
 C2S + 4.3H → C1.7-S-H4 + 0.3CH
32 From Feldman and Sereda, 1970

Some properties of C-S-H
 Is the binding glue in cement
 Crystalline in the nano-scale
 Amorphous in micro-scale
 Variable density (1.7-2.1 g/cm3)
 Variable Ca-Si ratio (1.5-2.1)
 Similarity to Tobermorite and Jennite
 Substitution of silicon crystal lattice
 Adsorbs sulfate ions
 Binds chlorides
33
What does C-S-H look like?
De Jong et al. 1967

34
Richardson 1999
35
Mathur 2007
36
From Patrick Juilland

37
Powers' model of the 'Gel'
Powers 1960
38
Feldman Sereda model
Feldman and Sereda 1968

39
Properties of Portlandite
 Calcium hydroxide
 Density of around 2.24 g/cm3
 Forms hexagonal crystals under free
conditions
 Shape and size of crystals depends on
ionic concentrations and space
constraints
 Cause of high pH in pore solution
40
Properties of monosulfate
 2C3A + C6AS3H32 + 4H → 3C4ASH12
 Is a crystalline material
 A later production of ettringite using
sulfates from monosulfate can occur
causing expansion and cracking
 Has not been studied in great detail!
41
Properties of Ettringite
 C3A + 3CSH2 + 26H → C6AS3H32
 2C3A + C6AS3H32 + 4H → 3C4ASH12
 Is an AFt phase
 Forms acicular crystals that grow
outwards
 Can lead to expansion
 Reacts with aluminate in the absence of
sulfates to produce monosulfate
42
Stages in cement hydration
From Bishnoi 2008

43
Enthalpies of exothermic reactions
From Kocaba 2009

44
Enthalpies of exothermic reactions
From Kocaba 2009

45
Reactivity of phases
From PCA
46
Formation of hydrates
From PCA
47
Evolution of phases
From PCA
48
Chemical shrinkage
Air
Water
Volume fraction
Hydrates
Unhydrated cement
Progress of hydration
49
Chemical shrinkage
50
Hydrated cement microstructures
From PCA
51
Distribution of hydrates
Powers' impression of cement microstructure

(gel contains 28% porosity)
52
Hydrating cement grain
Scrivener's impression of a hydrating cement grain (1984)

53
Microstructural development - 12h
From Kocaba 2009

54
1 day
From Kocaba 2009

55
2 days
From Kocaba 2009

56
7 days
From Kocaba 2009

57
28 days
From Kocaba 2009

58
SEM micrograph at 1 year
20°C, w/c = 0.5, (Zhang 2007)

59
Development of cement
microstructure
60
Factors afecting development
 Temperature
 Cement fneness
 Curing conditions
 Availability of water
 Drying, etc.
 Design of concrete, e.g. w/c ratio
61
Efect of temperature on kinetics
From Zhang 2007

62
Efect of temperature on kinetics
From Zhang 2007

63
Efect of temperature – 1 day
5°C, w/c = 0.5, (Zhang 2007)

64
20°C, w/c = 0.5, (Zhang 2007)

65
60°C, w/c = 0.5, (Zhang 2007)

66
Efect of temperature – 1 year
5°C, w/c = 0.5, (Zhang 2007)

67
20°C, w/c = 0.5, (Zhang 2007)

68
60°C, w/c = 0.5, (Zhang 2007)

69
Efect on compressive strength
From Zhang 2007

70
Efect of fneness on kinetics
From Tenoutasse 1969

71
Efect of fneness on kinetics
From Tenoutasse 1969

72
Efect of water-cement ratio
From Boumiz et al. 1996

73
Tests on cements
74
Fineness of cement
 Blaine fneness: IS 4031 (Part 2), ASTM
C204
 Measure of specifc surface area (m2/kg)
 Typical fneness can be 300-500 m2/kg
From PCA
75
Fineness of cement
 Wagner turbidimeter (ASTM C115)
 Electronic particle size analyser
From PCA
76
Laser granulometry
From Costoya 2008, Bishnoi 2008

77
Density of cement
 Le Chatelier test (IS 4031 (Part 11),
ASTM C 188) and helium pycnometry
From PCA
78
Setting time
 Vicat test
 Cement of standard
consistency – IS 4031
(Part 4)
 A certain given
penetration into fresh
paste using a
standard needle – IS
4031 (Part 5)
From PCA
79
Setting time
 Standard Consistency:
10mm plunger (G),
penetration 5-7 mm
from bottom
 Initial set: 1mm2
needle (C),
penetration 5 mm
from bottom
 Final set: 1 mm2
needle, only needle
(F) makes impression
80
Example setting times
From PCA
81
Setting
Mehta and Monteiro

82
Soundness test
 LeChatelier apparatus
(IS4031 (Part 3))
 Measurement of
expansion of cement
after being kept at
100°C for 3 hours
 30mm inner diameter,
30mm height, 165mm
long indicators
 Diference < 10mm
83
Soundness test
 Autoclave
expansion test,
ASTM C151
From PCA
84
Strength
 Strength measured on
mortar (1:3) cubes
(7.07 cm on side –
IS4031 (Part 6)
 Demoulded after 24
hours
 Tested at 3, 7 and 28
days
From PCA
85
BIS specifcations
 33 Grade cement
 16 MPa in 72 hours, 22 MPa in 168 hours,
33 MPa in 672 hours
 43 Grade cement
43 MPa in 672 hours
 53 Grade cement
53 MPa in 672 hours
86
Strength development: mortar cubes
From PCA
87
Strength developement: cements
From PCA
88
Bulk density
 Depends on packing
 Usually between 0.8 and 1.7 g/cm3
From PCA
89
Summary
 Production of cement
 Hydration of cement phases
 Microstructural development
 Tests on cements
90
Thank you!
91

CVL141 Civil Engineering Materials: Shashank Bishnoi

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CVL141

Civil Engineering Materials

Illustrations in this section from Portland Cement Association

 Hydration of cement phases

 There are many types of cements, e.g.:

Slide from K.L. Scrivener

Limestone quarry and trucking rocks to the crusher

 3CaO.SiO2 – Alite – C3S

 2CaO.SiO2 – Belite – C2S

 3CaO.Al2O3 – Aluminate – C3A

 4CaO.Al2O3.Fe2O3 – Ferrite - C4AF

From Bishnoi 2008

 C3A + 3CSH2 + 26H → C6AS3H32

 2C3A + C6AS3H32 + 4H → 3C4ASH12

Mehta and Monteiro

 C4AF + 3CSH2 + 30H → C6AS3H32 + CH

 2C4AF + C6AS3H32 + 12H → 3C4ASH12 +

 C2S + 4.3H → C1.7-S-H4 + 0.3CH

32 From Feldman and Sereda, 1970

De Jong et al. 1967

From Patrick Juilland

Feldman and Sereda 1968

From Bishnoi 2008

From Kocaba 2009

From Kocaba 2009

Powers' impression of cement microstructure

Scrivener's impression of a hydrating cement grain (1984)

From Kocaba 2009

From Kocaba 2009

From Kocaba 2009

From Kocaba 2009

From Kocaba 2009

20°C, w/c = 0.5, (Zhang 2007)

From Zhang 2007

From Zhang 2007

5°C, w/c = 0.5, (Zhang 2007)

20°C, w/c = 0.5, (Zhang 2007)

60°C, w/c = 0.5, (Zhang 2007)

5°C, w/c = 0.5, (Zhang 2007)

20°C, w/c = 0.5, (Zhang 2007)

60°C, w/c = 0.5, (Zhang 2007)

From Zhang 2007

From Tenoutasse 1969

From Tenoutasse 1969

From Boumiz et al. 1996

From Costoya 2008, Bishnoi 2008

Mehta and Monteiro

 Hydration of cement phases

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