01 Cement Chemistry

Cement Manufacturing, Chemistry
and Characterization
231M103
Learning Objectives
At the end of this presentation you will be able to:
Suggested video watch: http://www.youtube.com/watch?v=n-Pr1KTVSXo
Schlumberger Private
Define Portland Cement

Explain the 4 stages of the cement manufacture process and their impact on
cement quality
Describe the 4 main components of the Portland Cement and their role during
cement hydration
Explain the 5 periods of the hydration process and how each of them determines
the thickening time and compressive strength of a cement
Describe the 4 physical and 4 chemical properties of cement
Define the 8 main classes in which cement is classified
Name the 4 methods for cement characterization
Portland Cement
Definition:
Portland Cement is a hydraulic cement that reacts with water

to develop compressive strength
API ISO standards define oil well cements
Portland Cement is made by heating a mixture of limestone

and clay or similar materials to a temperature of 1500C and
grinding it with gypsum to form cement
4 Stages of the cement manufacture

Raw Material Preparation
Obtain the raw materials from mining the limestone, clay or

shale core
Limestone Quarry
Raw Materials
Calcareous - 2 Parts
Argillaceous - 1 Part
Clays
Calcite
Marl
Cement rocks
Shales
Chalk
Slate and Mudstone
Marine shells and coral
Blast furnace slag
Alkali wastes
Ashes (fly ash)
Limestone (CaCO3)

Obtain the raw materials from mining the limestone, clay or
shale core
Raw materials preparation
Raw Materials Preparation Dry Process
Grinding and Blending of DRY Materials

Cheapest Process
Less clinker quality
Raw Materials Preparation Wet Process
Grinding and Blending of SLURRIED materials

Expensive Process due to fuel required to evaporate the water
More uniform clinker quality

Burning Process
Cement Kiln
Burning Process
Preheated blend sent to Rotary kiln

Blend kiln-burned to partial fusion @ 1500oC (2700oF)
Complex series of reaction take place in the kiln whereby the raw materials are
converted to CLINKER
Cement Kiln
Inside of Kiln

Burning Process
Cement Kiln
Reaction Zones in a Rotary Cement Kiln
VI
Cooling
C3A and C4AF crystallization occurs
as liquid phase disappears

Burning Process
Cement Kiln
Clinker Components
Clinker Components
CLINKER - Grind and Heat Treat in kiln at 1500o C
: Tricalcium Silicate (Alite)
C2S
C3A
C4AF
: Dicalcium Silicate (Belite)

: Tricalcium Aluminate
: Tetracalcium Aluminoferrite
Ca + Mg Oxides, Ca(OH)2, CaCO3, Na2NO4. etc
C3S
Cement Clinker Grain Structure

C3S: Major Component
55-65% early CS
25-35% for D, E, F retarded cement
15-25% content
Later CS development
C3A: Lowest concentration, hydrates rapidly
3 - 8 % content
< 3% content for HSR
C4AF: Interstitial phase, highly reactive
8 - 12% content
C2S: Second most abundant, but very slow

reaction

Burning Process
Cooling Process
Clinker Cooling System
Clinker Cooling System
Cooling Process - Slow

Clinker quality VERY dependent on cooling rate
Cooling Rate: Slow (4-5oC/min)
C3A and C4AF develop a high degree of crystalinity
C3S and C2S crystals become highly ordered
Free Magnesia forms periclase crystals
Less hydraulically active with large particle size
Quicker early strength development (3-7 days)
Lower long term strength (28 days)
Lower sulphate resistance
Result
HIGHER DEGREE OF UNSOUNDNESS
Cooling Process - Fast
Result:
More hydraulically active with relatively small particle size
Lower early strength development (3-7 days)
Higher long term strength (28 days)
More sulphate resistance
Free MgO is less active
UNSOUNDNESS IS LESS LIKELY
Cooling Rate: Fast (18-20oC/min)

C3A and C4AF remains in glassy phase
C3S and C2S remain less ordered
Free magnesia remain in glassy phase

Burning Process
Grinding Process
Cooling Process
Finish Mill Grinding
Cement Kiln, Grinding and Storage
Grinding, Storage and Distribution
The addition of Gypsum occurs
The particle size distribution is determined also in this stage
Finally, Portland Cement is completed
Gypsum Addition
GYPSUM
(CaSO4.1/2H2O)
Pulverize Mixture and Blend to give PSD
Ca.SO4.2H2O
3 to 5 % Concentration
Blend Of Gypsum
Calcium Sulphate Hemihydrate
Anhydrate
(CaSO4)
Particle Size Distribution (PSD)

Also known as Fineness of Cement
Determines the Cement Reactivity
Slurry Rheology
Development of Compressive Strength
Thickening Time
Measured 3 different ways
Wagner
Blaine
BET
Effects of this stage on Cement Properties

GRINDING PROCESS AND GYPSUM ADDITION
Increased Proportion of cement reacts
Rate of Hydration Increased
Higher Early Strength Development
GYPSUM
Controlled Addition Difficult

Calcium Sulphate Hemi-Hydrate formation
leads to shorter Hydration times.
Too Little gives Gelation Problems

(rapid C3A)
FINER GRIND
Cement Clinker Grain Structure
Effects of Major Clinker Components

SILICATE PHASE
C3S, TRICALCIUM SILICATE
C2S, DICALCIUM SILICATE

Formed from CaO and SiO2
Hydrates very slowly with lowest heat of hydration
Affects long term compressive strength
Major component in cement (formed from CaO and SiO2)

Hydrates more rapidly than C2S (control setting time)
Contributes to all stages of strength development (esp. early)
C3S AND C2S Hydration
Effects of Major Clinker Components

ALUMINATE PHASE
C3A, TRICALCIUM ALUMINATE

Formed from CaO and Al2O3
Hydrates rapidly and produces highest heat of hydration
Plays an important role in:
Early strength development

Rheological behavior of slurry
Controlling setting and thickening time
Hydrated C3A is readily attacked by sulphate
C4AF, TETRACALCIUM ALUMINOFERRITE
Formed from CaO, Al2O3, and Fe2O3

Gives color to cement
Little effect on set properties
Produces low heat of hydration
Formation of
Cement
Hydrates
120
116
112
108
104
100
96
92
88
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
30
20
Hydration of Portland Cement

60
50
40
10
60
50
40
30
20
PRE-INDUCTION PERIOD
10
120
116
112
108
96
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
Pre-induction period lasts 30 sec - 4 mins (just after cement mixing)
Highly exothermic reaction
Initial C-S-H gel layer is formed over the C3S surfaces
Ettringite is formed and precipitates onto the C3A surfaces
Hydration reactions reduced because:
C3A inhibited by ettringite formation
C3S inhibited by C-S-H gel layer
C2S and C4AF naturally slow reactions
Ca(OH)2 (Portlandite) concentration starts increasing
60
INDUCTION PERIOD
20
50
40
30
10
120
116
112
108
96
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
Hydration activity low and heat liberation falls

Ca2+ and OH- ion concentration increasing to saturation with respect to Ca(OH)2
Period ends with increase in hydration activity and heat generation
Change C-S-H gel layer allows hydration of C3S to continue

Gypsum used up so C3A hydration resumes quickly
Only small percentage of C3S hydrated during this period
Ca2+ and OH- ion critical supersaturation level reached, Ca(OH)2 starts to precipitate
60
50
40
30
20
ACCELERATION PERIOD
10
120
116
112
108
96
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
Most rapid hydration occurs (Still most C3S available for reaction)
Solid Ca(OH)2 crystallizes from solution
Cohesive network is formed, strength is developed
DECELERATION PERIOD
System porosity decreases as more hydrates formed
Diffusion of water through hydrate layers is reduced
Transport of ionic species is hindered
Hydration rate decelerates
Hydrates interlink and grow, decreasing porosity
60
50
40
30
DIFFUSION PERIOD
Hydration continues very slowly
Reducing rate of heat evolution
Thickening of hydration products around cement phases = Porosity Reduction
No major structural changes occur
Total hydration is never attained under ambient conditions due to Portlandite engulfing
C3S grains
Period indefinite under ambient conditions
20
10
120
116
112
108
96
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
Hydrated C3S Grains

(Acceleration Period)
Hydrated C3S Grains

(Deceleration Period)
Physical & Chemical properties of Cement
Volume changes during setting (p)

Temperature Effects (p)
Flash & False set (c)
Effects of Aging (p)
Influence of Alkalis (c)
Influence of Surface Area (p)
Sulfate Resistance (c)
Strength Retrogression (c)
Volume changes during setting

Absolute Volume (Chemical Shrinkage)
It results from the reaction with water
4 -6 % by volume reduction
Bulk Volume
It can increase or decrease

If it decreases, is very low < 0.2% by volume
If it increases, is due to a porosity increase in the cement matrix
Flash & False Set

Flash set
Uncontrolled C3A hydration (low or no gypsum)
High clinker activity
Pseudo Set
False set
Precipitation of secondary gypsum due to dehydration of

gypsum and higher solubility of products formed
Slurry gelation inevitable
Reversible by vigorous agitation
Aging Effects
A Result Of:
Long Storage Periods
High Humidity
Hot Temperatures (False Set risk)
Carbonation
Affect Cement By:
Increased Thickening Time
Decreased Compressive Strength
Decreased Heat Of Hydration
Increased Slurry Viscosity
Unpredictable Slurry Viscosity
Bulk Handling More Difficult
Influence of Surface Area

Also called fineness
Influence the following
Cement reactivity
Slurry rheology
Thickening time
Compressive strength
Measured 3 different ways
Wagner
Blaine
BET
Sulfate Resistance
Expansion Loss of
Compressive Strength
Cracking Damage to
tubulars
Low C3A content are less likely to

sulfate attack
HSR (High sulfate resistant

C3A < 3%)
MSR (Medium sulfate

resistant 3% <C3A < 8%
Sulfates in downhole brines react

with cement hydration products
(Ca(OH)2) to form secondary
ettringite
This causes:
Strength Retrogression
2C3S + C2S + water
C-S-H GEL + PORTLANDITE (Ca(OH)2)
Above 230F
This causes
Decrease in Compressive Strength
Increase in Permeability
This phenomenon is know as Strength Retrogression

It can be prevented by the addition of silica
At higher temperatures C-S-H phase changes
Classification of Portland cements

Two main classifications
ASTM
API and ISO

API and ISO
Sulfate Resistance
Surface Area
Classifies Oil Well Cements

8 classifications (From A to H)
API-ISO Cement Classification

CLASS A : Similar to ASTM Type I cement., contruction cement
CLASS C : Available in all three degrees of sulphate resistance, and is

roughly equivalent to ASTM Type III. To achieve high early strength. The
C3S content and the surface area are relatively high.
CLASS D, E, and F are no longer used
CLASS B : Moderate to high sulphate resistance. Similar to ASTM Type

II, and has a lower C3A content than class A.
API-ISO Cement Classification (cont.)

CLASS G and H : Intended for use as a basic well cement and can be
use with accelerators and retarder to cover a wide range of well depths
of class G and H well cements. They are available in both MSR and HSR
types.
and temperatures. No additions other than calcium sulphate or water, or

both , shall be interground or blended with the clinker during manufacture
API Cement Typical Phase Compositions

API
CLASS
C3 S
C2 S
C3 A
C4AF
FINENESS
(cm2/g)
I
II
III
(II)
(II)
45
44
53
28
38
50
50
27
31
19
49
43
30
30
11
5
11
4
5
5
5
8
13
9
12
9
12
12
1600
1600
2200
1500
1500
1800
1600
A
B
C
D
E
G
H
ASTM
TYPE
Summary
Portland Cement definition

Stages of the cement manufacture process and their impact on cement quality
Main components of the Portland Cement and their role during cement hydration
Periods of the hydration process and how each of them determines the
thickening time and compressive strength of a cement
Physical and Chemical properties of cement
Cement Classification
Methods for Cement Characterization

01 Cement Chemistry

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01 Cement Chemistry

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Cement Manufacturing, Chemistry

Suggested video watch: http://www.youtube.com/watch?v=n-Pr1KTVSXo

Define Portland Cement

Portland Cement is a hydraulic cement that reacts with water

Portland Cement is made by heating a mixture of limestone

4 Stages of the cement manufacture

Obtain the raw materials from mining the limestone, clay or

Slate and Mudstone

Marine shells and coral

Blast furnace slag

Ashes (fly ash)

4 Stages of the cement manufacture

Raw materials preparation

Raw Materials Preparation Dry Process

Grinding and Blending of DRY Materials

Raw Materials Preparation Wet Process

Grinding and Blending of SLURRIED materials

4 Stages of the cement manufacture

Preheated blend sent to Rotary kiln

4 Stages of the cement manufacture

Reaction Zones in a Rotary Cement Kiln

Reaction Zones in a Rotary Cement Kiln

4 Stages of the cement manufacture

Reaction Zones in a Rotary Cement Kiln

: Dicalcium Silicate (Belite)

Ca + Mg Oxides, Ca(OH)2, CaCO3, Na2NO4. etc

Cement Clinker Grain Structure

25-35% for D, E, F retarded cement

C3A: Lowest concentration, hydrates rapidly

< 3% content for HSR

C4AF: Interstitial phase, highly reactive

C2S: Second most abundant, but very slow

4 Stages of the cement manufacture

Clinker Cooling System

Clinker Cooling System

Cooling Process - Slow

C3S and C2S crystals become highly ordered

Free Magnesia forms periclase crystals

Less hydraulically active with large particle size

Quicker early strength development (3-7 days)

Lower long term strength (28 days)

Lower sulphate resistance

HIGHER DEGREE OF UNSOUNDNESS

Cooling Process - Fast

Cooling Rate: Fast (18-20oC/min)

4 Stages of the cement manufacture

Finish Mill Grinding

Cement Kiln, Grinding and Storage

Grinding, Storage and Distribution

The addition of Gypsum occurs

The particle size distribution is determined also in this stage

Finally, Portland Cement is completed

Pulverize Mixture and Blend to give PSD

Particle Size Distribution (PSD)

Development of Compressive Strength

Effects of this stage on Cement Properties

Controlled Addition Difficult

Too Little gives Gelation Problems

Cement Clinker Grain Structure

Effects of Major Clinker Components

C3S, TRICALCIUM SILICATE

C2S, DICALCIUM SILICATE

Major component in cement (formed from CaO and SiO2)

C3S AND C2S Hydration