Cement Chemistry 2016 BL1

Cement Manufacturing, Chemistry and
Characterization
Dr. Bernhard Lungwitz

Institut fr Erdl- und Erdgastechnik
Wintersemester 2016/17
Learning Objectives
At the end of this presentation you will be able to:
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 6 main classes in which cement is classified
Name the 4 methods for cement characterization
Highly recommended: http://www.youtube.com/watch?v=nPr1KTVSXo&feature=related

Portland Cement
Portland Cement is made by heating a mixture of limestone
and clay or shale to a temperature of 1500C (2700F) and
grinding it with gypsum to form cement
Portland Cement is a hydraulic cement that hydrates

(reacts) with water to form solid masses and to develop
compressive strength
API/ISO standards define oil well cements

4 Stages of the cement manufacture

Raw Material Preparation
Burning (clinkering)
Cooling
Grinding

Raw Materials
Calcareous - 2 Parts
Argillaceous - 1 Part
Limestone
Clay
Calcite
Marl (lime rich clay)
Cement rock
Shale
Chalk
Slate and Mudstone
Marine shells and coral

Alkali waste
Blast furnace slag

Ash (fly ash)
Ground and processed in a kiln at 1500oC (2700oF)

Raw Material Preparation Dry Process
Grinding and Blending of DRY Materials
Cheapest Process
Less clinker quality

Raw Material Preparation Wet Process
-Grinding and Blending of SLURRIED materials

-Expensive Process due to fuel required to evaporate the
water
-More uniform clinker quality
7

Virtual Cement Plant tour - Web

Burning Process
- Preheated blend sent to Rotary kiln

- Blend burned to partial fusion @ 1500oC (2700oF)
- Complex series of reactions take place in the kiln
whereby the raw materials are converted to
CLINKERVirtual Cement Plant tour - Web
8

Inside Kiln

Effects of this stage on Cement Properties

Proportioning of Raw Materials
10
Material
Concentration
Too Low
Too High
CaO
65
Low early strength
Cracking,
unsoundness
SiO2
22
Rapid setting
Slow setting
Al2O3
Increased kiln
temperature
required
Rapid setting
Fe2O3
Rapid setting
MgO
Unsoundness
(>5%)

10
Reaction Zones in a Rotary Cement Kiln

25
200
800
1100
Zone
Reaction
Profile
What
occurs?
Zone
Reaction
Profile
What
occurs?
1300
11

1500
1250
11
Clinker Components
CLINKER - Product coming from kiln
12

C3S
: Tricalcium Silicate (Alite)
C2S
: Dicalcium Silicate (Belite)
C3A
: Tricalcium Aluminate
C4AF
: Tetracalcium Aluminoferrate
Ca + Mg Oxides, Ca(OH)2, CaCO3, Na2NO4. etc
12
Cement Clinker Grain Structure
C3S: Major Component

- 55-65%
- early CS
C2S: Second most abundant

- 15-25%
- Very slow reaction
- Later CS development
C3A: Lowest concentration

-
hydrates rapidly
Determines sulfate resistance
3-8%
< 3% content for HSR
C4AF: Interstitial phase

- highly reactive
- 8 - 12%
13

13
Clinker Cooling System

Clinker quality VERY
dependent on cooling rate
Courtesy of TXI Energy Services

14

14
Grinding, Storage and Distribution
-Gypsum is added
-Ground to required particle size distribution
-Process is complete: Portland Cement
18

18
Finish Mill Grinding
Virtual Cement Plant tour - Web

19

19
Gypsum Addition
- Ca.SO4.2H2O
- 3 to 5%
- Blend Of Gypsum
- Calcuim Sulphate Hemihydrate (CaSO4.1/2H2O)
- Anhydrate (CaSO4)
Pulverize Mixture to give PSD
20

20
Effects of Grinding on Cement Properties

FINER GRIND
Increased proportion of cement reacts

Rate of hydration increased
Higher early strength development
GYPSUM
Too little causes gelation
21

21
Cement Kiln, Grinding and Storage
Kiln
22

Storage
22
Cement Clinker Grain Structure

C3A, <3% for HSR,
rheology, setting
Aluminate
Phases
C3S, 55-65%, early

CS
Silicate Phases
23

C4AF, 1015%
C2S, long term CS
23
C3S AND C2S Hydration

Calcium
Hydration
Hydroxide
Stages
CSH Gel
Cement
Grains
25

25
Hydration of Portland Cement

I
II
III
IV
Rate of Hydration
60
Mix
50
T.T.
40
30
20
10

120
116
112
108
104
96
100
92
88
84
80
76
72
68
64
60
56
Time of Hydration
I. Preinduction Period
II. Induction Period
III. Acceleration Period
28
52
days
48
40
36
32
28
24
20
16
12
44
hr
min
0
IV. Decelertion Period
V. Diffusion Period
28

Pre-induction Period
Lasts 30 sec - 4 min
Highly exothermic reaction
-Initial CSH 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 CSH gel layer
-C2S and C4AF naturally slow reactions
Ca(OH)2 (Portlandite) concentration starts increasing
60
50
40
30
20
10
29

120
116
112
96
108
92
104
100
88
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
29

60
50
Induction Period
Hydration activity low and heat liberation falls
Ca++ and OH- ion concentration increasing to saturation
with respect to Ca(OH)2
Ca++ and OH- ion saturation level reached, Ca(OH)2 starts
to precipitate
Only small percentage of C3S hydrated during this period
Period ends with increase in hydration activity and heat
generation
-Change in CSH gel layer allows hydration of C3S to
continue
-Gypsum used up so C3A hydration resumes quickly
40
30
20
10
30

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
30
60
50
40
Acceleration Period
Most rapid hydration occurs (still most C3S available for reaction)
Ca(OH)2 crystallizes from solution
Hydrates interlink and grow, decreasing porosity
Cohesive network is formed, strength is developed
Deceleration Period
System porosity continues to decrease as more hydrates formed
Diffusion of water through hydrate layers is reduced
Transport of ionic species is hindered
Hydration rate decelerates
30
20
10
31

120
116
112
96
108
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
31

60
50
Diffusion Period
Hydration continues very slowly
Low rate of heat evolution
Additional hydration products formed around cement
phases = porosity reduction
No major structural changes occur
Total hydration is never attained under ambient conditions
40
30
20
10
32

120
116
112
96
108
92
104
88
100
84
80
76
72
68
64
60
56
52
48
44
40
36
32
28
24
20
16
12
32
Physical & Chemical Properties
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)
33

33
Volume changes during setting

Absolute Volume (chemical shrinkage)
-4 - 6 % by volume reduction
Cement Slurry
Cement
Set Cement
Hydrates
Water
Bulk Volume
VCement + VWater > VHydrates
Void
-can increase or decrease

-If it decreases, is very low < 0.2% by volume
-If it increases, causes a porosity increase in the cement
matrix
34

34
Cement Volume Changes
Shrinkage (%) - Temperature (10oC)
Temperature
Total Contraction
Bulk Shrinkage
0
Time (days)
35

35
Temperature Effects
250
Higher temperature, higher
Heat flow (mW)
200
150
25
45
65
85
100
50
hydration rate.
Add retarders to extend
induction period.
Add accelerators to reduce
induction period.
Above 230F, C-S-H gel not
stable and unstable
crystalline products formed.
0
0
10
15
20
Hydration tim e (hr)
36

36
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
37

37
Aging Effects
A Result Of:
- Long storage periods
- High humidity
- Hot temperatures (false set risk)
- Carbonation
Affects Cement:
- Increased thickening time
- Decreased compressive
strength
- Decreased heat of hydration
- Increased slurry viscosity
- Unpredictable slurry viscosity
- Bulk handling more difficult
38

38
Influence of Alkalis
Sodium (Na) & Potassium (K)
Affect setting and strength development

-Positive effect on early strength
-Negative effect on long term strength
Ca(OH)2 + Na2SO4 ------> CaSO4 + 2NaOH
---------> EROSION <---------
39

39
Influence of Surface Area

Called fineness (specific surface)
Influences the following
-Cement reactivity
-Slurry rheology
-Thickening time
-Compressive strength
Measured 3 different ways
-Wagner (m2/kg)
-Blaine (m2/kg)
-BET
41

41
Sulfate Resistance
Sulfates in downhole
brines react with hydration
products (Ca(OH)2) to form
secondary ettringite
This causes:
- Expansion loss of
strength
- Cracking damage to
tubulars
42

Low C3A content is less

susceptable to sulfate
attack
- HSR (High - C3A <3%)
- MSR (Medium - C3A
<8%
42
Strength Retrogression
2C3S + C2S + water
CSH gel + Portlandite (Ca(OH)2)
At higher temperatures CSH phase changes
- Above 230F (110C)
This causes
- Decrease in Compressive Strength
- Increase in Permeability
This is know as Strength Retrogression
It can be prevented by the addition of silica
43

43
API-ISO Cement Classification

CLASS A : Similar to ASTM Type I cement.
CLASS B : Moderate to high sulphate resistance. Similar to ASTM
Type II, and has a lower C3A than class A.
CLASS C : Available in all three degrees of sulphate resistance, and
is roughly equivalent to ASTM Type III. For early strength. The C3S
content and the surface area are relatively high.
CLASS G and H : Intended for use as a basic well cement and can
be used with accelerators and retarder to cover a wide range of well
depths and temperatures. No additions other than calcium sulphate
or water, or both , shall be interground or blended with the clinker
during manufacture. Available in both MSR and HSR types.
44

44
API Cement Typical Phase Compositions
API
CLASS
45
ASTM
TYPE
C3S
C2S
C3A
C4AF
FINENESS
(cm2/g)
A
B
I
II
45
44
27
31
11
5
8
13
1600
C
D
G
H
III
(II)
(II)
53
28
50
50
19
49
30
30
11
4
5
5
9
12
12
12
2200
1500
1800
1600

1600
45
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
50

50
THE MULTICOMPONENT
SYSTEM
12
10
Rate of Evolution
Dissolution: Ettringite
and C-S-H gel formation
Formation of
Monosulfate
Formation of
C-S-H & CH
6
Diffusion
Controlled
Reaction
Increase Ca++
and OH- concent.
Final Set
2
Initial Set
days
17
16
15
14
13
12
11
9
hours
10
min.
0
Time of Hydration
51

51
Questions
52

52

Cement Chemistry 2016 BL1

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Cement Manufacturing, Chemistry and

Dr. Bernhard Lungwitz

Dr. Bernhard Lungwitz

Portland Cement is a hydraulic cement that hydrates

API/ISO standards define oil well cements

Dr. Bernhard Lungwitz

4 Stages of the cement manufacture

Dr. Bernhard Lungwitz

Marl (lime rich clay)

Slate and Mudstone

Marine shells and coral

Blast furnace slag

Ground and processed in a kiln at 1500oC (2700oF)

Dr. Bernhard Lungwitz

Raw Material Preparation Dry Process

Grinding and Blending of DRY Materials

Less clinker quality

Dr. Bernhard Lungwitz

Raw Material Preparation Wet Process

-Grinding and Blending of SLURRIED materials

Dr. Bernhard Lungwitz

Virtual Cement Plant tour - Web

- Preheated blend sent to Rotary kiln

Dr. Bernhard Lungwitz

Dr. Bernhard Lungwitz

Effects of this stage on Cement Properties

Low early strength

Dr. Bernhard Lungwitz

Reaction Zones in a Rotary Cement Kiln

Dr. Bernhard Lungwitz

Dr. Bernhard Lungwitz

Cement Clinker Grain Structure

C3S: Major Component

C2S: Second most abundant

C3A: Lowest concentration

C4AF: Interstitial phase

Dr. Bernhard Lungwitz

Clinker Cooling System

Courtesy of TXI Energy Services

Dr. Bernhard Lungwitz

Grinding, Storage and Distribution

Dr. Bernhard Lungwitz

Finish Mill Grinding

Virtual Cement Plant tour - Web

Dr. Bernhard Lungwitz

Pulverize Mixture to give PSD

Dr. Bernhard Lungwitz

Effects of Grinding on Cement Properties

Increased proportion of cement reacts

Too little causes gelation

Dr. Bernhard Lungwitz

Cement Kiln, Grinding and Storage

Dr. Bernhard Lungwitz

Cement Clinker Grain Structure

C3S, 55-65%, early

Dr. Bernhard Lungwitz

C2S, long term CS

C3S AND C2S Hydration

Dr. Bernhard Lungwitz

Hydration of Portland Cement

Dr. Bernhard Lungwitz

IV. Decelertion Period