CEMENT 011400matthes.ppt

Cement Constituents
Winnie Matthes
HGRS / Product Innovation and Development

2
04.09.2022/MAT
© Holcim Group Support Ltd 2008
Learning Objectives
 Identify the role each cement constituent plays with
respect to final cement performance
 Understand how specific properties in the cement
applications can be achieved through appropriate use of
cement constituents
 Be aware of the importance of cement design to fulfil both
production needs and application requirements

3
04.09.2022/MAT
Question on Lotus Notes – October 31st, 2001
Any ideas how to increase our cement‘s 1 day
strength by 35%?
Regards
...

4
04.09.2022/MAT
Definition of Cements
 Cement is composed of
 Portland clinker
 Gypsum or other set regulators OPC
Composite
cements
MIC
 and one or a combination of the following
materials in relevant amount (normally >5%)
- a latent hydraulic component
- a pozzolanic component
- an inert component (filler)
and is produced by grinding (separate or compound)
or blending of the constituents

5
04.09.2022/MAT
Cement production consolidated Group companies 2007
(Data: Medos)
OPC
23.5%
Composite
cements
70.3%
Special
1.0%
White
0.1%
Oilwell
0.2%
Masonry
2.6%
MIC
2.2%
Total production: 195 Mio t

6
04.09.2022/MAT
MIC Volumes 1995 – 2007 (only consolidated companies)
0
2
4
6
8
10
12
1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Mio
t/y
Gbfs
LS
Fly Ash
Pozzolan

7
04.09.2022/MAT
Definition
 Main properties of OPC strictly derive from clinker properties
and its grinding fineness
 Main properties of composite cements are similar to OPC
because:
 they contain Portland cement clinker
 their products of hydration are identical to those of OPC
Latent hydraulic Portland cement Pozzolanic mat.
materials (ex: Slag) (ex: fly ash, pozzolan)
+ water alkaline siliceous + water
+ activator + water + lime
Calcium silicate hydrates
STRENGTH

8
04.09.2022/MAT
A cement is designed and optimised applying the Decision
Tree
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performance
Market
Definition of
requirements
composition,
process
adjust for best
2 / 28 days
grinding, beneficiation
influence MIC production
grinding process
total fineness
to achieve
properties

9
04.09.2022/MAT
Portland and Composite Cements
Early Strength of Cement vs. Clinker Factor
Clinker [%]
Data: Holderbank Product Handbook 2000
20 30 40 50 60 70 80 90 100
0
10
20
30
40
50
2-d
Compr.
Strength
on
EN
mortars
[MPa]
Slag
Pozzolanic
Portland
Limestone
Fly ash
Cement type
In composite cements, clinker is the key component, because it
provides the early strength
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

10
04.09.2022/MAT
 Apart from Portland cement clinker, clinkers for special cements can be
produced. However in many cases, composite cements can be used
beneficially to fulfil special application requirements.
 Selected properties of OPC clinker and special Portland cements:
Clinker
Main
phases
Ordinary Portland
cement clinker
High sulfate
resistant cement
(ASTM C 150, Type V)
Low heat of
hydration cement
(ASTM C 150, Type IV)
Low alkali cement
(ASTM C 150, DIN 1164-10)
C3S 60 – 65* Max 352
C2S 15 – 5* Min 402
C3A 7 – 10* Max 51 Max 72
C4AF 8 – 10* (C4AF+2*C3A):
Max 251
Na2Oeq Clinker: 0.6 (0.2-1.7)** Cement: Max 0.60
SO3 Clinker: 0.6 (0.1-1.7)** Cement: Max 2.3 Cement: Max 2.3
Comme
nts
- 1 not applicable if
sulfate expansion
specified
2 not applicable if Heat
of hydration specified
Limit for OPC
* Recommended composition ** Product Handbook 2000
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

11
04.09.2022/MAT
Early strength varies over  20 MPa
depending on composition and reactivity
Late strength of clinker is also
scattered over a > 20 MPa range
(Ex Product Handbook)
10
20
30
40
Compr.
strength
2-d,
MPa
1
2
3
4
5
6
7
8
9
1011
12
13
14
15
16
17
18
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
81
80
79
78
77
76
75
74
73
72
71
70
69
68
67
66
65
64
63
62
60
58
57
56
55
54
53
52
51
50
49
48
47
46
45
44
43
42
41
30
40
50
60
70
Compr.
strength
28-d,
MPa
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 17
18
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
81
80
79
78
77
76
75
74
73
72
71
70
69
68
67
66
65
64
63
62
61
60
58
57
56
54
53
5251
50
49
48
47
46
45
44
43
42
41
Clinker
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties
On Group level, the performance of the clinkers varies widely.
On plant level, maximum homogeneity of the clinker quality is
crucial for product acceptance.

12
04.09.2022/MAT
Clinker
Strength Development of Clinkers
Low reactive
clinkers develop
high late strength
and vice versa
28-d strength is
51 MPa for #20
62 MPa for #39
10 20 30 40
Compr. strength 2-d [MPa]
0.2
0.3
0.4
0.5
0.6
0.7
Ratio
2-
to
28-d
strength
in
clinker
61
39
53
21
10 62
58
63
54
11
65
8
66
55
6 7
57
67
22 60
48
41
9
17
68
36
26
73
49
78
69
16
5
12
45
72
38
44
64
2
14
20
42
24
28
32
34
13
15
29
1
5147
23
71
31
56
25
4
27
77
43
33
3
70
40
30
50
75
35
74
18
76
80
37
46
52
81
(Product Handbook)
2-d strength is 63% of 28-d
26%
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

13
04.09.2022/MAT
Factors influencing clinker reactivity
Clinker reactivity is determined by a variety of factors
Chemical composition and Bogue calculation are not sufficient to
predict clinker reactivity (more details in „Clinker optimization“)
Clinker
reactivity
Raw materials
and Fuels
Process
parameters
 Chemical composition
incl. minor and trace
elements
 Fineness
 Burnability
 AFR
 Raw meal preparation
 Uniformity
 Burning conditions
(Temp. profile, flame
length, underburning /
overburning)
 Redox
 Alkali/sulfur ratio
 Cooling rate
Equipment
 Kiln type
 Preheater, precalciner
 Bypass
 Burner
 Cooler
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

14
04.09.2022/MAT
Ca-sulfate
 In spite of its low content in cement, the Ca-sulfate
component may strongly influence important properties,
such as
 Setting
 Strength development
 Workability
 Stiffening
 Interaction with concrete admixtures
 Etc.
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
After any change in clinker composition or production
process, a sulfate optimization test should be carried out

15
04.09.2022/MAT
0
10
20
30
40
50
60
70
2 2.5 3 3.5 4 4.5 5
SO3 content [%]
1 day
2 days
7 days
28 days
Compr.
Strength
of
cement
[MPa]
Effect of Ca-sulfate Content on Strength Development
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
Ca-sulfate

16
04.09.2022/MAT
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
% SO3
Achieve stable
mill operation
Sample cement
at ≠ SO3 content
Increase gypsum
feed, then stop it
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
Ca-sulfate optimization

17
04.09.2022/MAT
MIC - Reactivity
Definition
Gbfs FA Pozzolan Limestone
Origin industrial industrial industrial
natural natural
Limited hydration
in presence of
water, requires an
activator for
further reaction
Hydration only in presence of
activator
Physical filler effect
dominating
Limited solubility
and contribution to
hydration
Reactivity Latent hydraulic Pozzolanic Pozzolanic -
Comments Some FA in US
(ASTM Type C)
have latent
hydraulic
reactivity
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

18
04.09.2022/MAT
MIC - Slag, Fly Ash and Pozzolan
Gbfs
 > 95 % glass content
 < 5% crystalline phases
Fly ash
 50 - 80% glassy particles
with minor inclusions
 20 - 50% mineral particles
(quartz, mullite, hematite,
anhydrite, coke)
Volcanic pozzolan
 All particles with
randomly varying
amounts of glass,
minerals and
impurities
Hydraulic reactivity increases with glass content and
CaO/SiO2 ratio of the glassy phase
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

19
04.09.2022/MAT
BFS Class C
fly ash
OPC
Metakaolin
Silica fume
Clays
CaO
SiO2
AI2O3
Natural
pozzolans
Class F
fly ash
MIC - Chemical Composition ranges vs OPC
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

20
04.09.2022/MAT
MIC
Contribution of different MIC to Strength
at 30% replacement
Type of MIC 2-d strength ratio 28-d strength ratio 91-d strength ratio
BF Slag 69.3 98.3 107.3
Class C pfa 72.7 103.6 110.5
Class F pfa 64.3 79.7 95.9
Pozzolan 69.6 81.3 88.6
Limestone 67.0 65.9 63.1
Latent
hydraulic
Pozzolanic
Filler
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

21
04.09.2022/MAT
Particle Size Distribution
* Gbfs fineness
Optimization of Fineness for Best Performance
Cement type Blaine CS 1d CS 28d
Reference 4711 24.3 46.7
40% Gbfs 5000* 12.3 59.1
40% Gbfs 4500* 12.3 55.6
40% Gbfs 4000* 12.0 53.5
40% Gbfs 3500* 10.5 50.7
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness

23
04.09.2022/MAT
Fineness: Particle size distribution vs Blaine
Test Particle size distribution, not only Blaine,
especially for composite cements
0
10
20
30
40
50
60
70
80
1 10 100
3/9 mm
0/3 mm
9/25 mm
25/30 mm
Days
Locher et al, 1966
 Finest fraction  early strength
 Medium fractions  later strength
 Coarse fraction  weak reactivity
10
20
30
40
0.8 0.9 1 1.1 1.2 1.3 1.4
0
25
50
75
CS, DIN EN, MPa of lab cements of
same Blaine and different PSD
Kuhlmann, 1985
n, RRSB of cements
x’,
RRSB,
mm
Steepness of PSD, Water demand
Particle size
2d
7d
28d
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
CS, DIN EN, MPa of Clk fractions +5% gypsum

24
04.09.2022/MAT
Cement Additives
 Simple compounds
 Increased mill output
 Reduction of vibration
in VRM
 Higher flowability of
cement
 Typical dosage
100 - 300 g/t
Improvement of
grinding process
 Grinding aids
Use QI as (further) quality enhancers, not
as solution for all problems!
Improvement of
cement quality
 Quality improvers
 Partially complex compounds
  Grinding aid + accelerator
 Accelerate setting, shorter
setting times
 Accelerate hydration, higher
early strength
 Plasticizers, lower water
demand, better workability
 Typical dosage 300 - 5000 g/t
Others
 Functional
additions
 Air entrainment
 Water retention
 Retardation, etc
 Typical dosage
100 - 2000 g/t
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness

25
04.09.2022/MAT
Cement Additives
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
40
55
11
31
13
34
14
35
14
35
15
36
16
38
0
10
20
30
40
50
60
2d 7d
CS
EN
Mortar,
MPa
100% OPC
35% OPC, 65% Ggbfs
35% OPC, 65% Ggbfs
+0.05/0.1% NaSCN
35% OPC, 65% Ggbfs
+ 0.1/0.2/0.5% NaCl
Data: Holcim (Schweiz)
Gain, %
Examples for
use of
accelerators /
quality
improvers
Group company Cement type Accelerator / QI
Holcim FBNL CEM I 52.5, 42.5
CEM III/A 42.5, 52.5, CEM III/C
CBA
NaCl
Holcim Schweiz CEM II/B-L CBN
1923 23 32 41 11 13 13 16 22

26
04.09.2022/MAT
Minor Constituents
 Normally enriched in alkali
sulphates/chlorides
 Difficult to dispose of
 Sometimes large quantities
available
 Can be used to accelerate
hydration of clinker
 Complies with cement
standards (EN197, ASTM1157)
CKD
 Up to 5% no major change in
strength performance
 Slight increase in early
strength possible, filler effect
 Helps to reduce production
costs
 Improves grinding process
Limestone

27
04.09.2022/MAT
Composite Cements - Standards
Example EN 197-1
EN 197-1: Physico-Mechanical Properties
Strength
Compr. strength [N/mm² - MPa] Initial Expansion
class
Early strength Standard strength setting
[mm]
2 days 7 days 28 days time [min]
32,5 N -  16
 32,5  52,5
32,5 R  10 -
 75
42,5 N  10 -
 42,5  62,5
42,5 R  20 -
52,5 N  20 -
 52,5 -
52,5 R  30 -
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
 10
 60
 45

28
04.09.2022/MAT
Example EN 197-1
0
10
20
30
40
50
60
70
80
Compr.
Strength
[MPa]
.
2d 28d
7d
OPC
Slag cement (CEM III)
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
Therefore, EN 197-4 (2004) was elaborated
CEM III: EN 197-4
Strength limits may not comply
with composite cement properties

29
04.09.2022/MAT
Example EN 197-4 (2004)
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
EN 197-4 considers slower strength development of
cements with high ggbfs content
Cement types
concerned
Clinker /
Ggbfs, %
CEM III/A 35-64 /
36-65
CEM III/B 20-34 /
66-80
CEM III/C 5-19 /
81-95
Cements Strength classes
Strength
class
CS, 2d,
MPa
CS, 7d,
MPa
CS, 28d,
Mpa, min
CS, 28d,
Mpa, max
32.5L -  12  32  52.5
42.5L -  16  42  62.5
52.5L  10 -  52 -
Lower 2d and 7d mortar strength
requirements vs EN 197-1

30
04.09.2022/MAT
Quality control in
production
Water demand
Setting time
Mortar strength
Compliance with
cement standards
Performance in
application
Workability
Setting time
Concrete Admix
Bleeding
Finishing
Strength
Durability
X
Performance in concrete not ensured by cement standard
requirements. Need for concrete testing
Performance in application
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness

31
04.09.2022/MAT
Performance in application
 Validate composite cement performance in reproducible
application conditions
 Test acc. to environmental conditions of concreting
(T, %RH, mix-design, aggregates)
 Test for workability – effect on strength development
 THINK CONCRETE!
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness

32
04.09.2022/MAT
Performance targets
 Know what you want to produce based on
 Customer requirements
 Production needs
 Business opportunities
 Available standards
 Define main properties of composite cement
involving
 Production
 Marketing
 Product Development
 Technical Customer Services
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performanc
e
Market
Definitionof
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness

33
04.09.2022/MAT
A cement is designed and optimised applying the Decision
Tree
Clinker
reactivity
Gypsum
addition
Mineral
components
Cement
fineness
Cement
admixtures
Cement
performance
Market
Definition of
requirements
composition,
process
adjust for best
2 / 28 days
grinding process
total fineness
to achieve
properties

34
04.09.2022/MAT
Portland and Composite Cements - Conclusions
 No universally valid recipes, but adopt a
systematic approach for Product Development – use the
Decision Tree
 Be aware of the properties of the individual constituents
and all influencing factors on cement performance
 Define targets precisely, taking into account customer
needs, local reference and practice, available standards
 Test for performance in application. Cement is not a
finished product, but a raw material for concrete
production

CEMENT 011400matthes.ppt

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