9.

Extended Cements
C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 111
9 . 1 I NT R ODUC T I ON
9 . 2 NON- C L I NK E R MAT E R I A L S
9 . 2 . 1 GR A NU L AT E D B L A S T F U R NA C E S L A G
9 . 2 . 2 F LY A S H
9 . 2 . 3 NAT U R A L P OZ Z OL A N
9 . 2 . 4 L I ME S T ONE
9 . 3 I NF L UE NC E ON C E ME NT GR I NDI NG
9 . 4 I NF L UE NC E ON C E ME NT P E R F OR MA NC E
9 . 4 . 1 I NT R ODU C T I ON
9 . 4 . 2 GR A NU L AT E D B L A S T F U R NA C E S L A G
9 . 4 . 3 F LY A S H
9 . 4 . 4 NAT U R A L P OZ Z OL A N
9 . 4 . 5 L I ME S T ONE
9 . 4 . 6 I NF L U E NC E OF C L I NK E R P R OP E RT I E S
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C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 112
9.1 INTRODUCTION
Extended or composite cements are cements in which a
proportion of the cement consists of non-Portland Cement
clinker. This proportion is usually greater than 5% (i.e. in line
with EN197 terminology - see section 7).
Materials commonly used are:-
- granulated blast furnace slag
- fly ash
- natural pozzolan
- limestone
- silica fume
These can effectively be inert fillers, pozzolanic or latently
hydraulic.
The production of composite cements is quite commonplace,
but there are notable exceptions such as North America.
The materials used can strongly influence:-
- mill performance
- final cement performance
Pozzolanic materials are low in CaO, but contain significant
levels of SiO
2
and Al
2
O
3
in a reactive (usually glassy) form.
These are able to react with calcium hydroxide to produce
additional cementitious calcium silicate and aluminate hydrates.
Latently hydraulic materials contain sufficient reactive CaO to
form calcium silicates and aluminate hydrates.
These reactions are however generally slower than those
involved in the hydration of Portland Cement clinker.
Consequently good curing is required to realise their
contribution to strength development.
Typical characteristics are shown in Figure 106.
During the 1990s there were a number of trends, which made
the utilisation of limestone more attractive in cement
production, i.e.
- slag availability limited, costs rising in relation to
clinker variable cost
- fly ash limited
- natural pozzolans limited to specific locations
- European standardisation
Limestones are generally available at the cement works at
comparatively low cost. However these will not always be
suitable for cement addition (e.g. Type II above 5%) since they
may contain levels of clay and/or organic carbon. These have
relatively stringent limits in EN197.
Figure 106. Typical Characteristics of Non-Clinker Additions.
9. EXTENDED CEMENTS
Fly Ash Pozzolan Slag Limstone
Si0
2
Al
2
0
3
Fe
2
0
3
Ca0
Mg0
S
S0
3
L0I
K
2
0
Na
2
0
38 - 64
20 - 36
4 - 18
1 - 10
0.5 - 2
0.3 - 2.5
2 - 7
0.4 - 4
0.2 - 1.5
60 - 75
10 - 20
1 - 10
1 - 5
0.2 - 2
0 - 1
2 - 12
1 - 6
0.5 - 4
30 - 37
9 - 17
0.2 - 2
34 - 45
4 - 13
0.5 - 2
0.05 - 0.2
0.02 - 1
0.3 - 1
0.2 - 1
3
0.5
0.5
51
2
0.3
42
0.1
0.02
Reactive
Phases
Low lime
silicate glass
Low lime
silicate glass
zeolite type
High lime
silicate glass
Essentially
inert
Physical
Properties
Dry similar
to cement
Humidity can
be abrasive
needs to be
crushed
Humidity
abrasive hard
to grind
Humidity
needs to be
crushed
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C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 113
9.2 NON-CLINKER MATERIALS
9.2.1 GRANULATED BLASTFURNACE SLAG
Slags can be air-cooled, pelletised or granulated. In order to
possess hydraulic properties the slag must be quenched rapidly
to preserve the molten slag in a glassy form. Granulation uses
excess water and this produces the highest glass content
producing a wet sand like material (8-12% moisture is
common). Pelletised slag can also contain sufficient glassy
material. Glass content is thus important in selecting slag.
Chemical reactivity can also be important in slag selection, and
a number of "hydraulic indices" have been proposed, e.g.
H.I. = CaO + MgO + Al
2
O
3
SiO
2
Strength increases with hydraulic index (H.I.), which is typically
in the 1.5 - 2.0 range.
Depending on the cooling water, slag can contain significant
levels of chloride and this also has to be considered.
9.2.2 FLY ASH
Variability between sources of fly ash (from base-load power
stations) does not lead to significant variations in the influence
on cement properties when interground and tested at a fixed
water cement ratio. The major concerns are:-
- carbon content, which can directly influence colour
and admixture use. This is limited by the maximum
LOI of 5.0%
- fineness, particularly residue, e.g. at 45 microns
The latter can adversely influence concrete water demand,
although this is less noticeable when interground.
Fly ash has an as-received SSA similar to that of cement, i.e.
200-500 m
2
/kg.
9.2.3 NATURAL POZZOLAN
The most common natural pozzolans are volcanic ashes, which
contain glassy phases similar to those of bituminous coal ash.
However the range of reactivity is greater than that of fly ash.
Some pozzolans have undergone alteration to yield zeolitic
type phases.
Chemical testing and determination of crystallinity can help to
assess their suitability. However, in most cases, practical testing
of cements, produced with blended or interground pozzolans is
carried out to assess their usefulness.
Some pozzolans, particularly those that are mainly glassy, have
little influence on water demand. However others, e.g. zeolitic
types, can have a significant influence and result in much higher
water demand.
9.2.4 LIMESTONE
Limestone is generally seen as an inert filter and the suitability is
therefore usually assessed in terms of the impurities present. For
this reason EN197 has placed a minimum of 75% calcium
carbonate, and maximum limits for clay (methylene blue
absorption) and organic carbon.
Their colour, hardness and availability (and impact on cement
making reserves) can also be important.
9. EXTENDED CEMENTS
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C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 114
9.3 INFLUENCE ON CEMENT GRINDING
The utilisation of non-clinker materials will have a direct
influence on the milling process depending on their properties
and percentage used.
The main impacts are on the relationship between mill output
(i.e. kWh/tonne) and fineness (i.e. Blaine) and the relationship
between the Blaine and residue (i.e. the psd).
The influence on the SSA:kWh/tonne relationship can be seen as
a change in the grindability.
The other main parameters affected are:-
- clinker grinding efficiency
- mill retention
- mill internals coating
- moisture input
- temperature
- flowability
Slag: The grindability characteristics of slag probably
most closely match that of the clinker, although
the relative grindability can be anywhere
between 100 - 200% of clinker, typically 150%,
i.e. harder.
There is a minimum fineness level required to
achieve acceptable strength development of the
slag (usually around 400m
2
/kg or higher when
ground alone) and thus kWh/tonne will tend to
be higher.
Coating will tend to be reduced when slag is
present although any increase in moisture input
will need assessing.
Fly Ash: The grindability of the mill feed when fly ash is
present will be perceived as being easier, on
account of the influence on SSA. The resultant
psd tends to be narrower for high levels of pfa.
Flowability is usually seen to be enhanced for fly
ash cements and as a result the mill retention can
be lower.
Natural The effects on grindability, fineness, psd and mill
Pozzolans: retention can be positive or negative depending
on the nature of the pozzolan.
However most pozzolans will tend to produce an
increase in SSA for a given kWh/tonne.
Limestone: Limestone tends to produce a wider psd for
the cement, although in terms of Blaine, the
grindability is perceived to be easier than
that of clinker.
The resultant higher residues tend to be
richer in clinker, although this depends on
the nature of the limestones. So-called soft
limestone tends to produce the wider psd's
and the residues can sometimes be richer in
limestone than the bulk of the cement.
Coating can often be worse with limestone
cements and retention time maybe
increased.
Because of the wider psd, mill operating
control procedures will need to be different
to when grinding pure Portland Cements.
For example grinding to a constant SSA
will produce:-
- a large increase in mill production
- a significant increase in residue levels
- a substantial reduction in strengths
Grinding to a constant residue, however,
will produce:-
- a large reduction in mill production
- a significant increase in the SSA
- a moderate reduction in the strengths
Grinding to a constant kWh/tonne will thus
provide intermediate influences on SSA,
residue and strength development.
9. EXTENDED CEMENTS
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C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 115
9.4 INFLUENCE ON CEMENT PERFORMANCE
9.4.1 INTRODUCTION
Slag cements are typically produced with a wide range of slag
contents, e.g. anywhere between 20-80%. Fly ash is generally
limited to 20-30%, which is similar to natural pozzolans,
although these can also be used at higher levels. Limestone
cements tend to have lower levels of addition, typically 10-25%,
but in lower strength cement types can be as a high as 40% (e.g.
Thailand).
In general, cements containing significant non-clinker additions
need good curing conditions in order to obtain the full benefits
of the addition.
The influence on durability is quite complex, although
equivalent performance to OPC's can be attained when concrete
is produced at equivalent strength grades.
9.4.2 GRANULATED BLAST FURNACE SLAG
Slag cements containing up to 50% clinker replacement can
reach the same 28-day strength as the control cement containing
no slag, depending on the quality of the slag. However the
earlier strengths will be somewhat lower than those of the
control e.g. only 50%.
Slag cement is often produced by separate grinding, followed by
blending. Optimum performance is often found with a slag
fineness of 400 - 450 m
2
/kg, which can produce blended cement
with 100% of OPC strength at 28-days. However in some
cases, e.g. North America, slag has been ground at 550 - 600
m
2
/kg and parity to OPC is virtually reached at 7-days, with 28-
day strengths higher than the OPC control.
In low temperature curing the strength development of slag
cements can be more significantly reduced when compared to
that of the control.
9.4.3 FLY ASH
Fly ash cements, with 20-30% fly ash, rarely produce similar
28-day strengths to those of the control OPC, although some of
this strength reduction can be offset by an improvement in
concrete workability characteristics. The performance of fly ash
is substantially improved with higher curing conditions.
When ground at constant kWh/tonne, the addition of fly ash
can be expected to:-
- reduce 28 day strength
- significantly reduce early strength
- produce similar or marginally reduced longer term
(e.g. 90-day) strength
- increase SSA
- reduce residue
- improve slump
A typical effect on some of these properties is shown in Figure
107 for UK fly ash tested at constant water/cement ratio.
Figure 107. Influence of Fly Ash on Cement Performance. As cement fineness is increased colour can become noticeably
darker for fly ash containing moderate levels of residual carbon.
9. EXTENDED CEMENTS
28d
7d
3d
1d
28d
7d
3d
1d
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C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 116
9.4.4 NATURAL POZZOLAN
As already discussed the range of natural pozzolans can be quite
large and hence their influence on cement performance can also
be quite large. Like many non-clinker additions, their relatively
slow reactivity (compared to clinker) can mean that their
influence at early ages, say up to 14-days, can be merely as inert
filler. When interground at constant kWh/tonne, compared to
control OPC with no pozzolan, their influence can give (e.g. at
20% addition level):-
- lower early strength, e.g. 40-80% of control
- similar or lower 28 day strength, e.g. 75-100% of
control
- higher SSA (generally)
Water demand can be significantly higher. Some typical results
are shown in Figure 108.
9.4.5 LIMESTONE
Limestones, when ignoring any deteterious influence of clay or
organic carbon, tend to be treated to have a relatively inert
influence on cement performance. The majority of performance
differences will probably arise from their influence on the
milling process and thus the resultant influence on the effective
clinker psd.
Figure 108. Examples of Using 20% Natural Pozzolan
Notes: % strength/slump at constant kWh/tonne
At 20% Pozzolan
Pozzolan A, B, C zeolitic type pozzolans
Pozzolan D, E, F glassy type pozzolans
At low levels the dilution of strength development may not be
significant. However the influence at higher levels can be
expected to give approximately a dilution influence (See Figure
109). The addition of limestone has a tendency to produce a
wider cement psd and thus a narrower strength development.
Thus at constant 28-days strength limestone can provide:-
- higher early strength
- shorter setting time
- less bleeding
Figure 109. Influence of Limestone on Cement performance.
9.4.6 INFLUENCE OF CLINKER PROPERTIES
For most composite cements the resultant strength development
is, as expected, very dependent on the inherent clinker
characteristics. As discussed, most composite cements will have:-
- similar or marginally lower 28-day strength
- significantly lower early strength
- greater deterioration in properties for poor curing
conditions and low ambient temperatures
Some of these negative properties can be partially overcome
where there is a greater activation of the non-clinker component
(i.e for pozzolanic, latently hydraulic). Activation by alkalis is
well known and thus it is not surprising that additions tend to
perform better with higher alkali clinkers, particularly those
with higher levels of water-soluble alkalis.
9. EXTENDED CEMENTS
Control A B C D E F
1 - day
2 - days
3 - days
28 - days
90 - days
Slump
100 70 40 50 60 60 50
100 75 60 65 75 75 70
100 70 60 65 70 70 65
100 75 85 85 75 80 85
100 85 95 95 80 80 85
100 25 20 75 75 110 90
28d
7d
3d
1d
28d
7d
3d
1d
contents chapter 9 chapter 10