CONSTRUCTION

MATERIALS 2
CONS2012 LECTURE 2
DR. D. WHITE

INTRODUCTION

ADMIXTURES

INTRODUCTION
Admixtures are chemicals that are added
to concrete during mixing and significantly
change its fresh, early age or hardened
state to economic or physical advantage.
They are usually added at rates of less
than 5% by weight of the cement, but the
typical range for most types is only 0.3
1.5%.
3

INTRODUCTION
They are normally supplied as
aqueous solutions.
This makes it easier for dispensing
and dispersion through the concrete
during mixing.
Trend of increasing use.
4

ACTION & CLASSIFICATION

Admixtures work by one or more of the
following mechanisms:
interference with the hydration reactions to
accelerate or retard the rate of hydration of
one or more of the cement phases
physical absorption onto the surface of
cement particles causing increased particle
dispersion
5

ACTION & CLASSIFICATION

altering the surface tension of the mix water
causing air entrainment
increasing the viscosity of the mix water
resulting in an increased plastic viscosity or
cohesion of the fresh concrete
incorporating chemicals into the hardened
cement paste to enhance particular properties
such as increased protection to embedded steel
or water repellence.
6

ACTION & CLASSIFICATION

Admixtures are usually classified or
grouped according to their mode of action
rather than by their chemical constituents.
The European standard (BS EN 934)
includes requirements for:
o water-reducing/plasticising admixtures
o high-range waterreducing/superplasticising admixtures
7

ACTION & CLASSIFICATION

o set and hardening accelerating
admixtures
o set retarding admixtures
o air-entraining admixtures
o water-resisting admixtures
o water-retaining admixtures
o set-retarding/waterreducing/plasticising admixtures
8

ACTION & CLASSIFICATION

o set-retarding/high-range waterreducing/superplasticising
admixtures
o set-accelerating/waterreducing/plasticising admixtures.

ACTION & CLASSIFICATION

This study will cover the five distinct
types, which constitutes more than 80%
of the total quantities of admixtures used
in concrete:
plasticisers,
superplasticisers,
accelerators,
retarders and
air-entraining agents.
10

PLASTICISERS
Also known as workability aids, were
developed in the 1930s.
Increase the fluidity or workability of a cement
paste or concrete.
They are long-chain polymers, with the main
types being based on either lignosulphonates,
derived in the processing of wood for paper
pulp, or polycarboxylate ether.
11

PLASTICISERS
They are relatively inexpensive but
lignosulphonates can contain
significant levels of impurities (based
on the amount of processing).
Their plasticising action is due to the
surfaceactive nature of the component
polymer molecules, which are adsorbed
onto the surface of the cement grains.
12

PLASTICISERS
In their normal state the surfaces of
cement particles have a mixture of
positive and negative residual
charges (a property of all surfaces).
Consequently, the particles coalesce
into flocs when mixed with water.

13

PLASTICISERS
This traps a considerable amount of
the mix water, leaving less available
to provide fluidity.

14

PLASTICISERS
The negative ionic groups of the aqueous
plasticiser molecules, produce an overall
negative charge (few millivolts) on the surface
of cement particles onto which it is absorbed.
This results in the particles electrostatically
repelling each other; becoming more dispersed.
The trapped water is released and fluidity
increased. See figure on next slide.
15

PLASTICISERS

16

PLASTICISERS
Additionally, the particles also become
surrounded by a sheath of oriented
water molecules.
Preventing close approach of the
cement grains.
This phenomenon is known as steric
hindrance or steric repulsion.
17

PLASTICISERS
The effect of steric repulsion is one of
greater lubrication and consequently,
increased fluidity of the paste or
concrete.
For a given consistence or fluidity,
less water is required when
plasticisers are employed.
18

PLASTICISERS
That is to say, a lower water:cement ratio
and increased strength.
This is why plasticisers are often known as
water-reducers.
BS EN 934 requires that the water reduction
for constant consistence should be greater
than 5% (usually between 5% and 12%).
19

PLASTICISERS
Plasticiser use can have significant,
undesirable, secondary effects, which
include:
o some plasticisers act as retarders, delaying
the set and decreasing the early strength
gain, and/or
o entrain air in the form of small bubbles.
o may also contain impurities that have other
undesirable side-effects at increasing doses
(based on the degree of processing).
20

PLASTICISERS
The magnitude of the primary effects
that can be satisfactorily achieved
with plasticisers is thus relatively
modest, though nevertheless useful
and cost effective.

21

SUPERPLASTICISERS
Superplasticisers are used to achieve
a much greater magnitude of
increases in fluidity and workability
than those obtainable with
plasticisers.
Also known as high-range waterreducers.
22

SUPERPLASTICISERS
Developed in the 1960s, they have higher
molecular weights and are manufactured
to higher standards of purity than
plasticisers
They therefore can achieve substantially
greater primary effects without significant
undesirable side-effects. And are a crucial
ingredient of many of the special or socalled high-performance concretes.
23

SUPERPLASTICISERS
BS EN 934 requires that the water
reduction for constant consistence
should be greater than 12%.
Values range between 12% and
about 30%, depending on the types
and efficiency of the constituent
chemicals.
24

SUPERPLASTICISERS
Currently three main chemical types are used
(Dransfield 2003):
1. Sulphonated melamine formaldehyde
condensates (SMFs), normally the sodium
salt.
2. Sulphonated naphthalene formaldehyde
condensates (SNFs), again normally the
sodium salt.
3. Polycarboxylate ethers (PCLs). These have
been the most recently developed, and are
sometimes referred to as new generation
superplasticisers.
25

SUPERPLASTICISERS
These basic chemicals can be used
alone or blended with each other or
lignosulphonates to give products with a
wide range of properties and effects.
A feature of polycarboxylates is that it
can be chemically modified or tailored
to meet specific requirements.

26

SUPERPLASTICISERS
The mode of action of superplasticisers
is similar to that of plasticizers, i.e. they
cause a combination of mutual
repulsion and steric hindrance between
the cement particles.
Opinions differ about the relative
magnitude and importance of these two
effects with different superplasticisers.
27

SUPERPLASTICISERS
One consensus (Collepardi, 1998;
Edmeades and Hewlett, 1998) is that:
o electrostatic repulsion is the dominant
mechanism with SMFs and SNFs,
o steric hindrance is equally if not more
importantwith PCLs.
The high density of polymer side-chains on
the polymer backbone, protrude from the
cement particle surface, leading to greater
efficiency.
28

SUPERPLASTICISERS
The term comb polymer has been
used to describe this molecular
structure.
See figure on next slide.

29

SUPERPLASTICISERS

Comb-type molecules of polycarboxylic

superplasticisers on the surface of a cement grain,
leading to steric hindrance between grains.

30

SUPERPLASTICISERS
A comparison of the efficacy of PCL
compared to a SNF based
superplasticiser and
lignosulphonate-based plasticiser is
on the next slide.

31

SUPERPLASTICISERS

Typical effects of plasticising and superplasticising

admixtures on flow of mortars after Jeknavorian et32

SUPERPLASTICISERS
The features of the behaviour of
superplasticisers, that effect their use
in concrete, are as follows:
o According to Aitcin et al., (1994)
the behaviour of any combination
of binder and superplasticiser will
depend on several factors other
than the admixture type, including:
33

SUPERPLASTICISERS
1.
2.
3.
4.

the
the
the
the

binder constituents,
cement composition,
cement fineness and
water:binder ratio.

o Best results with lignosulphonate and, SMF

and SNF based superplasticsers added a
short time (12 minutes) after the first
contact of the mix water with the cement.
34

SUPERPLASTICISERS
It appears that if these admixture are
added at the same time as the mix water, a
significant amount is incorporated into the
rapid C3A/gypsum reaction, hence reducing
that available for workability increase.
This effect has been reported as being less
significant for at least some PCLs, which
are therefore more tolerant of mixing
procedures.
35

SUPERPLASTICISERS
o The superplasticising action occurs for
only a limited time. Therefore, for
extended road transport:
1. a retarder maybe blended with the
superplasticiser
2. the superplasticiser can be added on
site just before discharge from the
mixer truck
3. repeated additions of small extra
doses of the admixture.
36

SUPERPLASTICISERS
NB:
Some PCLs have been shown to have
lower loss of action than with other
types, at least over the critical first
hour after mixing.

37

SUPERPLASTICISERS
o There is a saturation point or optimum
dosage for any binder/superplasticiser
combination beyond which no further
increases in fluidity occurs (See next
slide).
At higher dosages, detrimental effects
such as segregation, excessive
retardation or entrapment of air during
mixing which is suddenly released
can occur.
38

SUPERPLASTICISERS

The saturation point for a cement/superplasticiser

combination (after Aitcin et al., 1994).

39

ACCELERATORS
Accelerators increase the rate of
hardening of the cement paste, by
enhancing the early strength in the 24
48 hours period after placing.
Formwork can then be removed early.
Curing time for concrete placed in cold
weather is reduced.
40

ACCELERATORS
Setting times may also reduce.
The figure on the next slide shows
the effect of Calcium chloride (CaCl2),
a popular and readily available
accelerator.

41

ACCELERATORS
Setting times may also reduce.
The figure on the next slide shows
the effect of Calcium chloride (CaCl2),
a popular and readily available
accelerator.

42

ACCELERATORS

Typical effects of calcium chloride admixture on

(a) setting times and (b) early strength of
concrete (after Dransfield and Egan, 1988).

43

ACCELERATORS
This accelerating effect of CaCl2
diminishes with time, and the longterm strength is similar to that of
non-accelerated concrete.
CaCl2 gets involved in the
C3A/gypsum and C4AF reactions.

44

ACCELERATORS
The accelerator effect comes from
CaCl2 acting as a catalyst in the
hydration reactions C3S and C2S
(Edmeades and Hewlett, 1998).
The C-S-H produced has some
modification to its structure.
45

ACCELERATORS
One negative effect of CaCl2 is that it
increases the vulnerability of the
embedded steel to corrosion due to
the presence of the chloride ions.
CaCl2 use is prohibited in reinforced
and pre-stressed concrete.

46

ACCELERATORS
Consequently, a number of chloride
free accelerators have been
developed, namely:
o calcium formate,
o sodium aluminate or
o triethanolamine.

47

ACCELERATORS
As with plasticisers and
superplasticisers, the magnitude of
the effects of accelerators depends
on the binder constituents and
composition.
It cannot be predicted with certainty,
and so should be established by
testing.
48

RETARDERS
Retarders delay the setting time of a
mix.
They are to:
o counteract the accelerating effect
of hot weather, particularly if the
concrete has to be transported for
long distance
49

RETARDERS
o control the set in large pours, where
placing may take several hours
NB:The retarder facilitates concurrent
setting of all the concrete, hence
avoiding cold joints and
discontinuities, and achieving
uniform strength development.
50

RETARDERS
The retardation effect of three
chemicals are shown in the figure on
the next slide.

These retarders are:

Sucrose,
citric acid and
Calcium lignosulphonate.
51

RETARDERS

Influence of retarders on the setting time of

cement paste (after Ramachandran et al., 1981).

52

RETARDERS
Though sucrose and citric acid are
very effective retarders, it is difficult
to control their effects.
Lignosulphonates, often with a
significant sugar content, are
preferred.

53

RETARDERS
Plasticisers such as some
lignosulphonates and carboxylic
acids have retarding properties.
Thus retarders based upon these
compounds will have some
plasticising action as well

54

RETARDERS
The mode of action of retarders
involves modification of the
formation of the early hydration
products, including the portlandite
crystals.

55

RETARDERS
The degree of retardation (as the
efficacy of other admixtures) is
dependant on a variety of factors,
including:
o temperature,
o mix proportions,
o fineness and composition of the
cement and,
o time of addition of the admixture.
56

AIR-ENTRAINING AGENTS
Air-entraining agents (AEAs) are
organic materials which, when added
to the mix water, entrain a controlled
quantity of air in the form of
microscopic bubbles in the cement
paste component of the concrete.
The bubble diameters are generally in
the range 0.021 mm
57

AIR-ENTRAINING AGENTS
The average distance between
bubbles is about 0.2 mm.
Entrained bubbles are stable enough
to be unchanged during the placing,
compaction, setting and hardening of
the concrete.

58

AIR-ENTRAINING AGENTS
Entrained air should not be confused
with entrapped air.
Entrapped air is normally present in
concrete, because of incomplete
compaction.
Usually occurs in the form of larger
irregular cavities.
59

AIR-ENTRAINING AGENTS
AEAs are powerful surfactants.
They change (reduce) the surface
tension of the mix water and
Act at the airwater interface within
the cement paste.

60

AIR-ENTRAINING AGENTS
Their molecules have a hydrocarbon
chain or backbone terminated by a
hydrophilic (water loving) polar group,
typically of a carboxylic or sulphonic acid.
This becomes orientated into the
aqueous phase, with the hydrocarbon
backbone pointing inwards towards the
air.
61

AIR-ENTRAINING AGENTS
Thus forming stable, negatively
charged bubbles that become
uniformly dispersed .
See Figure on next slide.

62

AIR-ENTRAINING AGENTS

Schematic of air entrainment by surface-active

molecules. (a) Molecular structure; (b) stable air
bubble (adapted from Mindess et al., 2003).

63

AIR-ENTRAINING AGENTS
Only a limited number of materials
are suitable, for use as AEAs. These
include:
o Vinsol resins (extracted from
pinewood) and
o Synthetic alkylsulphonates and
alkylsulphates.

64

AIR-ENTRAINING AGENTS
Entrained air provide freezethaw
resistance to the concrete.
This is achieved by providing a
reservoir for water that is entrapped
in capillary voids to expand into.

65

AIR-ENTRAINING AGENTS
Entrained-air volumes of only about
47% by volume of the concrete are
required to provide effective
protection
Bubble diameter and spacing are
important factors.

66

AIR-ENTRAINING AGENTS
At normal doses, AEAs have little influence on
the hydration reactions.
However, air entrainment has two important
secondary effects:
1. There is a general increase in the consistence
of the mix, with the bubbles seeming to act like
small ball-bearings. The bubbles size means
that they can compensate for the lack of fine
material in a coarse sand, which would otherwise
produce a concrete with poor cohesion.
67

AIR-ENTRAINING AGENTS
2. The increase in porosity results in
a drop in strength, by a factor of
about 6% for each 1% of air. This
must therefore be taken into account
in mix design, but the improvement
in workability means that the loss
can at least be partly offset by
reducing the water content and
hence the water:cement ratio.
68

ADDITIONS

69

INTRODUCTION
Definition: finely divided materials used in
concrete in order to improve certain properties or
to achieve special properties (BS EN 206, 2000).
Alternative names for additions include:
cement replacement materials, fillers, mineral
additives, mineral admixtures, supplementary
cementing materials, cement substitutes,
cement extenders, latent hydraulic materials or,
simply, cementitious materials.

70

INTRODUCTION
Additions are usually:
1. inorganic materials,
2. have a particle size similar to or
smaller than that of the Portland
cement,
3. used to replace some of the
cement in the concrete mix (or
sometimes supplement it).
71

INTRODUCTION
The benefits of additions in concrete
include:
o Improved properties
o Can lower cost and reduced
environmental impact.
Cost and environmental benefits can
be linked to the fact that the byproduct of some industrial processes
can be additions .

72

INTRODUCTION
Additions can give a variety of useful
enhancements of or modifications to
the properties of concrete.
This is the main reason for their use.

73

INTRODUCTION
Additions are either sold separately, or
pre-blended with the PC.
Pre-blended mixes have a fixed dose
rate of additions.
Additions added at batching, can have
varied dose rate, but may complicate
materials handling.
74

INTRODUCTION
Additionally, the use of additions
have implication for water : binder
ratio (for additions that participate in
hydration).
For some additions, water : powder
ratio is considered (for additions that
do not participate in hydration).
75

INTRODUCTION
BS-EN 206 recognises two broad
divisions of additions:
1. Type 1: nearly inert additions
2. Type 2: pozzolanic or latent
hydraulic additions.

76

TYPE 1 ADDITIONS
Limestone powder is the most common
Type 1 addition in use.
As mention in LECTURE 1, it is added at
a rate of less than 5% of PC.
BS EN 197-1:2000 allows this amount to
be included in a CEM I cement as a
minor additional constituent.
77

TYPE 1 ADDITIONS
Self-compacting concrete uses
limestone powder at higher rates.
The high powder contents are
required for stability and fluidity of
the fresh concrete.

78

TYPE 1 ADDITIONS
The main enhancement of properties
by Type 1 additions is physical
The fine powder particles can
improve the consistence and
cohesiveness of the fresh paste or
concrete.

79

TYPE 1 ADDITIONS
Although there is no pozzolanic
reaction, there is some enhancement
to the rate of strength gain due to:
o The filler effect of improved
particle packing and,
o The powder particles acting as
nucleation sites for the cement
hydration products..
80

TYPE 1 ADDITIONS
The calcium carbonate in the
limestone powder reacts with the
aluminate phases in the cement.

81

TYPE 2 ADDITIONS
The pozzolanic reaction is as follows:
S + CH + H C-S-H
It occurs between amorphous or glassy
phase silica, portlandite, and water to
produce C-S-H which is similar to that
produced by the PC.
Thus, pozzolans add strength to the HCP.
82

TYPE 2 ADDITIONS
In the glassy or amorphous form,
silica has a disordered structure,
which is formed by rapid cooling from
a molten state.
Many of the inter-molecular bonds in
the structure are not at their
preferred low-energy orientation.
83

TYPE 2 ADDITIONS
Consequently, these bonds can be
readily broken and link with the
oxygen component of the calcium
hydroxide.
The uniform crystalline structure of
quartz and silica sand is formed by
slower cooling, and is not chemically
active.
84

TYPE 2 ADDITIONS
The main Type 2 additions in use worldwide
are:
o fly ash, also known as pulverised fuel ash
(pfa)
o ground granulated blast furnace slag (ggbs)
o condensed silica fume (csf), often called
microsilica
o calcined clay or shale
o rice husk ash and,
o natural pozzolans
85

TYPE 2 ADDITIONS: pfa

Fly ash is the ash left from the burning
of pulverised coal in power stations.
It is collected from the exhaust gases
before discharge to the atmosphere;
Not all ashes have a suitable
composition and particle size range for
use in concrete.
86

TYPE 2 ADDITIONS: pfa

Variability of fly ash due to changes in
the coal supply and power station
demands can be a significant
problem.
To ensure a more uniform, high-quality
material for use in concrete, some
processing of the ash is therefore
often carried out.
87

TYPE 2 ADDITIONS: pfa

This includes screening to remove
large particles, and the removal of
particles of unburnt carbon.
Unburnt carbon is very porous and
can reduce the consistence of the
fresh concrete.

88

TYPE 2 ADDITIONS: ggbs

The production of pig iron in the blast
furnace, is accompanied by the production of
slag.
The use of water to rapidly cooled cool the
slag, produces glassy phase silica.
When this slag is ground to a similar fineness
to Portland cement, It is called Ground
Granulated Blast furnace Slag (ggbs).
89

TYPE 2 ADDITIONS: csf

In the production of silicon metal,
extremely fine particles of silica are
condensed from the waste gases.
This material is known as Condensed
Silica Fume (csf)

90

TYPE 2 ADDITIONS: HRM

The heating of a clay or shale,
followed by rapid cooling and
grounding yields calcined clay.
High Reactivity Metakaolin (HRM) is
an example of calcined clay addition
used in concrete.

91

TYPE 2 ADDITIONS: others

After the rice grains have been separated
from the husk, the husk is burned under
controlled conditions to produce rice husk
ash.
Some volcanic ashes and diatomaceous
earth are examples of natural pozzolans.
Comparitive chemistry is shown on the next
slide.
92

TYPE 2 ADDITIONS
Typical composition ranges and properties of
additions

93

TYPE 2 ADDITIONS
From the table, it can be deduced:
The four (4) additions contain
substantially greater quantities of
silica than does Portland cement.
Microsilica is almost entirely active
silica.

94

TYPE 2 ADDITIONS
The alumina in the fly ash, ggbs and
metakaolin are also in an active
form, and becomes involved in the
pozzolanic reactions, forming
complex products.
The metakaolin comprises nearly all
active silica and alumina.
95

TYPE 2 ADDITIONS
High-lime fly ash and ggbs, also
contain significant quantities of CaO;
which also takes part in the hydration
reactions. Therefore neither material
is a true pozzolan, but both are to a
certain extent self-cementing.
Cement hydration seems to catalyse
C-S-H production.
96

TYPE 2 ADDITIONS
The maximum effective Portland cement
replacement levels of about:
o 90% for high-lime fly ash and ggbs,
o 40% for low-lime fly ash and metakaolin
and,
o 25% for csf.
o At higher levels than these, theres
insufficient PC to produce the required
quantities of CH for the secondary
reactions to be completed.
97

TYPE 2 ADDITIONS
Fly ash and ggbs have particle sizes
similar to those of PC,
Metakaolin particles are on average
nearly ten times smaller, and
Microsilica particles 100 times
smaller
98

TYPE 2 ADDITIONS
Due to surface area differences:
1. Microsilica reacts fastest, followed
by
2. Metakaolin, followed by
3. Fly ash and ggbs.
4. These are all secondary to PC
hydration.
5. Csf and metakaolin use results in
loss of fluidity in that order. Can be
counteracted by plasticiser or

99

TYPE 2 ADDITIONS
The spherical shape of the fly-ash
particles leads to an increase in
fluidity
Some increased fluidity is also
obtained with ggbs.

100

TYPE 2 ADDITIONS
All the listed additions have lower
relative densities than PC, and
therefore substitution of the cement
on a weight-for-weight basis will
result in a greater volume of paste.

101