CHAPTER 3

Air-Entraining Admixtures
for Concrete

1
 EFFECTS OF AIR ENTRAINMENT
Durability
• The main usage of air entrainment is to
enhance the durability of concrete against
cycles of climatic freezing and thawing and
against the effects of de-icing salts (Fig. 3.1).

2
Fig. 3.1 The effect of air-entraining admixtures on
durability

3
• When concrete freezes, there are two principal effects which
create internal stresses that can cause disruption:

1. A pressure build up resulting from a 9% increase in volume of the

water as it freezes in the capillaries, because ice is less dense than
water. For example, the pressure of ice in a confined system at -20 °C is
almost 200 N/mm2.

2. An osmotic pressure which develops as water diffuses from the gel

pores into the capillaries.
As pure ice crystals form and separate out from the water within the
capillaries, which has various salts dissolved in it, the solution
increases in concentration.
The flow of water from the gel pores takes place in order to
counteract this concentration effect, but in doing so there is a
resultant rise in hydraulic pressure.

4
• The action of de-icing chemicals has a more damaging
effect than frost alone.
– As ice melts when these chemicals are applied it takes up
the latent heat necessary for the change from the
underlying concrete.

• The cooling causes water in the pores at the surface to

freeze and also creates a more extreme thermal
gradient across the concrete section.

• The consequence is damage caused by a combination

of stresses due to ice expansion and differential
thermal movement.
5
 Mechanism of frost protection
• Millions of tiny air bubbles relieve the expansion pressures set up
in the capillaries as freezing proceeds.

• Being in the order of 1000 times larger than the capillary pores,
the entrained air voids block the pore structure within the cement
paste.

• The air bubbles do not fill with water owing to surface tension
effects, neither do they disappear as hydration products form
since hydration of the cement grains can only take place in water.

• As the concrete freezes and water in the capillaries expands, it

moves reversibly into the air voids preventing damaging pressure
build up (see Fig. 3.2).
6
Fig. 3.2 Diagram demonstrating the way air bubbles
relieve the water pressure as concrete freezes

7
• Critical considerations:
– volume of air entrained,
– the bubble spacing and size.

• The total volume of voids has a detrimental effect

on strength, and as close spacing is required it
follows that the smaller the bubbles the better.

• Entrained air voids are distributed over a range of

sizes, generally from 0.02 mm to 1 mm in diameter.

8
• There is a minimum volume of voids needed to give
adequate frost resistance in concrete and this has been
shown to be equivalent to 9% of the mortar volume.

• The volume of air required, in relation to the volume of

concrete, decreases with increasing maximum size of
the aggregate particles.

• The air bubbles are only contained in the cement paste

and the relative quantity of paste is less the larger the
stones used.

• This is illustrated by the recommendations laid down in

CP110 (see Table 3.1).

9
Table 3.1 CP 110 recommendations for average air content of
fresh concrete in relation to maximum aggregate size

Nominal maximum size of aggregate Air Content

mm %
40 4
20 5
14 6
10 7

10
• Figure 3.3 shows a typical relationship between the air content
of concrete and its resistance to freezing and thawing.

• It has been demonstrated both theoretically and by practical

experience that for substantially improved frost resistance the
average spacing between the air bubbles introduced should not
be more than 0.4 mm, and to maximise protection a distance of
less than 0.1 mm is warranted.

• Figure 3. 4 shows the relationship between the frost durability

of concrete and the air void spacing factor, a parameter which is
related to the maximum distance of any point in the cement
paste from the periphery of an air void.

• A spacing factor of less than 0.15 mm to 0.2 mm is generally

regarded as necessary for satisfactory resistance to freezing and
thawing.

11
Fig. 3.3 Influence of water/cement ratio and air entrainment
on resistance to cycles of freezing and thawing

12
Fig. 3. 4 Effect on durablity of bubble spacing of entrained air.

13
 Effect of air entrainment in general
durability of concrete
Reduction of bleeding and segregation
• Concrete which has segregated is obviously much less resistant to the
rigours of weathering and affords considerably less protection to steel
reinforcement than does dense, well compacted material.

• Results of bleeding can be almost as harmful, e.g. in producing

horizontal planes of weakness and increased permeability at lift
interfaces or at the top of slabs, and in reducing bond to the underside
of coarse aggregate particles and reinforcement bars where bleed water
may become trapped.

• Entrained air bubbles provide concrete with extra cohesiveness and

less tendency to bleed or segregate and with greater uniformity.

14
Effect on permeability
• It might be expected that because air-entrained concrete is more porous than
plain concrete its permeability would be increased. This, however, is not
necessarily the case for the levels of air entrainment usually required to give
satisfactory frost protection.

The reason for this is two-fold:

a) Air entrainment improves workability and consequently allows lower

water-cement ratios to be used, reducing the volume of capillary pores.

b) The air voids blocking the capillary structure act as 'impermeable open
pores' which only very slowly fill with water under normal conditions.
They therefore do not participate in the capillary transfer of liquid water through
concrete.

15
 F R E S H LY M I X E D C O N C R E T E
BLEEDING & SEGGREGATION
• A major benefit of air entrainment is a reduced tendency for
concrete to bleed, segregate, and suffer from plastic cracking.
This is due to:

1. Air bubbles attaching themselves to cement particles and linking

them.

2. An increase in interparticle attraction caused by the adsorption of

the air entrainer.

3. The air bubbles acting as extra fine filler and increasing the total
surface area of all constituents relative to the volume of water.

16
 WORKABILITY
• The presence of millions of microscopic air bubbles in
concrete incorporating an air-entraining admixture
increases the workability.

• The air bubbles act as minute compressible ball

bearings which assist the movement of the aggregate
particles relative to each other.

• Typically, for a concrete containing 5% air compared to

the same non-air-entrained mix, a 0.06 increase in the
compacting factor, and an increase in slump of between
20 mm and 50 mm.

17
 IMPROVEMENT of CONCRETE made with AGGREGATE
having POOR SHAPE & GRADING

• Entrained air acts as a fine aggregate with minimal surface

friction, making the concrete behave as an over-sanded mix.

• Therefore, an air-entraining admixture can compensate for the

lack of fine particles and poor shape of harsh sands and
aggregate.

• In a growing trend where poorly graded materials have to be

utilised, e.g. pumping concrete incorporating sea-dredged sand,
air entrainment shows benefit.

• For pumped concrete generally, the extra cohesiveness and

plasticity imported by entrained air is beneficial.
18
 OTHER EFFECTS
Strength
• The presence of air voids results in a loss in
strength proportional to the total volume of the
voids.

• A relationship has been established between the

compressive strength of a g.ven concrete and its
air content:

19
For each 1% of air included there will be a decrease in
strength of 5.5%.
For flexural strength the percentage reduction is somewhat less, generally
about half that for compressive strength.

It should be noted, however, that the loss in strength associated with air
entrainment is partially off-set by:
1. The water reduction that the entrained voids give, 8-12% typically,
depending on the cement content and the amount of air included.

2. The lower water requirement additional to 1) which can be achieved

if the sand content is reduced to capitalise on the extra cohesiveness
the air bubbles impart.
Sand may be reduced by up to 10% of its weight.

20
 Yield
• The presence of entrained air effectively provides within the
mix an extra quantity of 'weightless fine aggregate'.

• In practice the extra volume is not quite equal to the

theoretical difference in air content of the concrete modified
by the air-entraining admixture and that of a concrete with
only the voids due to entrapped air, since the consequent
water reduction has an opposing effect on the density.

• A 3% increase in yield would be typical for a concrete with

5% air entrainment.

21
 Finishes
• The ability of entrained air bubbles to reduce bleeding and segregation results
generally in better quality finishes.

• Problems with fair-faced concrete such as scouring, segregation, discolouration

and aggregate transparency can therefore be mitigated, as well as defects such as
plastic cracking, by use of air entrainment.

• The abrasion resistance of the wearing surfaces of floor slabs and pavements may
also be improved by the lower rate and capacity for bleeding which reduce the
risk of a weak laitance layer forming.

• Benefits in the production of extruded concrete products have been reported

when a combined water-reducing air entrainer was employed.

• In addition to providing units with a better surface finish, tear cracking is also
reduced, as is machinery wear and cleaning times.

22
 Shrinkage
• Air-entraining admixtures do not significantly alter
the drying shrinkage of concrete.

23
 Creep
• Researchers have shown that the creep of mixes
with the same workability and strength is
unaffected by the presence of air entrainment.

• At air contents greater than 6% there may be a

marginal increase in creep.

24
 CHEMISTRY OF AIR-ENTRAINING
ADMIXTURES
The most commonly used classes of materials used as air-entraining agents are:
1. Alkali salts of wood resins (sodium abietate)
Most widely used. The best known example is Vinsol resin.
Extracted from pinewood, neutralised as the sodium salt, or as by-products from
the production of tall oils.

2. Alkyl aryl sulphonates

These are also usually in the form of their sodium salt.
Typical of this group is sodium dodecyl benzene sulphonate.

3. Alkyl sulphates
These include materials such as sodium dodecyl sulphate, sodium cetyl sulphate,
and sodium oleyl sulphate.

25
4. Salts of fatty acids derived from animal and
vegetable fats and oils
The alkali metal or triethanolamine salts of fatty acids
such as oleic and caproic acid are used as air-
entraining agents for concrete.

This group are compatible with lignosulphonate and

hydroxycarboxylic acid water-reducing agents and are
therefore able to be used to produce combined
water-reducing/air-entraining agents.

26
 MECHANISM OF AIR BUBBLE FORMATION

• The common feature of the air-entraining chemicals are surface active agents, or
surfactants.

• This means that they function by interacting at the interfaces between the air,
water, cement and aggregate in the concrete mix.

• The basic structure of air-entraining surfactants is that of a long-chain molecule

with a hydrophilic (water-loving) head and a hydrophobic (water-hating) tail.

• This causes the surfactant molecules in an agitated solution to orientate at the air-
water interface with the polar head attracted towards the dipole charges on the
water molecules and with the organic, non-polar tail towards the air.

• This has the effect of reducing the surface tension of the water and thereby
stabilising bubbles that are formed when the solution is agitated.

27
There are two main reasons why air bubbles are more stable in
a surfactant solution:

1. The pressure, P, within a bubble is related to the surface tension, T, and its
diameter, D by P = 4T/D

– Hence the smaller the bubble the higher the pressure within it and the
greater the tendency to coalesce to form larger bubbles.
– Lowering the surface tension therefore reduces this tendency.

2. Because the air bubbles have a charged sheath of air-entrainer molecules

at their circumference there is a mutual repulsion between air bubbles
which again hinders coalescence and aids their uniform dispersion.
– In concrete the air-entraining agent stabilises bubbles as above but also acts
on the cement and aggregate surfaces with the reverse orientation to that at
the surface of the air bubbles so providing additional stability to the air void
system (see Fig. 3.9).

28
Fig. 3.9 Mechanism by which entrained air voids remain stable within concrete

29
 USE OF AIR-ENTRAINING
ADMIXTURES
Factors affecting air content:
• Numerous factors apart from admixture dosage
affect the air content achieved with a given
concrete mix (see Table 3.5).

• Table 3.5 provides broad outline guidance, but

there are other factors which also affect air
entrainment and it is useful to consider
individual effects in more detail.
30
Fig. 3.8 (a) Orientation of surfactant at air bubble surface (b) Anionic air-
entraining agent (most common)

31
• Cement content
The entrained air content decreases with increasing cement content,
particularly with low cement contents.

• Cement fineness
Figure 3.10 illustrates that the use of cement with a higher specific surface causes
a decrease in the volume of air entrained.

• Alkalis in cement
Increasing concentrations of alkali in cement increase the efficiency of air-
entraining agents in general, up to a level of about 1.5% (expressed as Na20).
The effect on the admixture could be such that an alteration in dosage of as much
as 30% is required. For this reason it is good practice to monitor the alkali level
of cement used.

• Impurities in cement
If large inexplicable changes in admixture dosage are required for a given air
content, then it is worth checking for impurities in the cement.

32
33
Fine aggregate
1. Sand content
• The quantity of air that is entrained in concretes
increases as the sand content of the mix
increases for concretes both with and without
air-entraining agents.
• A typical increase in sand from 35 to 45% increases the amount of
entrained air by about 1.5% (i.e. from 4.5 % to 6%).

2. Sand grading
• Reports dealing with the influence of fine
aggregate grading on the air content tend to be
conflicting and therefore somewhat inconclusive.

34
 Table 3.5 Factors influencing air content
Increasing air Decreasing air Example change Estimated effect
content content Target 5% air
content
Lower temperature Higher temperature 10-20 oC Reduction 1-1.25%
Higher slump Lower slump 50 to 100 mm Increase of 1%
Sand grading Sand grading BS882 Zone 3 to 2 Increase less than
coarser finer (1 zone width) 0.5%
Sand content Sand content 35 to 45% Increase 1-1.5%
increased decreased
Decrease in sand Increase in sand -50 kg/m3 Reduction of 0.5%
fraction passing 150 fraction passing 150
micron micron

Decrease in cement Increase in cement -50 kg/m3 Reduction of 0.5%

content inclusive of content inclusive of
sand content sand content
adjustment adjustment

35
 Table 3.5 Factors influencing air content
Increasing air Decreasing air Example change Estimated effect
content content Target 5% air
content
--- Inclusion of organic Inclusion Positive and
impurities negative effects
reported
--- Inclusion of PFA Inclusion Significant
reduction linked to
carbon in ash
--- Increase in water Increased hardness Reduction
hardness
Increase in mixing Decrease in mixing Better mixing Increased linked so
efficiency efficiency efficiency dispersion of
admixture
Positive dispensing Negative dispensing +/- 5% +/- 0.25%
tolerance tolerance
--- Prolonged agitation 1 hour Reduction of 0-0.25%
2 hours Reduction of 1%
36
Temperature
• Air entrapment varies inversely with temperature
for a number of reasons,
These are:
1. viscosity effects,
2. cement activity,

Higher temperatures thus cause a reduction in the

amount of air entrained in a concrete for a given
admixture dosage.

This is illustrated in Fig. 3.11.

37
38
Workability
• The quantity of air generated by a given dose of air
entrainer increases with workability.

• For low workability concrete, e.g. pavement quality,

admixture dosage levels appropriate to medium
workability mixes have to be increased by as much as
100% to achieve the same air content.

• Dosage levels at very high workability (above 200 mm

slump) also have to be increased to ensure a stable air
content during mixing, transportation and compaction.

39
 Pulverised-fuel ash (pfa)
• Characteristics of pfa affect the efficiency of air-entraining admixtures are its
residual carbon content, as measured by loss-on-ignition (LOI), the nature of
the carbon and to a lesser extent the fineness of the ash.

• The greater the carbon content the higher the admixture dosage required.

• It is beneficial to ensure that as far as possible the same source of ash supply is
maintained.

• For total cement contents containing 25-35% pfa, initial trials should be carried
out at 1, 2 and 3 times 'normal' admixture dosage.

• As a rule of thumb dosage can be based on a total cement content per m3

equal to the Portland cement content plus 1.5 times the ash content.

•
40
Ground granulated blast furnace slag

• There is no significant differences between the

performances of A.E.A.'s with plain Portland
cement concretes and those containing a
proportion of ground granulated blast furnace
slag.

41
Mixing, transportation, placing and
compaction
• The type of mixing action and the general efficiency of a mixer will affect both the
volume of air entrained and the time taken to produce this volume of air.

• The air content will increase with increased time of mixing up to about 2 minutes
in stationary mixers and to about 15 minutes in most transit mixers, after which
the air content may remain approximately constant for a considerable period
before any reduction occurs.

• Some slight loss of air inevitably occurs during transportation, placing and
compaction, the larger bubbles which are the least effective tending to be the first
to be expelled.

• Loss of air content during handling is illustrated in Fig. 3.12.

• With typical concretes of low workability a loss in air content of perhaps 0.5%
should be anticipated between the mixer and the compacted state, and a loss of
up to 1 % with higher workability concrete.
42
43
Use with other admixtures
• In general the advice of the admixture
supplier should be sought if more than one
admixture is to be used in a concrete mix.

• This is essential if it is intended to premix the

admixtures rather than add them separately.

44
45
Mix design for air-entrained concrete
• Guidance on the design of air-entrained concrete
mixes is given in Reference 29 (BRE method).
• The main principles are outlined below.

The mix design parameters that require

modification by inclusion of air are:
1. Strength
2. Workability
3. Density
4. Sand content

46
 Strength
• A loss of 5.5% in compressive strength and 4% in indirect tensile strength is
assumed for each additional 1% by volume of air entrained in the mix.

• Hence the target mean strength has to be adjusted compared to plain

concrete.

Target Mean Strength (air-entrained concrete) = fc + M/(1 – ra)

fc = the specified characteristic strength

M = the margin (the extra strength allowance required for the inherent variability
in concrete production)
a = the percentage by volume of air entrained
r = 0.055 when designing for a given compressive strength.

47
Workability
• Allowance has to be made for its effect on the
water requirement of the mix.

• For the purpose of determining the water content

of a designed mix with or without entrained air,
the workability range is divided into four levels
corresponding to
very low
low
medium
High

48
Density
• The air bubbles produce a lowering of the concrete
density and consequently an increase yield.

• The density and aggregate content of an air-entrained

mix are adjusted by subtracting from the estimated
mass per cubic metre of the same mix without an a
quantity of aggregate equivalent to the required
volume of entrained air.
• The weight of aggregate to be subtracted is given by
the formula:
Weight of aggregate = 10 (a)(D)
a = the required volume of entrained air (%)
D = specific gravity of the aggregate

49
Sand content
• Air-entrained concrete is more cohesive than
that which is not, because the air bubbles
themselves behave as very small aggregate
particles.

• This allows the sand proportion to be reduced

by up to 5% on total aggregate content
(approximately 20 kg/m3 for each 1% of extra
air).

50
 Applications of air-entraining agents
1. Air entrainment of structural concrete to provide
resistance to frost
attack and the effects of de-icing salts.

2. To act as a fines supplement in poorly graded concretes

producing a more cohesive, thixotropic mix to aid
compaction and improve surface finish.

3. At low levels of air entrainment, to act as a pumping aid.

4. To improve the strength and facilitate the de-moulding of

concrete blocks and to reduce equipment wear.

51
 Dispensing air-entraining agents

• It is essential that accurate equipment is used for

dispensing admixtures and particularly so for air-
entraining agents where the dosages are
generally very low for example 20 ml/50 kg
cement.

• Semi-automatic dispensing units are usually

designed such that the dosage is measured by
electrical contact between the admixture and a
pre-set probe in a sight glass.
52
 PERFORMANCE TESTS FOR
AIR-ENTRAINING ADMIXTURES
• Many countries now have Standard specifications for air-
entraining admixtures.
BS 5075:Part2 covers performance requirements for:
1. Repeatability of air content,
2. Stiffening time,
3. Saturated density,
4. Compressive strength,
5. Resistance to freezing and thawing.

• ASTM Standard ASTM C260 covers uniformity tests on pH, specific

gravity, air content in mortars made with the air entrainer and
performance requirements of concrete made with it relative to that
containing a reference (neutralised Vinsol resin) admixture

53
 Test methods
Freshly mixed concrete
• There are three basic ways of testing concrete for the volume of air voids it contains:
a) pressure method
b) volumetric method
c) gravimetric method

Pressure method. BS 1881:Part 106:1983 and ASTM Standard C231 both describe two procedures for
determination of air content by pressure methods based on Boyle's Law.

Method A operates by introducing water to a predetermined height above a known volume of concrete in the
apparatus (see Fig. 3.14) and measuring the amount the water level drops as the air in the concrete is
compressed when the working pressure of the apparatus is applied.

The decrease in water level is calibrated in terms of the percentage of air in the concrete sample.

Method B is based on the principle of equalising a known volume of air, at a set pressure in a sealed container, with
the unknown volume of air within the concrete sample. The pressure gauge dial is calibrated to read the
percentage of air, and hence the resulting pressure reading indicates the air content in the concrete.

54
55
Volumetric method. A volumetric method is laid down in ASTM C173. The method comprises
measuring the drop in level of water, which is placed in a sealed container above a known volume
of the concrete, after a sequence of agitating and rolling to remove the air from the concrete. The
neck of the apparatus is calibrated to read the drop in level of water as a percentage of the volume
of concrete.

Gravimetric method. ASTM C138 describes a gravimetric method for measuring air content of
concrete.
The measured compacted density, W, of the concrete in question is compared to the theoretical air-free
density,' T, calculated from the weights and specific gravities of the mix ingredients. The air content
A, is expressed as a percentage of the concrete volume by

A = 100 x (T-W)/T
• T: air free density (theoretical)
• Errors in the air content of up to 1% by volume of concrete are reported for this method.

Test for bleeding

• ASTM C232 describes a method of test for bleeding of concrete which is relevant
to the performance of air-entrained mixes.
– Bleeding water is withdrawn by pipette from the surface of a defined volume of concrete and
expressed either as a volume per unit area of surface or as a percentage of the net mixing water in
the test sample. Two methods are described, relating to compaction by tamping or by vibration with
further periods of vibration at intervals.

56
Characterisation of the air-void system
• There are no generally accepted methods of testing concrete in the
fresh state for the nature of the air voids.

• A test which gives a measure of the air void size distribution in

concrete by relation to the air loss due to vibration has been
devised.

• The main advantage of such a test is that it is simple, rapid,

inexpensive to perform and is carried out on fresh concrete in
comparison to linear traverse and freeze/thaw procedures.

• The method is based on the fact that vibration causes a reduction in

the average void diameter and that the volume of air lost after a
given period of vibration depends on the original void
characteristics (see Fig. 3.16).

57
58
 Hardened concrete
1. Freeze/thaw cycling
• There are several procedures documented for testing the frost
resistance of air-entrained concrete in the laboratory.

BS 5075: Part 2:1982 specifies a method by which concrete

prisms are subjected to 50 freezing and thawing cycles in
water. The effects
are monitored by observing
the change in length of the specimens

59
2. Microscopical analysis
• Procedures for the microscopical determination in hardened
concrete of air void content, their specific surface and spacing
factor, and the air-paste ratio are described in ASTM C457.

• Two methods are prescribed –

– the linear traverse technique and
– the modified point count method.
The measurements are made on finely ground sections of samples cut
from the concrete in question.

60