CONSTRUCTION

MATERIALS 2
CONS2012
DR. D. WHITE

Concrete Technology
The subject of concrete technology
involves:
The constituants,
The composition
The production,
The structure and
properties of concrete itself.
2

Terms and Definitions

Concrete can be defined simply as:
It is a mixture of cement, water and
aggregates (fine and coarse) in which
the cement and water combine to
bind the aggregate particles together
to form a monolithic whole.

Terms and Definitions

Addition :
Other materials such as fine powders
that can substitute for some of the
cement
Admixtures:
Chemicals that are added in small
quantities, that can alter and improve
some concrete properties.
4

Terms and Definitions

Binder:
A mixture of cement and additions
that participate in the hydration
reactions.

Terms and Definitions

Grout or cement paste:
Is a mixture of cement and water
only.
Rarely used for structural purposes
due to its much higher dimensional
changes than concrete under loading
or in different environments.
Much more expensive than concrete.
6

Terms and Definitions

Mortar:
Is a mixture of cement, water and
fine aggregate (sand), is more
commonly used for small volume
applications, for example in
brickwork.

Terms and Definitions

Aggregates:
Typically occupy 7080%of the concrete
volume.
Fine aggregate or sand has a diameter
less than 4mm.
Coarse aggregate (gravel or crushed
rocks) have diameters greater than
4mm.
Commonly 10, 20, and 40 mm.
8

Terms and Definitions

mix proportions:
The amounts of each of the constituents that are
mixed together to form a unit quantity of
concrete. These are most commonly expressed as
the weight of each material in a unit volume of
concrete.
Example:
o cement or binder: 350 kg/m3
o water: 200 kg/m3
o coarse aggregate: 1100 kg/m3
o fine aggregate: 750 kg/m3
9

Terms and Definitions

Water/cement ratio or the water/binder
ratio:
The ratio of the weight of water to
that of cement or binder.
Is an important factor influencing
many of the concretes properties.
Values are typically in the range 0.3
to 1.0.
10

Complexities of Concrete
Technology
1. The series of complex chemical reactions
of hydration between Portland cement
(PC) and water produce a hardened
cement of equally complex composition
and microstructure. Additionally, PC is
not a single uniform material but, has a
range of compositions and hence
properties when obtained from different
sources or even from the same source
over a period of time.
11

Complexities of Concrete
Technology
2. The use of admixtures and additions
increases the complexity.
3. The aggregates are normally obtained
from local sources and, though carefully
selected for size, strength etc., a range of
types, are used, [including both natural
and artificial (mainly lightweight) ], each
of which will affect the concretes
properties to some extent.
12

Complexities of Concrete
Technology
4. The properties in the newly mixed, fresh
(or fluid) state must be such that the
concrete can be transported from the
mixer, handled, placed in the moulds or
formwork and compacted satisfactorily.
This requirement can be demanding, for
example with in-situ concrete being
placed in extreme weather conditions in
parts of a structure with difficult access.

13

Complexities of Concrete
Technology
This is one of the great advantages
of concrete its ability to be placed
in complex shapes and forms.
In this respect concrete is different
to most other structural materials,
which are supplied in a ready-to-use
state, with the exception of factoryproduced pre-cast elements.
14

Complexities of Concrete
Technology
5. Even when hardened, the structure and
properties of concrete continue to change over
time. For example, about 5060% of the
ultimate strength can be developed in 7 days,
8085% in 28 days, and small but measurable
increases in strength have been found in 30year-old concrete.
6. Long term movements due to both load (i.e.
creep), and changes in moisture (i.e. swelling
and shrinkage) can be significant.
15

Complexities of Concrete
Technology
7. The concrete and any steel
contained within in it can
deteriorate for a variety of reasons,
and so ensuring adequate durability
as well as mechanical properties is a
major consideration.

16

INTRODUCTION

PORTLAND CEMENT (PC)

17

INTRODUCTION
Patented in 1874 by Joseph Aspdin.
Produced from a calcined (burnt)
mixture of clay and calcined
limestone.
So named by its inventor because he
found the hardened product
resembled Portland stone.
18

INTRODUCTION
Hydrated PC binds the aggregate in
hardened concrete
PC accounts for more than 95% of
the global cement use.

19

MANUFACTURE
Either by Dry method or Wet method
(TCL).
In the dry method, calcium carbonate
rich raw material (chalk or limestone)
and a silicon dioxide rich raw
material (clay or shale) are carefully
blended, typically in an 80/20
proportion.
20

MANUFACTURE
The mixture is interground to less
than 90 m in either a ball mill or
roller mill.
Grounded sand and iron oxide may
be added.
The mixture may be heated to 1400
-1500 C in one or two stages.
21

MANUFACTURE
For the two stage process, the meal
is introduced from the top of a preheater tower, which may include a
pre-calcining vessel.
The meal is flash heated to 900C for
as few seconds as it falls.
90% of the CO2 is removed here.
22

MANUFACTURE

The main processes in the heating of raw

meal to produce Portland cement clinker.

23

MANUFACTURE
The hot mixture is then passed into
the heated rotary kiln, that is inclined
at about 3 to the horizontal.
The combustion of fossil fuels
produce the heat the enables the
bottom end of the kiln to reach
1500C.
24

MANUFACTURE
After about 20 30 minutes, the
meal has moved down through the
kiln and out as granules of clinker.
De-carbonization is completed at
1100C.
The burning zone is between 1200
and 1500C.
25

MANUFACTURE
The oxides start to combine in the
burning zone, to form a mixture
consisting mainly of:
o calcium silicates,
o calcium aluminates and
o calcium aluminoferrites.

26

MANUFACTURE
Compound formation at 1400
1500C is enhanced by the presence
of small quantities of alumina and
iron oxide that are present (typically
5% and 3% respectively).
These act as a molten flux.

27

MANUFACTURE
The ejected clinker cooled from
1200C to about 60C.
35% of gypsum (calcium sulphate
dihydrate, CaSO4.2H2O) is added
before milling.
Small quantities of limestone powder
maybe added as a filler.
28

MANUFACTURE
The grinding of the clinker/gypsum
mixture in the ball mill results in an
increase in temperature.
The increased temperature causes
some dehydration of the gypsum.
The outside of the grinding mill is
cooled by spraying water onto it.
29

MANUFACTURE
In the wet method, water is added to
the crushed clay-limestone mixture to
form a slurry.
This is then introduced into the kiln and
dried at 200C.
It is then fired in the same kiln at
1300C (TCL).
30

MANUFACTURE
The rest of the process is the same as
for the dry method.
TCL uses limestone alone as it contains
both calcareous and siliceous materials.
The action of the molten flux results in a
slightly lower firing temperature than
mentioned.
31

PHYSICAL PROPERTIES
Relative density or specific gravity:3.15
Particle Size Distribution:- particles
too small for sieve analysis.
Specific Surface Area (SSA) used
instead.
32

PHYSICAL PROPERTIES
The Blaine method, is most commonly used
for SSA.
Based on measuring the rate of flow of air
under a constant pressure through a small
compacted sample of the cement.
Blaine values of SSA range between 300 and
500 m2/kg for most cements in common use.
33

CHEMICAL COMPOSITION
The shorthand notation for the
principal oxides present are as
follows:
CaO (lime) = C;
SiO2 (silica) = S;
Al2O3 (alumina) = A;
Fe2O3 (iron oxide) = F.
34

CHEMICAL COMPOSITION
The four main compounds/phases in cement are:
Tricalcium silicate: 3CaO.SiO2
in short C3S
Dicalcium silicate: 2CaO.SiO2
in short C2S
Tricalcium aluminate: 3CaO.Al2O3
in short C3A
Tetracalcium aluminoferrite 4CaO.Al2O3.Fe2O3
in short C4AF
35

CHEMICAL COMPOSITION
Strictly speaking, C4AF is not a true
compound.
It represents the average
composition of a solid solution.

36

CHEMICAL COMPOSITION
C2S or belite begins to form from about
700C.
C3S or alite starts to form at about
1300C.
Most of the belite formed at lower
temperatures is transformed into alite as
the temperature approaches maximum.
37

CHEMICAL COMPOSITION
C3A and C4AF both start to form at about
900C.
It is difficult to determine the amounts
of each by direct analysis.
The compound composition is calculated
from the oxide proportions these using
equations developed by Bogue (1955).
38

CHEMICAL COMPOSITION
It is assumed that:
1. All the Fe2O3 is combined as C4AF.
2. The remaining Al2O3, not combined
in the C4AF, is combined as C3A.

39

CHEMICAL COMPOSITION
The equations in shorthand form are:
(C3S) = 4.07(C) - 7.60(S) - 6.72(A)
- 1.43(F) - 2.85() (eqn.1)
(C2S) = 2.87(S) - 0.754(C3S)

(eqn.2)

(C3A) = 2.65(A) - 1.69(F)

(eqn.3)

(C4AF) = 3.04(F)

(eqn.4)
40

CHEMICAL COMPOSITION
Where: = SO3, (C3S), (C2S) etc. are the
percentages by weight of the various
compounds.
(C), (S) etc. are the percentages by
weight of the oxides from the oxide
analysis.
The value of (C) should be the total from
the oxide analysis minus the free lime.
41

CHEMICAL COMPOSITION
The Bogue equations do not give
exact values of the compound
composition.
This is because alite and belite are
slightly impure forms of C3S and C2S
respectively, containing some of the
minor oxides in solid solution.
42

CHEMICAL COMPOSITION
This is why the calculated composition
is often called the potential compound
composition.
It is however, accurate enough for the
consideration of the variations in the
composition for different types of
Portland cement, and their effect on
its behaviour.
43

CHEMICAL COMPOSITION
The CaO : SiO2 ratio PC is
approximately 3 : 1.
The Table on the following slide,
compares the composition of 4
commercially available PCs: A, B, C,
and D.

44

CHEMICAL COMPOSITION

45

CHEMICAL COMPOSITION
Oxide proportions do not vary much
between them.
Compound proportions vary
significantly.
C3S and C2S, together account for
7176% of the cements.
46

CHEMICAL COMPOSITION
A: Typical PC (C3S: 45 - 65%, C2S: 10
30%).
B: High early strength.
C:Low heat.
D:Sulphate resistant.
47

CHEMICAL COMPOSITION
Similar chemistry, different
mineralogy yields great variations in
properties.
Great care must be taken to control
both input and processing to ensure
consistent output, i.e. product.

48

HYDRATION
The addition of water to PC sets a
series of chemical reactions in
motion.
These reactions are exothermic (heat
evolving).
They result in the reduction of grain
size.
49

HYDRATION

Typical rate of reaction of hydrating cement paste

at constant temperature (after Forester, 1970). 50

HYDRATION
Peak A is short and sharp.
Mainly due to the rehydration of
calcium sulphate hemihydrate: a
product of the decomposition of the
gypsum in the grinding process.

51

HYDRATION
Gypsum is re-hydrated as follows:
2C(0.5H) + 3H 2C.2H
[H = H2O in shorthand form]

52

HYDRATION
Additional contributions to peak (A)
come from:
o The hydration of the free lime,
o The heat of wetting,
o Heat of solution, and
o The initial reactions of the
aluminate phases, C3A.
53

HYDRATION
C3A is the most reactive phase in PC.
Responsible for early strength.
Gypsum is used to temper is
reactivity.

54

HYDRATION
The initial reaction of the gypsum and C 3A is:
C3A + 3C.2H + 26H C3A.3C.32H
The product, calcium sulphoaluminate, is
also known as ettringite.
Ettringite insoluble and forms a protective
layer on the C3A phase, preventing the rapid
reaction.
55

HYDRATION
When all the gypsum is consumed,
ettringite reacts with the remaining
C3A as follows:
C3A.3C.32H + 2C3A + 4H
3(C3A.C.12H)
The reaction product, calcium
monosulphoaluminate, has a lower
sulphate content than ettringite.

56

HYDRATION
The C4AF phase reaction with gypsum is
similar to that of the C3A, but it is
somewhat slower.
The products have an imprecise and
variable composition, but include highand low sulphate forms approximating to:
o C3(A.F).3C.32H and
o C3(A.F).C.16H, respectively
57

HYDRATION
The hydration products of the calcium
silicates give hardened cement most of its
significant engineering properties such as:
o Strength and
o Stiffness
Therefore their reactions and reaction rates
dominate the properties of the hardened
cement paste (HCP) and concrete.
58

HYDRATION
Alite reacts faster than belite.
The calcium silicate hydrate (C-S-H) of
alite has a Ca:Si ratio of between 1.5 and
2.
A somewhat simplified form of the
reaction is:
2C3S + 6H C3S2.3H + 3CH
59

HYDRATION
CH is Calcium Hydroxide (Ca(OH)2).
The CH is deposited in a crystalline
form.
It is often referred to by its mineral
name, portlandite.
60

HYDRATION
The hydration reaction of alite is
responaible for the majority of the
heat evolved in the main peak B.
C-S-H is responsible for the strength
of the HCP.

61

HYDRATION

Typical rate of reaction of hydrating cement paste

at constant temperature (after Forester, 1970). 62

HYDRATION
Belite reacts much more slowly than
alite, but produces identical products.
The reaction in its simplified form is
written as:
2C2S + 4H C3S2.3H + CH
This reaction contributes little heat in the
timescales.
63

HYDRATION
Belite makes an important
contribution to the long-term
strength of HCP.
Low heat cements have a higher
proportion of belite than alite.

64

HYDRATION

Typical rate of reaction of hydrating cement paste

at constant temperature (after Forester, 1970). 65

HYDRATION
Peak C is not always present.
It is the result of the direct hydration
of C3A to its hydrate, C3A.6H.
This occurs when all the gypsum and
ettringite are consumed leaving
unreacted C3A.
66

HYDRATION

Typical development of hydration products of

Portland cement (after Soroka, 1979).

67

HYDRATION
From the graph, it is apparent that:
C-S-H is dominant after a day or so.
The increase in C-S-H is accompanied
by an increase in CH.

68

HYDRATION
It must be noted, that the presence
of CH and the minor oxides, results in
the HCP being highly alkaline, with a
pH between of 12.5 and 13.
Alkalinity has a significant influence
on some aspects of the durability of
concrete construction.
69

HYDRATION

Development of strength of compounds in Portland

cement on hydration (after Bogue, 1955).
70

HYDRATION
From the graph, it can be seen that:
C3S dominates the early strength
gains.
The strength-giving reactions of the
calcium silicates, particularly C2S are
of a long-term nature.

71

HYDRATION
The hydration processes are never
complete.
The extent of the completeness of
the hydration reactions is termed the
degree of hydration.

72

HYDRATION

Illustration of the hydration of a single grain of

Portland cement.

73

HYDRATION
Consider a single cement grain in a
large volume of water as in the
previous slide.
The important features are listed on
the following slides:

74

HYDRATION
The processes take place at the solidliquid
interface, with solid products being
deposited in the region around the
diminishing core of unhydrated cement in
each cement grain.

The very early products form a surface layer

on the cement grain, which acts a barrier to
further reactions during the dormant period.
75

HYDRATION
The dormant period ends when this
layer is broken down by either a
build-up of internal pressure by
osmosis, or by portlandite (Ca(OH)2),
or both, enabling hydration to
proceed more rapidly.

76

HYDRATION
The hydration products (known as the gel) consist
of:
o needle-like crystals of ettringite, deposited early
in the hydration
o an amorphous mass, mainly C-S-H, of small,
irregular fibrous particles, some solid, some
hollow and some flattened, typically 0.52 m
long and less than 0.2 m diameter, with very
high surface area estimated to be of the order of
200,000 m2/kg, i.e. approaching a thousand times
greater than the fresh cement grains from which
it has been formed
77

HYDRATION
o large hexagonal crystals of
portlandite interspersed in the
fibrous matrix.

78

HYDRATION
The gel contains:
o many small gel pores, typically
between 0.5 and 5 nm wide, in
between the fibrous particles,
o as hydration continues, new
product is deposited within the
existing matrix, decreasing the gel
porosity.
79

HYDRATION
There are differences in density and
structure between the hydrates
deposited within the original surface
of the cement grain, known as inner
product, and the less dense hydrates
deposited in the original water-filled
space, which contain morecrystals of
portlandite and aluminoferrite and
are known as outer product.
80

HYDRATION
The rate of hydration reduces over a long
period after peak B owing to the increased
difficulty of diffusion of water through the
hydration products to the unhydrated cement.
o It has been estimated that, for this reason,
complete hydration is not possible for
cement grains of more than 50 m in
diameter.
o Even after many years there is a residual
core of unhydrated cement.
81

HYDRATION
At complete hydration:
o the gel porosity reaches a lower limit
of about 28%
o the volume of the products of
hydration is little more than twice that
of the unhydrated cement, but about
two-thirds of the combined initial
volume of the unhydrated cement and
the water which it consumes.
82

HYDRATION
Hydration occurs at (nearly) constant overall
volume, i.e. the mixture does not swell or
contract
The HCP or concrete is approximately the same
size and shape when hardened as the mould in
which it was placed after mixing.
Using this fact, and the measured properties of
the fresh and hydrated materials it can be shown
that:
83

HYDRATION
At a water:cement ratio of about 0.43,
there is just sufficient mix water to
hydrate all the cement and fill all of
the resulting gel pores.
Therefore at water:cement ratios
lower than this, full hydration can
never occur unless there is an
available external source of water,.
84

HYDRATION
In practice, in a sealed specimen the
hydration will cease somewhat before all of
the available water is consumed, and an
initial water:cement ratio of about 0.5 is
required for full hydration.
At a water:cement ratio of about 0.38, the
volume of hydration products, i.e. the gel,
exactly matches that of the fresh cement
and water.
85

HYDRATION
At values lower than this, hydration
will be stopped before completion,
even if an external source of water is
available.
This is called the condition of
insufficient volume.

86

HYDRATION
At water:cement ratios higher than this
there is an increasing amount of
unfilled space between the original
grains in the form of capillary pores,
between about 5 nm and 10 m wide.
On average, the capillary pores are
about a hundred times larger than the
gel pores within the gel itself.
87

HYDRATION
Calculations give the relative
volumes of unhydrated cement, gel
and capillary pores at complete
hydration shown in the next slide.

88

HYDRATION

Volumetric composition of fully hydrated cement

paste after storage in water (after Hansen, 1970).

89

HYDRATION

Illustration of the structure of cement pastes of

high and low water:cement ratios.

90

HYDRATION
Cement pastes with high
water:cement ratios, say of about 0.8,
have grains that are initially fairly
widely dispersed in the mix water.
When mature, say after several
months there is still a significant
capillary pore volume.
91

HYDRATION
On the other hand, in cement pastes
with low water:cement ratio, say of
the order of 0.4, the grains are
initially more closely packed.
The hydrates occupy a greater
volume of the mature paste.

92

HYDRATION

Pore size distribution in 28-day-old hydrated

cement paste (adapted from Mehta, 1986).

93

STRUCTURE & STRENGTH

OF HCP
Thus far, we have seen that, at any stage of
hydration, the HCP consists of:
A residue of unhydrated cement, at the
centre of the original grains,
The hydrates (the gel), chiefly C-S-H but also
some calcium aluminates, sulphoaluminates
and ferrites, which have a complex fibrous
form and contains the gel pores, which are
between 0.5 and 5 nm wide
94

STRUCTURE & STRENGTH

OF HCP
Crystals of portlandite (CH)
The unfilled residues of the spaces
between the cement grains the
capillary pores, between about 5 nm
and 10 m wide.

Additionally, air voids due to trapped air

are also present.
95

STRUCTURE & STRENGTH

OF HCP
The significant strength of HCP
derives from van der Waals type
bonds between the hydrate fibres.
Although each individual bond is
relatively weak, the cummulative
effect over the enormous surface
area is considerable.
96

STRUCTURE & STRENGTH

OF HCP
Unhydrated cement material is not
detrimental to overall strength.
It can be beneficial, as it can hydrate if
exposed to water, and produce new C-S-H to
seal a crack that may have formed, and
restore some structural integrity.
No other common structural materials have
this self-healing property.
97

STRUCTURE & STRENGTH

OF HCP
the compressive strength of HCP
specimens stored at constant
temperature and humidity increases
with age and decreasing
water:cement ratio.
See next slide

98

STRUCTURE & STRENGTH

OF HCP

Compressive strength development of Portland cement

paste stored in water at 20C (after Domone and
99

STRUCTURE & STRENGTH

OF HCP
The change with age reflects the
progress in hydration reactions, i.e.
the degree of hydration.
At 28 days (a typical testing age
when comparing cements) the
reactions are about 90% complete
for a typical PC.
100

STRUCTURE & STRENGTH

OF HCP
The size and volume of the capillary
pores reduce with age and increases
with water:cement ratio
In simple terms: less porosity (due to
either increasing age or lower
water:cement ratio or both), means
higher strength.
101

STRUCTURE & STRENGTH

OF HCP
The relationship between the two
was shown by Powers (1958) to be of
the form:
= k(1 P)3
where:
k is a constant,
= compressive strength and
P = porosity = pore volume/total
paste volume.
102

STRUCTURE & STRENGTH

OF HCP

The dependence of the strength of hardened

cement paste on porosity (after Roy and Gouda,

103

STRUCTURE & STRENGTH

OF HCP
According to Roy and Gouda:
= A log(P/Pcrit)
where:
A is a constant and
Pcrit is a critical porosity giving zero
strength, shown to be about 55%.
This result is consistent with Powers.
104