The importance of the

waterecement and 1
waterebinder ratios
P.-C. Aïtcin
Université de Sherbrooke, QC, Canada

1.1 Introduction
It may be surprising to start a book on the science and technology of concrete admix-
tures by a chapter devoted to the importance of the waterecement (w/c) and the
waterebinder (w/b) ratios, before even explaining what Portland cement is and how
it reacts with water. We agree with Kosmatka (1991) that the w/c and w/b ratios are
the most important characteristics of concrete; they govern its properties in the fresh
and hardened states and also its durability. It is therefore fundamental to understand
their profound significance in order to optimize the use of concrete with the help of
admixtures and thus to maximize its economic value while minimizing at the same
time its carbon footprint.
Despite what many cement chemists think, the most important parameters that con-
trol concrete compressive strength are not:
• the cement dosage expressed in kg/m3
• the strength of the small cubes used to test the “cement compressive strength”
• the C3S and C3A content of the clinker
• the fineness of the cement, or
• the “gypsum” content.
In fact, the most important parameters have always been the w/c and w/b ratios, as
was found in the nineteenth century by Féret (1892) for cement pastes and later on by
Abrams, 1918 for concrete. As will be shown later, these ratios control the microstruc-
ture of the cement paste in both the fresh and hardened states, and consequently its
rheology, mechanical properties, permeability, durability, and sustainability.
When batching concrete, each of its solid components is weighed; thus, it is com-
mon to express the w/c ratio as a mass ratio instead of a volumetric ratio. In this book,
the symbols w/c and w/b will be used for the mass ratio, whereas W/C and W/B will
be used for the volumetric ratios, according to American Concrete Institute (ACI)
terminology. Note that the RILEM (Rassemblement International des Laboratoires
d’Essais sur les Matériaux) terminology is the opposite.
It is always possible to transform the mass ratio into a volumetric one by taking into
account the specific gravity of the cement. In this book, the theoretical specific gravity
of Portland cement is taken as 3.14, which is an easy number to remember and a

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Copyright © 2016 Elsevier Ltd. All rights reserved.
4 Science and Technology of Concrete Admixtures

number very close to that of an actual “pure” Portland cement. The specific gravity of a
blended cement containing a filler or supplementary cementitious materials with spe-
cific gravities different from 3.14 will be usually less than 3.14. In this chapter, it will
be shown that w/c and w/b ratios are more than simple abstract numbers with an
inverse relationship to concrete compressive—they do have a physical meaning.

1.2 The hidden meaning of the w/c

Using a sophisticated three-dimensional model, Bentz and Aïtcin (2008) demonstrated
that the w/c ratio is a number directly related to the average distance between cement
particles within a cement paste after it is mixed with water just before it begins to hy-
drate. This distance between the cement and/or binder particles influences the hydra-
tion conditions and the microstructure of the hardened cement paste and, consequently,
its mechanical properties and durability.
To illustrate this fundamental concept, we will instead use a very simple two-
dimensional (2D) model to provide a qualitative explanation of the meaning of the
w/c. Consider four circular cement particles having a radius a that are placed at the
corners of a square with a side equal to 3a, as represented in Figure 1.1. The minimum
distance between these cement particles is their distance along the sides of the square:
it is equal to a.
This arrangement of the cement particles can be represented by the unit cell shown
in Figure 1.2.
Now calculate the W/C of this unit cell. The surface area of the unit cell is
3a
3a ¼ 9a2. The surface of the cement particles is 4
1/4 (3.14
a2) ¼ 3.14a2.
The mass of the cement particles in this unit cell is equal to 3.14 (3.14
a2)
because our theoretical cement has a specific gravity of 3.14. Because the value of
3.142 is close to 10 (9.86 exactly), we can assume that the mass of cement in the

2a

3a

Figure 1.1 Schematic representation of the 2D model used to calculate the w/c and the distance
between cement particles.
Courtesy of William Wilson.
The importance of the waterecement and waterebinder ratios 5

Water

Cement

Figure 1.2 Unit cell corresponding to the previous arrangement of cement particles.
Courtesy of William Wilson.

unit cell is equal to 10a2. The volume (and mass) of water contained in the unit cell is
equal to 9a2  3.14a2 ¼ 5.86a2. Therefore, the w/c (mass ratio) of this unit cell is
w/c ¼ 5.86a2/10a2 ¼ 0.586, which can be rounded up to 0.60. This is the w/c of an
ordinary concrete that has a compressive strength in the order of 25 MPa.
Now, as shown in Figure 1.3, let us place another cement particle having a radius a
at the center of the unit cell, which diagonal is 4.24 long. In this case, the minimum
distance between two cement particles along the diagonal is 1/2(4.24a e 4a) ¼ 0.12a.
A calculation similar to the previous case shows that the w/c of this new unit cell
is now 0.14. This w/c is somewhat lower than that of an ultra high in strength concrete
having a compressive strength of over 200 MPa (Richard and Cheyrezy, 1994).

Figure 1.3 2D model of a more compact system.

Courtesy of William Wilson.
6 Science and Technology of Concrete Admixtures

Figure 1.4 Hydration of cement particles in the previous system.

Courtesy of William Wilson.

Thus, by replacing the water in the center of the first unit cell by a cement particle,
it is possible to decrease the following:
• The minimum distance between two cement particles to 0.12a instead of a (about an order of
magnitude shorter)
• The w/c of the unit cell to 0.14 instead of 0.60 and to increase the compressive strength
from 25 to 200 MPa
Moreover, in this second unit cell (Figure 1.4), it may be seen that the cement
particles are so close to each other that the hydrates formed on the surface of one
cement particle have only to grow a very short distance before reaching the hydrates
growing on the surface of the adjacent cement particles (Granju and Maso, 1984;
Granju and Grandet, 1989; Richardson, 2004).
The proximity of the cement particles in this unit cell results in the rapid develop-
ment of very strong bonds and very low porosity. Therefore, in such an arrangement of
cement particles, it is not necessary to use cements having high C3A and C3S contents
and a high fineness in order to produce a rapid hardening of the cement paste. More-
over, it may also be seen that in such a unit cell, it is only necessary to form a very small
amount of “glue” to obtain a high strength and it is not necessary for all of the cement
particles be fully hydrated to obtain a high strength material. Finally, it will be seen
later that in such a dense system, the unhydrated parts of the cement particles act as
hard and rigid inclusions that serve to strengthen the resulting hydrated paste.

1.3 The waterecement and waterebinder ratios in a

cement paste made with a blended cement
To lower the carbon footprint of Portland cement, modern cements are increasingly
becoming blended cements in which a certain amount of the ground clinker is replaced
by a supplementary cementitious material or a filler (Kreijger, 1987; Mehta, 2000).
Such a system can be characterized by its w/c and w/b ratios, which are different. In
the first case, we are considering only the Portland cement contained in the system;
in the second case, we are considering the amount of cement and supplementary
The importance of the waterecement and waterebinder ratios 7

particles in the system. Using the same 2D model, we can show that knowing both
numbers is very important to explain some of the physical and mechanical properties
of a cement paste made with a blended cement.

1.3.1 Case of a blended cement containing a

supplementary cementitious material
Let us go back to Figure 1.2 and replace one of the four cement particles with a circular
particle of a supplementary cementitious material having the same diameter as the
cement particles as shown in Figure 1.5. For this purpose, it is not necessary to
know whether it is a slag or a fly ash particle, as long as it has the same radius of
our theoretical circular cement particle. The substitution of one cement particle of
the unit cell by a supplementary cementitious particle having the same diameter
represents a volumetric substitution rate of 25%.
Now, the new unit cell can be characterized by two numbers, namely its w/c and
w/b ratios. The w/b ratio of this new unit cell is the same as the w/c ratio of the
unit cell shown in Figure 1.2, but its w/c ratio is greater because only three particles
out of four are Portland cement particles. A simple calculation shows that now the
w/c value of this unit cell is 0.78. The higher value of the w/c ratio is due to the
fact that the Portland cement content of this unit cell has been diluted.
Because supplementary cementitious materials are initially less reactive than
Portland cement particles, the initial strength of this blended cement will be lower
than that of the pure Portland cement. The Portland cement particles adjacent to
supplementary cementitious particles will have to develop their hydrates over a dis-
tance twice as long as in Figure 1.2 to reach the adjacent supplementary cement
particle because the supplementary cementitious particle will not develop any hydrates

Supplementary
cementitious
material

Figure 1.5 2D model of a blended cement containing 25% by volume of a supplementary

cementitious material.
Courtesy of William Wilson.
8 Science and Technology of Concrete Admixtures

on a short-term basis. Therefore, in the short term as far as compressive strength is con-
cerned, the system is performing less well than the previous one.
Over the long term, when the supplementary cementitious particles will have
reacted with the lime liberated by the hydration of the Portland cement particles, the
system will be as strong as, or even stronger, than the one represented in Figure 1.2.
However, to reach the same compressive strength, a long water curing period is a
must. The compressive strength of a well-cured system containing supplementary
cementitious materials will be greater than the equivalent pure Portland cement
system. The lime crystals (portlandite) that are a byproduct of the hydration of the
anhydrous calcium silicates that make up most of the Portland cement do not bring
any strength to the hydrated cement paste in a pure Portland cement system. However,
in a system with supplementary cementing materials, they are transformed into second-
ary calcium silicate hydrates that are the same as the “glue” developed in pure cement
paste.
It is very important to note that the dilution of Portland cement results in a decrease
in the short-term compressive strength of the concrete if the chemical composition of
the clinker is not changed. However, in the long term, it results in equivalent (or even
higher) strength.
The network of the capillary pores in this new system is characterized by its w/b
ratio, which is much lower than the w/c ratio of the system. We will see later that
the w/b ratio is a very important parameter when analyzing the different forms of
shrinkage that develop in such a system.
Returning to Figure 1.2, let us introduce a particle of cementitious material having
the same radius a as the cement particles in the center of the unit cell, as shown in
Figure 1.6. In such a system, the substitution rate by volume of Portland cement is
now 50%, double that of the previous one.

Supplementary
cemetitious
material

Figure 1.6 2D model of a unit cell containing a particle of supplementary cementitious material
in the middle of the four cement particles.
Courtesy of William Wilson.
The importance of the waterecement and waterebinder ratios 9

Supplementary
cemetitious
material

Figure 1.7 Hydration of the previous system.

Courtesy of William Wilson.

The w/b ratio of this new unit cell is 0.14 and its w/c ratio is 0.27. We can see in
Figure 1.7 that as soon as the cement particles start to hydrate, the superficial hydrates
will have to grow only a very short distance to surround this central supplementary
cementitious particle and to create strong bonds.
This matrix will become even stronger when the supplementary cementitious par-
ticle starts to react with the lime liberated by the hydration of Portland cement particle,
in spite of the fact that the volumetric rate of substitution of the Portland cement is now
50%. Therefore, both the early and the long-term compressive strength of blended
cements do not essentially depend on the substitution rate of Portland cement, but
rather on the w/b ratio of the system.
With superplasticizers, we are able to drastically decrease the w/b ratio of such
systems that contain a large volume of supplementary cementitious materials. In the
case of fly ash, Malhotra and Mehta (2008) refer to such concretes as high-volume
fly ash. ACI (2014) published the “ACI 232.3R-14 Report on High-Volume Fly Ash
Concrete for Structural Applications.” High-volume fly ash concretes have been
used in California in various civil engineering projects (Mehta and Manmohan, 2006).
Of course, high-volume slag concrete can be produced in the same way. It is important
to note that in order to obtain an increase in the long-term strength, some water has to be
available for hydrating the supplementary system on a long-term basis in such a system.

1.3.2 Case of a blended cement containing some filler

In our initial unit cell represented in Figure 1.2, let us replace one of the cement par-
ticles with a filler particle having the same diameter as the cement particles, as shown
in Figure 1.8.
We now obtain a unit cell similar to that of Figure 1.5, with the difference being that
one of the cement particles is replaced by a nonreactive limestone filler particle instead
10 Science and Technology of Concrete Admixtures

Limestone
filler

Figure 1.8 2D model of blended cement where one particle of filler has been substituted for one
particle of cement.
Courtesy of William Wilson.

of a reactive supplementary cementitious material particle. The nonreactivity (or very

low reactivity in the case of some limestone filler particles) of the substituted particle
means that in this type of blended cement, Portland cement has been diluted. Conse-
quently, on both a short-term and long-term basis, the system will underperform from a
mechanical point of view.
To increase both the early and 28-day compressive strengths of their small cubes
cast to test the strength of their cement, cement chemists usually modify the chemical
composition of their clinker and the fineness of their blended cement to promote the
formation of rapidly growing hydrates. This is not, in our opinion, a good approach
when considering long-term concrete durability and sustainability.
When a filler particle is introduced among four cement particles, as shown in
Figure 1.9, the system will be stronger than the previous one once the hydrates

Limestone
filler

Figure 1.9 2D model representing a system in which a particle of filler has been placed at the
center of the four cement particles.
Courtesy of William Wilson.
The importance of the waterecement and waterebinder ratios 11

developed from the surfaces of the four cement particles reach the filler particle, in
spite of the fact that the substitution rate is twice as high (50% instead of 25%).
In this system, the size of the capillaries in the hardened matrix is governed by the
w/b ratio, which is very important from an autogenous shrinkage point of view.
Therefore, instead of changing the chemical composition of their clinkers, cement
chemists should instead recommend to their customers that they decrease the w/b ratio
of their concrete if they absolutely want to obtain with their blended cement the same
initial compressive strength as with a “pure” Portland cement. This solution will be
much better from both durability and sustainability points of view.

1.3.3 The relative importance of the w/c and w/b ratios

When part of the Portland cement has been substituted with a supplementary cemen-
titious material or filler, this new cementing system can be characterized by two ratios:
its w/c and w/b ratios. Which one of these two ratios is more useful in characterizing
the system? The answer is both: the w/c ratio is not passé (Barton, 1989).
In the short term, the early mechanical properties are linked primarily to the w/c
ratio, because the first hydrates that give the cement paste its strength are the ones
that develop on the surface of the cement particles; supplementary cementitious mate-
rials and fillers are not as reactive as Portland cement particles, and their reactivity de-
pends on their type. Very roughly, it can be assumed that silica fume begins to react
significantly within the first 3 days, slag within the first 28 days, and fly ash within
the first 56e91 days following the casting of concrete, and filler never.
However, the initial network of capillaries of the cement paste is generally
governed by the w/b ratio and no longer by the w/c ratio. Therefore, the w/b ratio
will determine the size of the menisci that form in the cement paste as a consequence
of the chemical contraction that is observed when Portland cement hydrates in the
absence of an external source of water, as will be seen in the following chapter.
In the long term, the w/b ratio also influences the compressive strength and
durability of cement pastes made with blended cements containing supplementary
cementitious materials.

1.4 How to lower the w/c and w/b ratios

Until recently, it was not possible to make 100-mm slump concretes with w/c or w/b
ratios lower than 0.40 or 0.45 because the water reducers available in the market
were not efficient enough to fully deflocculate the cement particles. As pointed out by
Kreijger (1980), when cement particles come into contact with water molecules, they
have a natural tendency to flocculate and to trap a certain amount of water inside the
cement flocs. Because this water is then not available to provide workability to the con-
crete, it is necessary to increase the water dosage to increase the workability. However,
increasing the water dosage means increasing the w/c or w/b ratio, and therefore
decreasing concrete compressive strength and durability. As will be seen in Chapter
2, cement flocculation is due to the presence of positive and negative charges on the
12 Science and Technology of Concrete Admixtures

surfaces of each cement particle because of the polyphasic nature of Portland cement
clinker and of the electrical polarity of water molecules.
Once the very efficient dispersing properties of certain new synthetic molecules
known as superplasticizers were discovered, it became possible simultaneously to
decrease the w/c or w/b ratio, while increasing the slump of the concrete. With certain
cements, it is possible to decrease the w/c or w/b ratio down to 0.25 and even in some
cases to 0.20, while maintaining a slump of 200 mm long enough to place the concrete.
These concretes do not contain enough water to fully hydrate all of their cement
particles (Powers, 1968). However, we will see that it is not the full hydration of
cement particles that is determining concrete compressive strength, but rather their
closeness in the cement paste.
The compressive strength of the hydrated cement paste can increase so much when
decreasing the w/c or w/b ratio that finally, in some cases, the rupture of the concrete
starts within the coarse aggregates particles. Therefore, when decreasing the w/c or w/b
ratios below 0.30, it is necessary to use coarse aggregates made from very strong
natural rocks (granite, trap rock, basalt, or porphyry) to increase concrete compressive
strength or even some artificial aggregates, such as calcined bauxite (Bache, 1981).
However, even with such strong aggregates, it is difficult to obtain concrete compres-
sive strengths greater than 150e180 MPa. To obtain Portland cement-based materials
having compressive strength greater than 200 MPa, it is necessary to completely
eliminate the coarse aggregates and make what Pierre Richard called reactive powder
concrete (now referred to as ultra-high strength concrete; Richard and Cheyrezy,
1994). In such concretes, the coarsest sand and quartz particles have a maximum
size of 0.2 mm, as will be shown in Chapter 27. By replacing the sand and quartz
particles with iron powder, Pierre Richard was able to increase the compressive
strength of its reactive powder concrete up to 800 MPa.
These impressive strengths were not obtained because we learned how to fully
hydrate Portland cement particles, but rather because we have been able to lower
the w/b ratio to around 0.20 so that the cementitious particles are very close to each
other in these very dense fresh cement pastes.

1.5 Conclusion
The numerical values of the w/c and w/b ratios are directly related to the distance
separating the particles in a cement paste when the hydration process starts. The lower
the w/c or w/b ratio is, the stronger, more durable, and more sustainable the hydrated
cement paste is.
Before the discovery of the very efficient properties of superplasticizers, when
water reducers were essentially lignosulfonates (a byproduct of the pulp and paper
industry), it was not possible to produce concrete having a 100-mm slump with a
w/c or w/b ratio lower than 0.45 in the best circumstances. This is no longer the
case. Currently, it is possible to produce concretes having a w/c or w/b ratio as low
as 0.30, which are easier to place than a 0.45 w/c concrete having a slump of
100 mm in 1960.
The importance of the waterecement and waterebinder ratios 13

As will we see in Chapter 2, this is in spite of the fact that in such concrete there is
not enough water to fully hydrate all of the cement. Concrete compressive strength
continues to increase as the w/c or w/b ratio decreases because concrete compressive
strength depends on the proximity of the cement or the binder particles in the hardened
matrix rather than on the amount of cement hydrates formed.
This ability of superplasticizers to lower almost at will the w/c or w/b ratio in
modern concretes is the key factor that has resulted in the use of high-performance
and self-consolidating concrete, with concrete even starting to displace steel in the
construction of high-rise buildings (Aïtcin and Wilson, 2015).

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