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Chemical Shrinkage of High-Strength / High-Performance Cementitious

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Article  in  International Review of Chemical Engineering (IRECHE) · March 2010

DOI: 10.15866/ireche.v10i1.15794

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 International Review of Civil Engineering (I.RE.C.E.), Vol. 1, n. 1
March 2010

CHEMICAL SHRINKAGE OF HIGH-STRENGTH / HIGH-

PERFORMANCE CEMENTITIOUS MATERIALS

Semion Zhutovsky1 and Konstantin Kovler1

Abstract – Chemical shrinkage is important property of cementitious materials. It is considered

the main cause of autogenous shrinkage of high-strength / high-performance concretes, which are
made at low water/cement (w/c) ratio. It is generally assumed that chemical shrinkage varies
directly as the degree of hydration and is independent of w/c, since it has its origin in the
hydration reaction stoichiometry. The methods of measurements of chemical shrinkage, which
include dilatometry, pycnometry and gravimetry (buoyancy), are briefly reviewed. The
interpretation of the experimental data on chemical shrinkage of hydrating cement paste is revised
in the paper. The chemical shrinkage of cement pastes with w/c ratios of 0.45, 0.33, 0.25 and 0.21
was tested by gravimetry method. The degree of hydration of the pastes was determined by
thermogravimetric analyzer (TGA). The effect of water/cement ratio on chemical shrinkage of
hydrating cement pastes cured in saturated and sealed conditions was established and compared
with the literature data. Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved.

Keywords: Portland cement, Le Chatelier, chemical shrinkage, autogenous shrinkage, hydration

considering the degree of hydration measured on

I. Introduction
An interest to chemical shrinkage of cementitious
construction materials has grown with the wide spread of
high-strength / high-performance concrete (HSC/HPC). It
is well-known that the major problem of HSC/HPC is
their early-age cracking sensitivity, which is caused by
autogenous shrinkage and self-desiccation. Chemical
shrinkage is considered the main driving force of self-
desiccation and autogenous shrinkage. Thus, correct
calculation is indispensable in autogenous shrinkage
modeling and internal curing applied mix design.
Extensively studied, chemical shrinkage is considered
an intrinsic property of Portland cement. For the most
part, it is assumed proportional to degree of hydration,
since it has its origin in the hydration reaction
stoichiometry. Furthermore, generally accepted point of
view is that chemical shrinkage is independent of
water/cement ratio. However, traditional way of data
representation of chemical shrinkage experimental results
does not take into account the actual degree of cement
hydration. Although the chemical shrinkage is produced
only by hydrated cement, the measured chemical
shrinkage volume is conventionally related to initial total
cement content.
In this paper, the degree of hydration of the saturated
Portland cement pastes with water/cement ratios of 0.45,
0.33, 0.25 and 0.21 was determined by TGA. The
experimental chemical shrinkage data were analyzed
saturated cement pastes. The effect of water/cement ratio
and degree of hydration on chemical shrinkage of cement
paste was evaluated and compared with the literature
data. Based on the chemical shrinkage of the saturated
cement pastes, the chemical shrinkage of sealed cement
pastes was calculated.
This paper is an extended version of the work
originally presented in parts at International Conferences
on Microstructure Related Durability of Cementitious
Composites in 2008 [1] and Concrete Durability and
Service Life Planning in 2009 [2].
II. Theoretical Background
II.1. Chemical Shrinkage Terminology
The volume of products of cement reaction with water
is smaller than the sum of the volumes of reactants
(Fig. 1). This phenomenon is variously known as
chemical shrinkage, hardening shrinkage or Le Chatelier
contraction after the name of the scientist that first
discovered it [3] (Fig. 2). Le Chatelier measured the
volume reduction of cement pastes by means of a simple
dilatometer representing a glass beaker connected with
the water filled tube. He showed that total chemical
shrinkage for normal Portland cement was 4.6% by
cement weight.

Manuscript received February 2010, revised March 2010 Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved
 S. Zhutovsky, K. Kovler
Fig. 1: Phenomenon of chemical shrinkage of cement system
Fig. 2. Henry Louis Le Chatelier (8 Oct. 1850 - 17 Sept. 1936) - French/Italian chemist, discovered chemical shrinkage
Though, chemical shrinkage is sometimes referred as
“internal autogenous shrinkage” [4] and autogenous
shrinkage is sometimes called “external chemical
shrinkage” [5], chemical shrinkage should not be
confused with autogenous shrinkage, which is the
variation of external dimensions of the material.
Generally speaking, external dimensions can either
decrease due to self-desiccation (autogenous shrinkage)
or external drying (drying shrinkage), or increase due to
water intake (swelling), while the volume of hydration
products will be anyway smaller than volume of cement
and water, i.e. chemical shrinkage takes place even if the
material undergo external expansion. Furthermore,
chemical shrinkage is commonly one-two orders higher
than autogenous shrinkage [6]. The chemical shrinkage is
strongly dependent on the degree of hydration.
Additionally, chemical shrinkage depends on the
stoichiometry of hydration reaction. Thus chemical
shrinkage is different for different cement mineral, and
thus for various cement types and complementary
cementitious materials.
Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved
II.2. Chemical Shrinkage Research: Why Namely in
High-Strength / High-Performance Concrete?
It has to be emphasized that extremely low w/c ratios
are inherent for HSC/HPC. For this reason, a growing
popularity of HSC/HPC rekindled an interest to chemical
shrinkage research.
In general, the phenomenon of chemical shrinkage has
been known since the dawn of concrete technology.
However, in the ordinary concretes the chemical
contraction did not produced substantial problems for the
several reasons. Since ordinary concrete does not develop
especially impermeable structure, proper water cuing can
avoid appearance of empty pore space. High-strength /
high-performance concretes, in their turn, develop
extremely low permeability which results in development
of empty porosity, menisci creation in gas/water interface
and subsequent reduction of relative humidity. On the
other hand, substantial role plays pore structure of
concrete which is extremely fine in HSC/HPC. Very fine
pore size distribution is the reason of extensive shrinkage
in desiccating concrete. Additionally, cement content in
HSC/HPC is much higher than in ordinary concrete.
International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

Therefore, the total chemical shrinkage in HSC/HPC is
considerably higher than in ordinary concretes. By this
means, chemical shrinkage is the driving force of self-
desiccation and consequent autogenous shrinkage [7, 8],
which can lead to cracking and even failure of concrete
made at low w/c ratio.
The mechanisms, which can result in cracking of high-
strength / high-performance concrete are illustrated
schematically in Fig. 3. They start from chemical
shrinkage, which serves a driving force for creation of
empty porosity, causing in turn self-desiccation,
autogenous shrinkage, and finally cracking of concrete at
early age under restrained conditions.

RH reduction Capillary Early-age

Autogenous
(self- tension cracking
Creation of shrinkage
desiccation) in pore water under restraint
Chemical
empty porosity
shrinkage
0.002-10 μm
Reduction of Lower degree
hydration rate of hydration

Fig. 3: Chemical shrinkage of cement system as a driving force of early-age cracking in high-strength / high-performance concrete

(alite C3S, belite C2S, tricalcium aluminate C3A and

II.3. Modeling
Portland cement is poly-mineral compound and its
hydration is extremely complex. However, it is
conventional practice to represent the hydration of
Portland cement by a set of simplified equations, such as
shown in Table 1. This set of equations represents the
hydration reactions of the main Portland cement minerals
ferrite C4AF) and also pozzolanic reaction - equation (9).
Each reaction has its own stoichiometry resulting in
different chemical shrinkage. If, for instance, when
equation (1) is considered, using the reaction
stoichiometry and known molar volume, which is molar
mass divided by density, the chemical shrinkage of alite
can be calculated as shown in Table 2.

TABLE 1
HYDRATION REACTIONS OF THE MAIN PORTLAND CEMENT PHASES
Hydrating phase Hydration reaction

Alite C3S + 5.3 H → C1.7SH4 + 1.3 CH (1)

Belite C2S + 4.3 H → C1.7SH4 + 0.3 CH (2)

Tricalcium C3 A  3 CSH 2  26 H  C3A  3CS  H 32 (3)

aluminate
Tricalcium 2C3A  C3A  3CS  H32  4H  3 C3A  CS  H12  (4)
aluminate
Ferrite C4 AF  3 CSH2  27 H  C3  AF  3CS  H32  CH (5)

Ferrite 2 C4 AF  C3  AF  3CS  H32  6 H  3 C3  AF  CS  H12   2 CH (6)

Tricalcium C3A  CH  12 H  C4 AH13 (7)

aluminate
Ferrite C4 AF  2 CH  10 H  2 C3  AF H6 (8)

Silica (pozzolanic 1.1 CH  S  2.8 H  C1.1SH3.9 (9)

reaction)

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

TABLE 2
HYDRATION REACTION OF ALITE AND CALCULATION OF CHEMICAL SHRINKAGE

C 3S + 5.3 H = C1.7SH4 + 1.3 CH

Molar volume (Vm),
cm3/mole 71.13 18.07 107.82 33.08
Density (), g/cm3 3.210 0.997 2.110 2.240
Molar mass (Mr),
g/mole 228.330 18.016 227.490 74.096
71.13 cm3 + 95.4 cm3 107.82 cm3 + 43.00 cm3
166.53 cm3 = 150.82 cm3
Chemical
3
cm /mole of cm3/g of C3S
= -15.71 = -0.069 hydrated
Shrinkage C3S hydrated

It can be seen that hydration of each gram of alite
results in reduction of volume by 69 mm3, i.e. to
chemical shrinkage of alite is 69 mm3/g of C3S hydrated.
Let us define specific chemical shrinkage as the total
volume reduction of solid and liquid substances per unit
weight of cement hydrated, in cement paste. If Powers
model of cement paste [9] is accepted and both molar
mass and density of cement gel are assumed constant,
then the chemical shrinkage of any cement mineral
(Vics) at any time (t) can be calculated as product of
specific chemical shrinkage of the given mineral (CSi),
the percentage of the mineral in cement ([i]), the initial
weight of cement (C) and degree of hydration of the
mineral (i):
Vcsi (t )  CSi  [i ]  C   i (t )
Total chemical shrinkage of cement is the sum of
chemical shrinkage of its constituting minerals. If the
cement composition is known, chemical shrinkage of
cement can be quantified from the volume stoichiometry
of the hydration reaction for any of general-type cement.
Then the total chemical shrinkage can be calculated as a
sum of chemical shrinkages of individual minerals:
Vcstotal (t )   Vcsi (t )
i
hydration and w/c ratio. For this reason, chemical
shrinkage measurement is often put forward as a method
of the determination of the degree of cement hydration
[12] and has a good correlation with chemically bound
water [9, 13], heat of hydration [14, 15] and even
compressive strength [3, 16, 17].
II.4. Experimental Techniques
Chemical shrinkage is measured on fully saturated
samples with excess water as distinct from autogenous
shrinkage which is measured on sealed samples. The
extra water is absorbed into hydrating cement paste and
the reduction of volume can be measured. Accordingly,
the thickness of cement paste specimen should be small
(10) enough to allow the water penetration to the whole depth
of the cast specimen all the way. It should be emphasized
that autogenous and chemical shrinkage are equal until
the moment of setting commencement.
Chemical shrinkage of cement paste can be measured
by two general approaches – volumetric and gravimetric.
The first approach implies the measurement of volume
changes of the cement paste during hydration under
controlled top water level. This methodology was
originally developed by Le Chatelier [3] and is
(11)
commonly referred as dilatometry method [18] (Fig. 4).

Multi-mineral hydration model that is able to predict

degree of hydration of individual minerals is required in
order to use equations (10) - (11). Such models are
generally very complicated and their application on a
regular basis is often problematic. Therefore, it is
common practice to simplify equations (10)- (11) by
means of averaged degree of hydration and averaged
specific chemical shrinkage:

Vcstotal (t )  C   (t )    CSi  [i ]  C   (t )  CS (12)

i

Expressions for the calculation of the total chemical

shrinkage similar to (12) were used by several
researchers [10, 11]. This approach assumes that the Fig. 4. Dilatometry method
specific chemical shrinkage is independent of degree of

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

Another volumetric method that was proposed by Since the distance between cement particles in lower w/c
Swayze [19] is pycnometry (Fig. 5). It implies keeping ratio pastes is shorter, there is less space for outer
the total volume of paste and water constant, during hydration products, i.e. for LD CSH. Hence, the LD/HD
continuous weighing that allows automatic data logging. CSH ratio will decrease with w/c ratio. For the similar
reasoning, the LD/HD CSH ratio will decline with
increase in degree of hydration for cement pastes with
w/c ratio below 0.4 [29]. Since the LD and HD CSH
have different density, and thus the different molar
volume, it is expected that variation of LD/HD CSH ratio
would affect the specific chemical shrinkage.
The main features of outer (LD) and inner (HD) CSH
gel are shown in Table 3.
Fig. 5. Pycnometry method
TABLE 3
PROPERTIES OF OUTER AND INNER CSH GEL
The second approach uses Archimedes' principle in
order to evaluate volume changes of hydrating cement Outer gel Inner gel
paste. Hydrating cement paste with excess water is - forms during early - forms during later
weighed in water or oil. Accordingly, the measured hydration hydration, when the
weight change corresponds to the chemical shrinkage - forms away from the process is diffusion
cement particle surface, controlled
divided by the density of the liquid used for weighing.
filling water-filled space - CSH grows inwards and
This method is generally referred as gravimetry method,
- has higher porosity outwards from the CSH
buoyancy method or simply weighing method (Fig. 6). - contains high levels of “barrier”
This method was initially proposed by Rey [20] and impurities - CSH formed takes shape
further developed by Knudsen and Geiker [6]. - probably admixed with of cement grains
nanoscale C4ASH12 - has lower porosity
- has fewer impurities
- more resistant to physical
change on drying
- more abundant as
hydration degree
increases or w/c
decreases

Fig. 6. Gravimetry (buoyancy) method
The advantage of gravimetry method is very easy
implementation of the measurement automation by
connecting the balance to a data logging system.
Although not so simple as for gravimetry, dilatometry
and pycnometry measurements can also be automated by
means of photocell [15] and balance, respectively. It is
also worth noting that there is a standard for chemical
shrinkage measurement in North America that includes
both volumetric and gravimetric approaches [21].
II.5. Concept of outer and inner CSH gel
Recently Tennis and Jennings published a model of
calcium silicate hydrate (CSH) that based on two types of
gel: low-density (LD) CSH and high-density (HD) CSH
[29, 30]. Relying on the experimental data of nitrogen
sorption, they deduced that in cement paste exist HD
CSH and LD CSH, which can be associated,
respectively, with inner and outer hydration products.
II.6. Motivation
Since chemical shrinkage causes a number of
problems in cementitious systems with low w/c ratio,
scientific interest to chemical shrinkage aroused with the
growth of the popularity of HSC/HPC. The effect of
cement composition, temperature, mineral and chemical
admixtures, w/c ratio, and degree of hydration on
chemical shrinkage as well as correlation between
chemical and autogenous shrinkage has been investigated
[18-20, 22-28]. Several researchers [23-26] reported the
experimental data which support the contention that
specific chemical shrinkage is independent of degree of
hydration and w/c ratio. However, there are publications
that report increase of chemical shrinkage with increase
of w/c ratio [6, 13-15, 27, 28]. Nevertheless, the method
of data representation casts some doubts upon the
conclusions.
Traditionally results of chemical shrinkage
measurements are described as the volume reduction
related to the initial cement content. However, since only
hydrated cement causes chemical shrinkage, it cannot be
concluded from such data representation in which
manner the specific chemical shrinkage is affected by

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x

w/c ratio or degree of hydration. The applicability of
equation (12) comes into question, considering that in
cement pastes with lower w/c ratio the initial cement
content is higher, while the final degree of hydration is
lower. Moreover, there is experimental evidence that
cement gel has uneven microstructure.
Summarizing the above argumentation, further
research is required in order to assess the effect hydration
degree and w/c ratio on specific chemical shrinkage. In
the case that experimental data provide a proof to LD and
HD CSH model, equation (10) should be adopted for
each of the two types of cement gel.
III. Materials and Methods
The chemical shrinkage of cement pastes with
water/cement ratios of 0.45, 0.33, 0.25 and 0.21 was
tested by weighing-in-water method. The degree of
hydration of the pastes was examined by TGA.
III.1. Materials
Commercially available ordinary Portland cement of
CEM I 52.5 N type manufactured by Nesher - Israel
Cement Enterprises Ltd. was used. The chemical
composition of the cement according ASTM C114-85 is
given in Table 4. The loss on ignition was 4.2 % by
weight.
Specific surface area of the Portland cement, tested
according ASTM C204, was 421.7 m2/kg. Setting times
were determined in accordance with ASTM C191. The
initial setting time comprised 160 minutes and final
setting time 220 minutes.
TABLE 4
CHEMICAL COMPOSITION OF PORTLAND CEMENT
Oxide CaO SiO2 Al2O3 Fe2O3 MgO TiO2 K2O Na2O SO3
% by 63.03 18.53 5.60 3.43 1.37 0.38 0.45
weight
Cement paste samples were made at water to cement
ratios of 0.21, 0.25, 0.33 and 0.45. Commercially
Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved
S. Zhutovsky, K. Kovler
available high range water reducing agent
"RHEOBUILD 2000b" of the naphthalene
formaldehyde sulfonate type was used for mixes with
w/b ratio of 0.21, at content of 3% and w/b ratio of 0.25
at content of 2% by weight of cement.
III.2. Chemical shrinkage
Chemical shrinkage of hydrating cement pastes were
tested by means of gravimetry method. This method
implies weighing the hydrating cement paste in water.
According to Archimedes' principle, the measured weight
change corresponds to the chemical shrinkage. The
experimental set up is depicted in Fig. 6. The test was
performed in temperature-controlled room at 30°C.
III.3. Degree of hydration
The degree of hydration was determined by means of
thermogravimetric analyzer (TGA). The degree of
hydration was calculated by the dividing of weight loss
between 105°C and 1000°C by 0.23. The samples were
cast simultaneously and kept sealed in temperature-
controlled room at 30°C until the target age and then
dried at 105°C. After drying, the samples were ground to
powder and tested using Perkin-Elmer® Thermo-
Gravimetric Scanner (TGS-2).
IV. Results and Discussion
The chemical shrinkage results are shown in Fig. 7.
Here, chemical shrinkage is presented traditionally as
volume reduction per gram of cement initially present in
the mix. It can be seen that all the curves are very similar
in the conventional representation. Neither effect of w/c
ratio, nor that of degree of hydration can be recognized.
The determined degree of hydration for cement pastes
0.14 2.53
cured at saturated and sealed conditions is shown in Fig.
8 and Fig. 9, respectively.
International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

80

mm3 per g of cement

Chemical shrinkage, 60 7d

3d
2d
40
1d
18h 0.21
12h
9h 0.25
20 8h
7h 0.33
6h
0.45
4h 5h
0
1 10 100 1000
Age, hours
Fig. 7. Chemical shrinkage of saturated cement pastes made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

0.7

0.6
Degree of hydration

0.5
7d
2d 3d
0.4 1d
18h
12h 0.21
0.3 9h 0.25
8h
7h 0.33
0.2 6h 0.45
4h 5h
0.1
1 10 100 1000
Age, hours
Fig. 8. Degree of hydration of saturated cement pastes made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

0.7

0.6
Degree of hydration
0.5

0.4 2d 3d 7d
1d
18h
0.21
0.3 12h
9h 0.25
8h 0.33
0.2 7h
6h 0.45
4h 5h
0.1
1 10 100 1000
Age, hours
Fig. 9. Degree of hydration of sealed cement pastes made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

As can be seen in Figure 8, the degree of hydration
varies for different w/c ratios at given time for the
cement pastes with sealed curing. This effect, which is
more pronounced after the age of 24 hours, is most likely
the result of self-desiccation that is higher for lower w/c
ratio. Consequently, pastes that were cured at saturated
condition demonstrate closer values of degree of
hydration, except for the paste with extremely low w/c
ratio of 0.21. Since only the hydrated cement produced
chemical shrinkage, it would be more relevant to relate
chemical shrinkage to weight of hydrated cement, instead
of initial cement content. This parameter, which earlier
related as specific chemical shrinkage, can be estimated
by dividing the values of chemical shrinkage in Fig. 7 by
the degree of hydration shown in Fig. 8. The calculated
specific chemical shrinkage is plotted in Fig. 10, where
the effect of w/c ratio can be seen readily.

140
mm3 per g of hydrated cement

7d

120 3d
Chemical shrinkage,

2d

100 9h 18h
1d
8h
7h 12h
6h
80 5h
4h
0.21
60 0.25
0.33
40 0.45

20
1 10 100 1000
Age, hours
Fig. 10. Specific chemical shrinkage of saturated cement pastes made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

In Fig. 10, the specific chemical shrinkage is depicted
versus the time scale, whereas, at given time point, the
degree of hydration for different w/c ratios is still
different. Furthermore, the majority of the modeling
approaches predict the chemical shrinkage as function of
degree of hydration. It can be seen that specific chemical
shrinkage increases with the degree of hydration (Fig.
11), and that at very low w/c ratio (0.21) the specific
chemical shrinkage is significantly higher. In the
literature (for example, in [31]), one can find chemical
shrinkage curves as function of degree of hydration, as
presented in Fig. 12. However, the curves are usually cut
at 24 hours, while the trend is more pronounced beyond
the age of 1 day.

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler

140

mm3 per g of hydrated cement

7d
3d
120
Chemical shrinkage,
2d

100 1d
18h
7h 8h 9h 12h
80 5h 6h
4h
0.21
60 0.25
0.33
40 0.45
Modeled
20
0.1 0.2 0.3 0.4 0.5 0.6 0.7
Degree of hydration
Fig. 11: Specific chemical shrinkage of saturated cement pastes vs. degree of hydration made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

80
0.21
Chemical shrinkage,
mm3 per g of cement

0.25 7d
60 0.33 3d
0.45 2d

Modeled 1d
40 18h
12h
9h
7h 8h
20 5h 6h
4h

0
0.1 0.2 0.3 0.4 0.5 0.6 0.7
Degree of hydration
Fig. 12: Chemical shrinkage of saturated cement pastes vs. degree of hydration made with w/c ratios of 0.21, 0.25, 0.33 and 0.45

The widespread concept suggests constant specific
chemical shrinkage. It is intensively used in chemical
shrinkage calculations, including autogenous shrinkage
modeling [32] and internal curing design [11, 33]. The
chemical shrinkage predicted by this modeling concept is
illustrated in Fig. 11 and Fig. 12 by dotted line. It can be
seen that chemical shrinkage is considerably
underestimated by the hypothesis of constant specific
chemical shrinkage. Moreover, the underestimation
increases with the lower w/c ratio and the higher degree
of hydration. Consequently, the autogenous shrinkage,
which is predicted assuming constant specific chemical
shrinkage, is underestimated also. When it comes to the
calculation of internal curing water, using this
methodology may result in inappropriate mix design.
The concept of LD and HD CSH, referred earlier,
provides adequate explanation to the specific chemical
shrinkage behavior demonstrated in Figure 11. Indeed, if
LD CSH corresponds to the outer gel and HD CSH to the
inner gel products, the LD/HD CSH ratio will decrease
with w/c ratio and degree of hydration. This is because
the space between cement particles in lower w/c ratio
pastes is lower; there is less room for outer hydration
products, i.e. for LD CSH. Furthermore, in cement pastes
with w/c ratio below 0.4, where the pore space is
insufficient, an inflection point is expected when the
interparticle space is filled with LD hydration products.
Certainly, there is additional effect of aluminate phases,
which contribute to higher chemical shrinkage at later
age, since they have triple-stage reaction of ettringite
formation and conversion to monosulphate, calcium
aluminate hydrate and hydrogarnet formation – see

Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved International Review of Civil Engineering, Vol. x, N. x
 S. Zhutovsky, K. Kovler
equations (3)-(8).
IV.1. Chemical shrinkage in sealed cement paste
Additional point, which is often ignored, is that
chemical shrinkage tests are essentially performed on
saturated cement pastes, while autogenous shrinkage
develops in cementitious systems cured under sealed
conditions [21]. Chemical shrinkage, calculated with the
assumption that chemical shrinkage in sealed cement
pastes corresponds to the chemical shrinkage in saturated
pastes at the same degree of hydration, is presented in
80
mm3 per g of cement
Chemical shrinkage,
60
40
12h
8h 9h
7h
20 6h
5h
4h
0
1 10
Fig. 13. Calculated chemical shrinkage of sealed cement pastes with w/c ratios of 0.21, 0.25, 0.33 and 0.45
V. Conclusions
1. Specific chemical shrinkage depends on w/c ratio
and degree of hydration: the lower w/c ratio the
higher specific chemical shrinkage, and the higher
the degree of hydration the higher is the specific
chemical shrinkage.
2. The currently used model for degree of hydration,
which assumes constant specific chemical shrinkage
and, accordingly, the total chemical shrinkage is
proportional to degree of hydration, considerably
underestimates chemical shrinkage after the age of
24 hours.
3. The concept of constant specific chemical shrinkage
leads to underestimation of autogenous shrinkage
and improper design of internal curing.
4. Further research is required in order to measure
chemical shrinkage on sealed samples and study the
direct effect of self-desiccation on chemical
shrinkage.
Copyright © 2010 Praise Worthy Prize S.r.l. - All rights reserved
Fig. 13. Here we can see that the effect of w/c ratio in the
sealed cement pastes would be noticeable. At the same
time, it has to be emphasized that such approach is rather
simplified, because does not consider a possible direct
influence of self-desiccation on chemical shrinkage.
Further research is needed in order to study the direct
effect of self-desiccation on chemical shrinkage. For this
purpose, a method for direct measurement of the
chemical shrinkage of sealed samples is required, which
is going to be a challenge for a future research.
7d
3d
2d
1d
18h
0.21
0.25
0.33
0.45
100 1000
Age, hours
Acknowledgements
The authors acknowledge German-Israeli Foundation
for Scientific Research and Development.
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Authors’ information
1
National Building Research Institute – Faculty of Civil and
Environmental Engineering, Technion – Israel Institute of Technology,
Haifa 32000, Israel.
Semion Zhutovsky was born in Novgorod,
Russia in 1975, and since 1995 has been living
in Israel. He received his B. Sc. (cum laude) in
1999 followed by M. Sc. in 2001 in Civil
Engineering at the Technion – Israel Institute
of Technology, Haifa. Been from 2001 to
2007 a practicing engineer, presently
he is a Ph.D. student at the Technion.
He has a number of papers in professional journals and conference
proceedings. His main fields of interest include High-Strength and
High-Performance Concrete, Autogenous and Chemical Shrinkage,
Internal curing.
Mr. Semion Zhutovsky is a member of Israel Engineering Society.
Dr. Konstantin Kovler was born in
Moscow in 1957, received his M. Sc.
(summa cum laude) in Industrial and Civil
Construction, followed by a Ph.D. in
Structural Engineering (1978, 1986
respectively) at the Moscow State
University of Civil Engineering (MGSU),
Russia. Since 1991, upon immigrating to
Israel, Dr. Kovler has been employed at the
Technion – Israel Institute of Technology,
Haifa. He is Assoc. Professor at the Faculty of Civil and Environmental
Engineering. In 2005 Dr. Kovler has been appointed as Head of the
Building Materials and Technology Department at the National
Building Research Institute.
Dr. Kovler’s most documented area of research focuses on three main
topics: testing and behavior of early-age concrete, waterproof gypsum-
cement materials and radioactivity of building materials. He published
seven books, sixteen book chapters and over a hundred peer-refereed
papers on the subject.
A fellow of RILEM, in 2006 and 2009 Dr. Kovler organized and
chaired two international conferences on concrete durability and life
cycle planning (ConcreteLife’06, Dead Sea; and ConcreteLife’09,
Haifa). In 2002-2007, he had chaired the RILEM’ Internal Curing of
Concrete technical committee. He also served as the convener of
RILEM’ Materials Characterization, Properties Evaluation and
Processing cluster, and contributed in other multiple technical
committies. At present he serves as a member of RILEM’ Self-Healing
of Concrete, and Application of Super Absorbent Polymers committies.
At ACI, Kovler is a member of the Materials Science of Concrete
technical committee.
Dr. Kovler is a member of the editorial boards of several international
journals.
International Review of Civil Engineering, Vol. x, N. x