INTERFACE SCIENCE 12, 411421, 2004

c 2004 Kluwer Academic Publishers. Manufactured in The Netherlands.

The Interfacial Transition Zone (ITZ) Between Cement Paste and Aggregate
in Concrete
KAREN L. SCRIVENER
Ecole Polytechnique Federale de Lausanne, Switzerland
karen.scrivener@epfl.ch

ALISON K. CRUMBIE
Lyon, France
PETER LAUGESEN
Dansk Beton Technik, Denmark

Abstract. This paper describes the so called interfacial transition zoneITZin concrete. This is the region of
the cement paste around the aggregate particles, which is perturbed by the presence of the aggregate. Its origin lies
in the packing of the cement grains against the much larger aggregate, which leads to a local increase in porosity
and predominance of smaller cement particles in this region. The ITZ is region of gradual transition and is highly
heterogeneous, nevertheless the average microstructural features may be measured by analysis of a large numbers
of backscattered electron images of polished concrete samples. Such measurements show that the higher porosity
present initially is significantly diminished by the migration of ions during hydration.
Keywords: cement, concrete, image analysis, scanning electron microscopy, porosity
Introduction, Importance of the ITZ
The interfacial transition zone (ITZ) between cement
paste and aggregate is the most important interface
in concrete. Concrete is often considered to be a two
phase composite materialcement paste plus aggregates. However even in the most basic phenomena the
critical role of the ITZ is clear. This is graphically illustrated by comparison of the stress strain curves for cement paste, aggregates and concrete under compression
loading (Fig. 1). Individually cement paste and aggregates both show brittle elastic behaviour, that is to say,
linear, reversible deformation up to a limit, followed by
sudden failure. In contrast, concretethe composite
materialshows significant quasi-ductile behaviour.
The load bearing capacity continues to increase beyond the linear elastic limit and there is a progressive
To

whom all correspondence should be addressed.

decrease in load bearing capacity after the peak load.

Such behaviour, which has important practical consequences, is due to the development of multiple microcracking predominantly in the ITZ. This well known
behaviour leads to the common view of the ITZ as the
weak link in concrete.
The origin of the ITZ lies in the so called wall effect
of packing of cement grains against the relatively flat
aggregate surface (Fig. 2). This is directly responsible
for the features of the ITZ, particularly its higher porosity. Due to the way it is formed the ITZ is not a definite
zone, but a region of transition. It effective thickness
varies with the microstructural feature being studied
and during the course of hydration. As cement is a
particulate material, the details of this transition zone
are different around each aggregate particle. The effect
of the ITZ on mechanical properties has already been
alluded to. The impact on transport properties is less

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Scrivener, Crumbie and Laugesen

this affects the properties of concrete. The Interfacial

Transition Zone has already been the subject of three
technical committees of RILEM, which have published
state of the art reports [1, 2].

The Origin of the ITZPacking of Cement Grains

Against Aggregate

Figure 1. Comparative stress strain curves for aggregate, paste and

concrete, the quasi-brittle behaviour of concrete illustrates the importance of the ITZ on the macroscopic properties of concrete.

straightforward, but nevertheless significant. Methods

of modifying the ITZ are critical in the development
of high performance concrete. The ITZ is also critical
in determining the effective water to cement ratio of
mortars and concretes.
The aim of this article is to present the features that
give rise to the formation of the ITZ and to discuss how

Cement grains range in size from less than a micron to

up to 100 microns. Aggregate particles are several orders of magnitude larger. This difference in size means
that each aggregate particle is a mini wall which disrupts the packing of the cement grains, resulting in the
wall effect as illustrated in Fig. 2. If a large object
were placed in a random assembly of grains, it would
cut through many grains. As this is physically impossible in the case of aggregate particles in cement paste,
the normal packing of the grains is disrupted. The result is that a zone closest to the aggregate contains predominately small grains and has a significantly higher
porosity, while larger grains are found further out.
In concrete this means that the size of the ITZ is comparable with the size of the cement grains. As packing
is a random process, each individual region of ITZ will
be differentthe ITZ is heterogeneous on the same
scale as the cement grains, therefore the average effects may not be immediately apparent in images of
concrete microstructure, as for example Fig. 3. Most
diagrams of the ITZ found in the literature do not give
a correct idea of scale. As will be discussed there is no
discrete boundary between the ITZ and the bulk paste.
The changes are progressive and are most significant
in the first 1520 m closest to the aggregate (white

Figure 2. Illustration of the wall effect. A flat solid object placed at random in an assembly of cement grains would cut through grains. As
this is impossible the packing of grains is disrupted to give a zone of higher porosity and smaller grains in the zone close to the aggregate.

Interfacial Transition Zone (ITZ) in Concrete

Figure 3.

413

Backscattered electron (BSE) image of concrete, aggregate on left. The white lines indicates distances of 20 and 50 m from interface.

lines marked on Fig. 3 are at approximately 20 and

50 m from the interface). Therefore in good quality
concretes the ITZ is NOT apparent as distinct band of
higher porosity in, for example, thin sections impregnated with florescent resin, by light microscopy.
However, even in good quality concretes, it is quite
usual to observe heterogeneities in the microstructure
on a scale of several hundred microns. Figure 4, illustrates such a case where several aggregates are clustered
together. In the oval labelled 1 the microstructure has
a significantly higher porosity. In the oval labelled 2
there is a concentration of calcium hydroxide along the
lower edge of the aggregate, but such concentrations are
not observed around all aggregates.
The challenge in characterising the ITZ is to measure
the average microstructure in real concretes. This can
be done by backscattered electron (BSE) image analysis of polished sections of concrete [36]. Results obtained from this technique (mainly from the PhD thesis
of Crumbie [6]) form the bulk of this paper. The major advantage of this technique is that the ITZ can be

studied in context in normally prepared concretes. The

disadvantages of the technique are that it is very time
consuming and that observations are made on a twodimensional sections through a three dimensional microstructure. The sectioning effect means that the distance measured on 2D sections are on average greater
than the perpendicular distances in the 3D microstructure, it has been estimated that the average lengthening
factor is around 1.2 [6]. The distances quoted here are
the uncorrected distances measured on 2D sections.
In the development of the BSE/image analysis techniques considerable work was done to establish the
number of fields which needed to be measured to obtain representative results from a concrete. With image analysis, the compromise must always be made,
between having the best resolution (highest magnification) to observe the features of interest, whilst analysing
a large enough area to be statistically significant. Different magnifications, band widths and number of fields
were studied in the PhD thesis of Crumbie [6]. As a result of these investigations the fractions of anhydrous

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Scrivener, Crumbie and Laugesen

Figure 4. BSE image of concrete illustrating typical inhomogeneities. Several aggregate grains are clustered together resulting in the formation
of a porous zone (1). Along the bottom of one aggregate there is a high concentration of calcium hydroxide (2).

cement, calcium hydroxide, other hydration products

and porosity were evaluated in 30 bands of about 3 m
in width around aggregate in 100 randomly chosen images for each concrete. Taking into account the specimen preparation, image acquisition and image analysis, several days were needed to analyse each concrete.
Therefore, this is not a technique to be applied routinely to concretes. However, the detailed study made
by Crumbie allows the way in which the ITZ forms to
be understood.
The measured distribution of unhydrated cement in
a standard concrete at a w/c = 0.4 at different ages are
shown in Fig. 5. The earliest age at which it is practical
to prepare a polished section is 1 day; by which time,
considerable reaction of the cement has already taken
place. However the original distribution can be backcalculated from the amount of unhydrated cement at
one day and the amount of hydration products. This
curve indicates that a deficit in anhydrous grains is only
significant in a region of about 15 m adjacent to the

aggregatesimilar to the size of the average cement

grain.
As hydration continues, the more detailed effects of
the disrupted packing on the grading of the cement
particles becomes apparent. The small grains quickly
hydrate completely, while the larger grains have a core
of unhydrated cement. At any given time the thickness
of each grain that has reacted will be the roughly the
same, so the unhydrated fraction will be greater for
larger grains. This explains the observation that, the
width of the zone with a reduced amount of anhydrous
material increases with age up to one year. At 1 year a
reduction in the amount of anhydrous cement is apparent over a zone of more than 40 m.
The secondary minimum at around 35 m, was
found to occur in all the concretes measured. From
this it is deduced that as smaller grains pack close
to the interface, the region further out is depleted of
small grains, so for the large grains remaining there
is less reaction of anhydrous materials between 1 and

Interfacial Transition Zone (ITZ) in Concrete

415

Figures 5 and 6. Distribution of unhydrated cement in concrete (w/c = 0.4) at various ages. From the way in which this changes during
hydration, the effect of the aggregate on the grading of the cement grains in the ITZ can be deduced (Fig. 5). Schematic representation of grading
of cement grains in ITZ (Fig. 6).

28 days. These effects are shown schematically in

Fig. 6.
Given the relatively large zone in which the packing
of the cement grains is disrupted by the aggregate particles, it is debatable if the term bulk paste really has
any meaning in concretefrom the surface area of the
aggregate and the volume of paste it can be calculated
that the average thickness of paste around aggregate
particles is only of the order of 50 m and the typical
maximum distance between aggregates seen in sections
of concrete is only a few hundred microns. However, as
already indicated, and as will be discussed further, the
most significant differences occur in a much narrower
zone.

Effective Water to Cement Ratio of Concrete

The measurements discussed above, show that the
wall effect produced by the aggregate leads to a zone
of the order of 15 m in width around each aggregate
particle, in which there are less cement grains in the
fresh state. This is equivalent to a zone of higher water
to cement ratio. In a typical concrete some 2030% of
the cement paste lies within 15 m of the aggregate.
Therefore, a higher water to cement ratio in this zone,
means that the water to cement ratio of the bulki.e.
paste more than 15 m from the aggregate must be reduced. For a concrete with an overall w/c ratio of 0.4,
the w/c ratio of this bulk paste is only around 0.35.

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Scrivener, Crumbie and Laugesen

Figure 7. Fluorescent light micrographs of thin sections of mortars with the same water to cement ratio but different sand contents. At lower
sand contents the lighter appearance of the paste indicates a higher water to cement ratio. The apparent water to cement ratio decreases with
increasing sand content.

The impact of aggregate content on the effective w/c

ratio, can be seen more dramatically in Fig. 7, from
work by Laugesen [7]. This shows a series of mortars
all with the same w/c (0.45), but with different sand
contents. The mortars are impregnated with fluorescent
resin and thin sections prepared. The individual pores

are not resolved, but the average luminosity of the hydrated areas is proportional to the amount of resin they
contain and so to their porosity.
It can be seen that as the sand content increase, the
paste areas become darker, indicating a lower porosity
due to a lower effective w/c ratio in the bulk of these

Interfacial Transition Zone (ITZ) in Concrete

417

paste areas. It is estimated that for a standard mortar

the overall w/c of 0.45 gives an effective w/c in the
bulk paste of 0.38.

Distribution of Hydration Products in the ITZ

The packing of the anhydrous cement grains is the
origin of the ITZ, but its eventual structure is also
determined by the way in which the hydration products are deposited in this region. During hydration,
the microstructural development of Portland cement is
dominated by the formation of the two major hydrate
phasescalcium silicate hydrate, C-S-H1 and calcium
hydroxide, Ca(OH)2 , CH1 . After the first few seconds,
the concentration of silicate in solution remains very
low and consequently the C-S-H phase is mostly deposited directly around the cement grains. In contrast
the concentration of calcium in solution is much higher
and calcium hydroxide is mainly deposited in the open
pores. Furthermore, it has been suggested that silica
inhibits the nucleation of calcium hydroxide, which
favours the precipitation of this phase as far from the
cement grains as possible. The resulting microstructure
is shown schematically in Fig. 8.
As explained above, the packing of cement grains
leaves an initially more porous zone around the aggregate. This favours the deposition of more calcium

Figure 8. Schematic representation of the microstructure of

Portland cement pasteC-S-H product deposits around the cement grains, while calcium hydroxide precipitates in the pore
spaces.

Figure 9.

Average distribution of calcium hydroxide in the ITZ.

hydroxide in this region as can be seen from the experimental results shown in Fig. 9. As the quantity of anhydrous material in this region is low, most of this calcium
hydroxide must form from calcium ions coming from
the reaction of anhydrous cement outside the interfacial
region. From the calculated initial distribution of the
anhydrous cement grains and the amount remaining at
a given time the amount of calcium hydroxide, coming
from the cement grains in each band can be calculated.
By comparison with the actual amounts, the amount
of excess or deficit, relative to the case of local deposition can be calculated. These calculated amounts are
shown in Fig. 10. From Figs. 9 and 10 it can be seen that
the zone of increased calcium hydroxide corresponds
very closely to the zone which is deficit in anhydrous
material on mixingi.e. has excess porosity. Most of
the excess calcium hydroxide is precipitated in the first

Figure 10. Redistribution of calcium hydroxide in the ITZthe

area of excess is the % area above that which would have been
formed from the local reaction of anhydrous material. This indicates
that there has been a net diffusion of calcium and hydroxide ions into
the 10 m closest to the aggregate.

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Scrivener, Crumbie and Laugesen

day, with a slight increase to 28 days, but negligible

further increase to one year.
Although it has been shown that the ITZ contains
excess calcium hydroxide compared to the bulk, this
amount in the ITZ is by no means a continuous layer
around all aggregates, as Fig. 3 illustrates. Even in the
3 m band closest to the aggregate the amount of calcium hydroxide is only on average around 13%i.e.
about one eighth of the total volume. Higher excesses
of calcium hydroxide may be seen locally as in Fig. 4.
These heterogeneities are a normal feature of well formulated concrete. In poorly formulated concrete microbleeding may occur and lead to the formation of
lenses of water beneath aggregate particles which become filled with calcium hydroxide. Such features were
not included in any of the measurements shown in this
paper.
With the BSE imaging technique it is not possible to
measure the orientation of the calcium hydroxide. Earlier work from the group at Toulouse University using
X-ray diffraction and progressive polishing on model
specimens, with cement paste cast against a single massive aggregate indicated that there is a preferential orientation of Calcium hydroxide with the c-axis parallel
to the aggregate surface [8].
The distribution of C-S-H and its redistribution compared to formation solely from anhydrous material in
the immediate area is shown in Figs. 11 and 12. Despite
the lower mobility of silica, there is still significant redistribution of this product between the interfacial zone
and the bulk during the first day. However, it is apparent that redistribution occurs at a more local scale
material deposited in the first 5 m is compensated by
a deficit in the next 10 (515) m. After the first day,
there is little further change over 1 year. These obser-

Figure 11. Average distribution of other hydration products, predominantly C-S-H.

Figure 12. Redistribution of C-S-H in ITZ (excess of C-S-H over

that which would be formed by the local reaction of anhydrous material).

vation confirm the lower mobility of silica (needed to

form C-S-H) compared to calcium.
The other hydrate whose distribution in the ITZ has
been studied is ettringite. Monteiro and Mehta [9] measured an increase in ettringite in the ITZ (using in model
specimens by the Toulouse XRD technique). The small
crystals of ettringite cannot be easily resolved in BSE
images, so it has not been possible to confirm this measurement in real concretes. The ions forming ettringite
are highly mobile in cement pastes, as witnessed by
the recrystallisation of ettringite into pores and voids
in mature concretes. Therefore an increased concentration of this phase in the more porous ITZ would be
expected.

Porosity in the ITZ

Porosity is the volume not filled by cement grains or
hydration products and therefore is the result of all the
effects described above. The variation in distributions
with age is shown in Fig. 13. The importance of hydrate redistribution in modifying the excess porosity
in the ITZ are clear. On mixing the porosity adjacent
to the interface is some 40% higher than that in the
bulk. After the first day this difference is reduced to
only 1020 % and the gradient is less steep. At greater
ages the porosity in the ITZ reduces by about the same
amount as it is reduced in the bulk. As there is much
less anhydrous material remaining in the ITZ, this reduction must be attributed to the deposition of hydrates
from the migration of ions from the reaction of cement
further from the interface.
These results of image analysis show how the overall amount of porosity changes in the ITZ. This overall

Interfacial Transition Zone (ITZ) in Concrete

Figure 13.

419

Average porosity in ITZ at various ages.

amount will be the major factor determining the mechanical properties of this region. However, the transport properties will depend more on the connectivity
of the porosity. It is not possible to obtain information
about connectivity from a two-dimensional polished
section of a three-dimensional structure. Nevertheless,
some other work [10] gives some indication that the
connectivity of the ITZ is increased. In this study, concrete specimens were subject to mechanical testing.
At various load levels the samples were intruded with
Woods metal while under load and subsequently sectioned and polished. In the polished sections it was
observed that the penetration of the Woods metal occurred preferentially around the aggregate particles,
which suggests a higher connectivity of the porosity
in the ITZ (Fig. 14). It must be borne in mind that the
samples treated with Woods metal were dried prior
to the experiment and heated to 80C to allow the intrusion of the Woods metal. Although this treatment
could have led to microcracking, linking pores which
were not connected in the original state, such cracks
were not seen.
What Happens Right at the Interface
We have seen that the ITZ arises from the packing of
the anhydrous cement grains, which produces a region
of high porosity in the first 1520 mm. However, the
other feature of the ITZ is what happens right at the in-

Figure 14. Concrete impregnated with Woods metal, which has

penetrated better through the ITZ.

terface. Early work on model systems [11] found that

a film of calcium hydroxide frequently precipitated in
this region. However, observations in real concretes
and mortars indicate that there is more often the precipitation of a thin layer of C-S-H directly at the interface [12]. As discussed above during the very early
stages of hydration both calcium hydroxide and C-S-H
form through solution, so the aggregate surface may

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Scrivener, Crumbie and Laugesen

act as a heterogeneous nucleation site for both phases.

Siliceous rock types are essentially inert (leaving aside
the possibilities of alkali silica reaction on much longer
time scales) and there is no chemical bonding at the interface. Calcareous aggregates may react very slightly
leading to the formation of calcium alumino monocarbonate in the ITZ.

Modification of the ITZ

Quantitative image analysis clearly shows that the ITZ
is caused by the disruption of packing the anhydrous
cement grains in this region. Thus the ITZ may be modified by changing the particle size distribution of the
cementitious materials. This is now done routinely by
adding around 510% of silica fume, which consists
of particles of amorphous silica ranging in size down
to about 100 nm (0.1 m). This technology is used
widely in the production of high strength concretes.
Early work with the backscattered electron image analysis technique by the author and Bentur [4] showed how
additions of silica fume densified the packing in the interfacial transition zone (Fig. 15). Even at 1 day the
porosity in this region is much reduced.

Consequences of the ITZ

Despite the clear difference of the ITZ from a bulk paste
it is still very difficult to precisely quantify its effect.
This is first because it is not a discrete zone but a re-

gion of gradually changing microstructure. Secondly,

the preparation of model specimens in which the properties of the ITZ can be measured separately tend to
produce different ITZs from those in real concrete.
As described in the introduction the impact of the
ITZ on mechanical properties is not in doubt. Nevertheless, evaluation of the mechanical properties of the
ITZ from those of the overall concrete is an inverse
problem. Monteiro has reviewed the possibilities for
mechanical modelling [13] and recently published an
analysis with Hashin [14] based on the generalised self
consistent scheme in which the elastic modulus of the
ITZ was estimated to be about 50% lower then the
bulk paste.
The impact of the ITZ on Transport properties, which
determine durability, is more complex and has been
well reviewed by Marchand and Delagrave [15]. Although the higher porosity and probable higher connectivity of this porosity suggest that transport of species
should be faster in the ITZ, this effect is counteracted
by several other effects:
The overall volume of the cement paste (the permeable component of concrete) is reduced.
The presence of aggregates increases the tortuousity
of the path for transport.
The porosity of the bulk paste is reduced compared
to a pure paste with the same overall w/c ratio.
Experimental studies (such as [16, 17]) in which the
aggregate content has been varied keeping the water
to cement ratio constant indicate that rates of transport are decreased as aggregate content increases, despite the increase in the amount of ITZ. This indicates
that the effects of decreasing paste volume and tortuousity outweigh any effect of increased transport in the
ITZ.
Summary

Figure 15. Distribution of Porosity in the ITZ of concretes with

and without silica fume. Adapted from [4].

The ITZ is a zone of transition not radically different to the rest of the cement paste and its effective
width depends on the microstructural feature being considered and the degree of reaction.
Quantitative characterisation of the interfacial transition zone (ITZ) between aggregate and cement paste
in concrete, confirms that it arises due to the packing
of cement grains against the larger aggregate particles. This initial packing leads to a more porous
zone some 15 to 20 m in width. The deposition of

Interfacial Transition Zone (ITZ) in Concrete

hydration products, especially calcium hydroxide

tends to fill this zone, but even in mature pastes the
ITZ still has a significantly higher porosity.
Because of the packing effect extra water is incorporated in the ITZ and the effective water to cement
ratio of the bulk paste in reduced by around 0.05.
The most effective way to modify the ITZ is to add
a proportion of fine particles, such as silica fume,
which can pack closer to the aggregate surface.
The impact of the ITZ on mechanical properties is of
considerable significance, leading to increased ductility amongst other effects.
Any impact of the ITZ on transport properties is
counteracted by other factors which generally lead
to a reduction of transport rates with increasing aggregate content if other variables are held constant.

Note
1. These abbreviations use cement chemist notation, C = CaO;
S = SiO2 ; A = Al2 O3 ; F = Fe2 O3 ; H = H2 O; the nomenclature C-S-H indicates the variable stoichiometry of this phase.

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421

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