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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 zone—ITZ—in 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.
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 413
Figure 3. Backscattered electron (BSE) image of concrete, aggregate on left. The white lines indicates distances of 20 and 50 µm from interface.
lines marked on Fig. 3 are at approximately 20 and studied in context in normally prepared concretes. The
50 µm from the interface). Therefore in good quality disadvantages of the technique are that it is very time
concretes the ITZ is NOT apparent as distinct band of consuming and that observations are made on a two-
higher porosity in, for example, thin sections impreg- dimensional sections through a three dimensional mi-
nated with florescent resin, by light microscopy. crostructure. The sectioning effect means that the dis-
However, even in good quality concretes, it is quite tance measured on 2D sections are on average greater
usual to observe heterogeneities in the microstructure than the perpendicular distances in the 3D microstruc-
on a scale of several hundred microns. Figure 4, illus- ture, it has been estimated that the average ‘lengthening
trates such a case where several aggregates are clustered factor’ is around 1.2 [6]. The distances quoted here are
together. In the oval labelled “1” the microstructure has the uncorrected distances measured on 2D sections.
a significantly higher porosity. In the oval labelled “2” In the development of the BSE/image analysis tech-
there is a concentration of calcium hydroxide along the niques considerable work was done to establish the
lower edge of the aggregate, but such concentrations are number of fields which needed to be measured to ob-
not observed around all aggregates. tain representative results from a concrete. With im-
The challenge in characterising the ITZ is to measure age analysis, the compromise must always be made,
the “average” microstructure in real concretes. This can between having the best resolution (highest magnifica-
be done by backscattered electron (BSE) image analy- tion) to observe the features of interest, whilst analysing
sis of polished sections of concrete [3–6]. Results ob- a large enough area to be statistically significant. Dif-
tained from this technique (mainly from the PhD thesis ferent magnifications, band widths and number of fields
of Crumbie [6]) form the bulk of this paper. The ma- were studied in the PhD thesis of Crumbie [6]. As a re-
jor advantage of this technique is that the ITZ can be sult of these investigations the fractions of anhydrous
414 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 aggregate—similar to the size of the average cement
and porosity were evaluated in 30 bands of about 3 µm grain.
in width around aggregate in 100 randomly chosen im- As hydration continues, the more detailed effects of
ages for each concrete. Taking into account the spec- the disrupted packing on the grading of the cement
imen preparation, image acquisition and image analy- particles becomes apparent. The small grains quickly
sis, several days were needed to analyse each concrete. hydrate completely, while the larger grains have a core
Therefore, this is not a technique to be applied rou- of unhydrated cement. At any given time the thickness
tinely to concretes. However, the detailed study made of each grain that has reacted will be the roughly the
by Crumbie allows the way in which the ITZ forms to same, so the unhydrated fraction will be greater for
be understood. larger grains. This explains the observation that, the
The measured distribution of unhydrated cement in width of the zone with a reduced amount of anhydrous
a standard concrete at a w/c = 0.4 at different ages are material increases with age up to one year. At 1 year a
shown in Fig. 5. The earliest age at which it is practical reduction in the amount of anhydrous cement is appar-
to prepare a polished section is 1 day; by which time, ent over a zone of more than 40 µm.
considerable reaction of the cement has already taken The secondary minimum at around 35 µm, was
place. However the original distribution can be back- found to occur in all the concretes measured. From
calculated from the amount of unhydrated cement at this it is deduced that as smaller grains pack close
one day and the amount of hydration products. This to the interface, the region further out is depleted of
curve indicates that a deficit in anhydrous grains is only small grains, so for the large grains remaining there
significant in a region of about 15 µm adjacent to the 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 Effective Water to Cement Ratio of Concrete
Fig. 6.
Given the relatively large zone in which the packing The measurements discussed above, show that the
of the cement grains is disrupted by the aggregate par- “wall effect” produced by the aggregate leads to a zone
ticles, it is debatable if the term “bulk” paste really has of the order of 15 µm in width around each aggregate
any meaning in concrete—from the surface area of the particle, in which there are less cement grains in the
aggregate and the volume of paste it can be calculated fresh state. This is equivalent to a zone of higher water
that the average thickness of paste around aggregate to cement ratio. In a typical concrete some 20–30% of
particles is only of the order of 50 µm and the typical the cement paste lies within 15 µm of the aggregate.
maximum distance between aggregates seen in sections Therefore, a higher water to cement ratio in this zone,
of concrete is only a few hundred microns. However, as means that the water to cement ratio of the “bulk”—i.e.
already indicated, and as will be discussed further, the paste more than 15 µm from the aggregate must be re-
most significant differences occur in a much narrower duced. For a concrete with an overall w/c ratio of 0.4,
zone. the w/c ratio of this bulk paste is only around 0.35.
416 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 are not resolved, but the average luminosity of the hy-
ratio, can be seen more dramatically in Fig. 7, from drated areas is proportional to the amount of resin they
work by Laugesen [7]. This shows a series of mortars contain and so to their porosity.
all with the same w/c (0.45), but with different sand It can be seen that as the sand content increase, the
contents. The mortars are impregnated with fluorescent paste areas become darker, indicating a lower porosity
resin and thin sections prepared. The individual pores due to a lower effective w/c ratio in the bulk of these
Interfacial Transition Zone (ITZ) in Concrete 417
act as a heterogeneous nucleation site for both phases. gion of gradually changing microstructure. Secondly,
Siliceous rock types are essentially inert (leaving aside the preparation of model specimens in which the prop-
the possibilities of alkali silica reaction on much longer erties of the ITZ can be measured separately tend to
time scales) and there is no chemical bonding at the in- produce different ITZs from those in “real” concrete.
terface. Calcareous aggregates may react very slightly As described in the introduction the impact of the
leading to the formation of calcium alumino monocar- ITZ on mechanical properties is not in doubt. Never-
bonate in the ITZ. theless, evaluation of the mechanical properties of the
ITZ from those of the overall concrete is an inverse
problem. Monteiro has reviewed the possibilities for
Modification of the ITZ mechanical modelling [13] and recently published an
analysis with Hashin [14] based on the generalised self
Quantitative image analysis clearly shows that the ITZ consistent scheme in which the elastic modulus of the
is caused by the disruption of packing the anhydrous ITZ was estimated to be about 50% lower then the
cement grains in this region. Thus the ITZ may be mod- “bulk” paste.
ified by changing the particle size distribution of the The impact of the ITZ on Transport properties, which
cementitious materials. This is now done routinely by determine durability, is more complex and has been
adding around 5–10% of silica fume, which consists well reviewed by Marchand and Delagrave [15]. Al-
of particles of amorphous silica ranging in size down though the higher porosity and probable higher connec-
to about 100 nm (0.1 µm). This technology is used tivity of this porosity suggest that transport of species
widely in the production of high strength concretes. should be faster in the ITZ, this effect is counteracted
Early work with the backscattered electron image anal- by several other effects:
ysis technique by the author and Bentur [4] showed how
additions of silica fume densified the packing in the in- • The overall volume of the cement paste (the perme-
terfacial transition zone (Fig. 15). Even at 1 day the able component of concrete) is reduced.
porosity in this region is much reduced. • The presence of aggregates increases the tortuousity
of the path for transport.
• The porosity of the “bulk” paste is reduced compared
Consequences of the ITZ to a pure paste with the same overall w/c ratio.
Despite the clear difference of the ITZ from a bulk paste Experimental studies (such as [16, 17]) in which the
it is still very difficult to precisely quantify its effect. aggregate content has been varied keeping the water
This is first because it is not a discrete “zone” but a re- to cement ratio constant indicate that rates of trans-
port are decreased as aggregate content increases, de-
spite the increase in the amount of ITZ. This indicates
that the effects of decreasing paste volume and tortu-
ousity outweigh any effect of increased transport in the
ITZ.
Summary
hydration products, especially calcium hydroxide 2. M.G. Alexander, G. Arliguie, G. Ballivy, A. Bentur, and J.
tends to fill this zone, but even in mature pastes the Marchand, “Engineering and Transport Properties of the Inter-
ITZ still has a significantly higher porosity. facial Transition Zone in Cementitious Composities,” Report 20
(RILEM Publications S.A.R.L., 1999).
• Because of the packing effect extra water is incor- 3. K.L. Scrivener and E.M. Gartner, in Bonding in Cementitious
porated in the ITZ and the effective water to cement Composites (Proc. Mat. Res. Soc. Symp., 114, 1988), p. 77.
ratio of the “bulk” paste in reduced by around 0.05. 4. K.L. Scrivener, A. Bentur, and P.L. Pratt, Adv. Cem. Res. 1, 230
• The most effective way to modify the ITZ is to add (1988).
a proportion of fine particles, such as silica fume, 5. K.L. Scrivener, A.K. Crumbie, and P.L. Pratt, in Bonding in Ce-
mentitious Composites (Proc. Mat. Res. Soc. Symp., 114, 1988),
which can pack closer to the aggregate surface. p. 87.
• The impact of the ITZ on mechanical properties is of 6. A.K. Crumbie, PhD Thesis, University of London, 1994.
considerable significance, leading to increased duc- 7. P. Laugesen, presentation 4th Euroseminar on Microscopy Ap-
tility amongst other effects. plied to Building Materials, June 1993.
• Any impact of the ITZ on transport properties is 8. J. Grandet and J-P. Ollivier, in Proceeding of 7th International
Congress of the Chemistry of Cement (Editions Septima, Paris,
counteracted by other factors which generally lead 1980), vol. III, pp. VII 63–68 and 85–89.
to a reduction of transport rates with increasing ag- 9. P.J.M. Monteiro and P.K. Mehta, Cement and Concrete Research
gregate content if other variables are held constant. 15, 378 (1985).
10. K.L. Scrivener and K.M. Nemati, Cement and Concrete Re-
search 26, 35(1996).
Note 11. B.D. Barnes, S. Diamond, and W.L. Dolch, Cement and Concrete
Research 8, 233 (1978).
12. K.L Scrivener and P.L. Pratt, in Proc. 8th Int. Cong. on the
1. These abbreviations use cement chemist notation, C = CaO;
Chemistry of Cements, Rio de Janeiro (1986), vol. III, p. 466.
S = SiO2 ; A = Al2 O3 ; F = Fe2 O3 ; H = H2 O; the nomencla-
13. P.J.M. Montiero, in ref. 1, p. 64.
ture C-S-H indicates the variable stoichiometry of this phase.
14. Z. Hashin and P.J.M. Montiero, Cement and Concrete Research
32, 1291 (2002).
15. J. Marchand and A. Delagrave, in ref. 2, p. 157.
References 16. A. Delagrave, J. Marchand, and M. Pigeon, Advanced Cement
Based Materials 7, 60 (1998).
1. J.C. Maso (ed.), “Interfacial Transition zone in Concrete,” RILEM 17. N.R. Buenfeld and E. Okundi, Magazine of Concrete Research
report 11 (E&FN Spon, London, 1996). 50, 339 (1998).