LECTURE 3

MICROSTRUCTURE OF CONCRETE
DEFINITION
The type, amount, size, shape, and distribution of phases present in a solid constitute its
microstructure.

The gross elements of the microstructure of a material can readily be seen from a cross
section of the material, whereas the finer elements are usually resolved with the help of a
microscope.
The term macrostructure is generally used for the gross microstructure visible to the human
eye; the limit of resolution of the unaided human eye is approximately one-fifth of a
millimeter (200 μm).
The term microstructure is used for the microscopically magnified portion of a
macrostructure.
SIGNIFICANCE
Progress in the field of materials has resulted
primarily from recognition of the principle
that the properties originate from the internal
microstructure; in other words, properties
can be modified by making suitable changes
in the microstructure of a material
 COMPLEXITIES
At the microscopic level, the complexities of the concrete microstructure
are evident. It becomes obvious that the two phases of the microstructure
are neither homogeneously distributed with respect to each other, nor are
they themselves homogeneous.

A low-magnification (200μm) hydrated cement paste shows that the

structure is not homogeneous; while some areas are dense, the others are
highly porous.

In the porous area, it is possible to resolve the individual hydrated phases

by using higher magnifications.
For example, massive crystals of calcium hydroxide, long and slender
needles of ettringite, and aggregation of small fibrous crystals of calcium
silicate hydrate can be seen at 2000 X and 5000 X magnifications
What is Ettringite
Ettringite Ettringite
 Ettringite is a hydrous calcium aluminum
sulfate mineral with formula:
Ca6Al2(SO4)3(OH)12·26H2O
 Ettringite is formed in hydrated Portland
cement system as a result of the reaction
of calcium aluminate with calcium
sulfate, both present in Portland cement.
 It is a colorless to yellow mineral
crystallizing in the trigonal system
 COMPLEXITIES

Concrete is a composite material that consists of three phases: a cement paste,

the aggregate, and the interfacial transition zone (ITZ) between them, each of
the three phases is itself a multiphase in character.

Interfacial transition zone, which represents a small region next to the

particles of coarse aggregate. Existing as a thin shell, typically 10 to 50 μm
thick around large aggregate, the interfacial transition zone is generally
weaker than either of the two main components of concrete, namely, the
aggregate and the bulk hydrated cement paste; therefore, it exercises a far
greater influence on the mechanical behavior of concrete than is reflected by
its size.
Microstructure of the Aggregate Phase
The aggregate phase is predominantly responsible for the unit weight, elastic modulus, and dimensional stability
of concrete also largely depends on bulk density and strength of aggregates.

Determined by physical rather than chemical characteristics, the chemical or the mineralogical composition of the
solid phases in aggregate is usually less important than the physical characteristics, such as volume, size, and
distribution of pores.

Being stronger than the other two phases of concrete, the aggregate phase has usually no direct influence on the
strength of normal concrete except in the case of some highly porous and weak aggregates, such as pumice. The
size and the shape of coarse aggregate can, however, affect the strength of concrete in an indirect way.

The larger the size of aggregate in concrete and the higher the proportion of elongated and flat particles, the
greater will be the tendency for water films to accumulate next to the aggregate surface, thus weakening the
interfacial transition zone. This phenomenon, known as bleeding,
Shape and surface texture of a coarse aggregate particles

(a) gravel, rounded and smooth

(b) crushed rock, equi-dimensional

(c) crushed rock, elongated

(d) crushed rock, flat

(e)lightweight, angular and rough

(f ) lightweight, rounded & smooth

Microstructure of the Hydrated Cement Paste
The microstructure of the hydrated cement paste develops as a result of chemical reactions
between portland-cement compounds and water.

Portland cement is a gray powder composed of angular particles typically in the size range from 1
to 50 μm produced by high-temperature reactions between calcium oxide and silica, alumina, and
iron oxide. The chemical composition of the principal clinker compounds corresponds
approximately to C3S, C2S, C3A and C4AF In ordinary portland cement their respective
amounts usually range between 45 and 60, 15 and 30, 6 and 12, and 6 and 8 percent.

When portland cement is dispersed in water, the calcium sulfate and the high-temperature
compounds of calcium begin to go into solution, and the liquid phase gets rapidly saturated with
various ionic species.
Model of a well-hydrated portland-cement paste
 “A” represents aggregation of poorly crystalline C-S-H
particles which have at least one colloidal dimension (1 to
100 nm). Inter-particle spacing within an aggregation is
0.5 to 3.0 nm (avg. 1.5 nm).
 H represents hexagonal crystalline products such as
CH==C4AH19==C4AS−H18. They form large crystals,
typically 1 μm wide.
 C represents capillary cavities or voids which exist
when the spaces originally occupied with water do not get
completely filed with the hydration products of cement.
The size of capillary voids ranges from 10 nm to 1 μm,
but in well-hydrated pastes with low water/cement, they
are less than 100 nm.
Solids in the hydrated cement paste
Calcium silicate hydrate. The calcium silicate hydrate phase, abbreviated as CS-H, makes up 50 to 60
percent of the volume of solids in a completely hydrated portland cement paste and is, therefore, the most
important phase determining the properties of the paste.

Calcium hydroxide. Calcium hydroxide crystals (also called portlandite) constitute 20 to 25 percent of the
volume of solids in the hydrated paste. It tends to form large crystals with a distinctive hexagonal-prism
morphology. Compared with C-S-H, the strength-contributing potential of calcium hydroxide is limited as a result
of considerably lower surface area.

Calcium sulfoaluminate hydrates occupy 15to 20 percent of the solid volume in the hydrated paste and,
therefore, play only a minor role in the microstructure-property relationships.

Un-hydrated clinker grains Depending on the particle size distribution of the anhydrous cement and the degree
of hydration, some un-hydrated clinker grains may be found in the microstructure of hydrated cement pastes,
even long after hydration.
Voids in the hydrated cement paste
Interlayer space in C-S-H :- This void size is too small to have an adverse effect on the
strength and permeability of the hydrated cement paste. However, as discussed below, water
in these small voids can be held by hydrogen bonding, and its removal under certain
conditions may contribute to drying shrinkage and creep.
Capillary voids :- Capillary voids represent the space not filled by the solid components
of the hydrated cement paste. The total volume of a typical cement-water mixture remains
essentially unchanged during the hydration process. The space not taken up by the cement or
the hydration products consists of capillary voids.
Air voids :- Whereas capillary voids are irregular in shape, air voids are generally
spherical. A small amount of air usually gets trapped in the cement paste during concrete
mixing. Entrapped air voids may be as large as 3 mm; entrained air voids usually range from
50 to 200 μm.
Dimensional range of solids & pores in a hydrated
cement paste
Water in the hydrated cement paste
 It is not the total porosity but the pore size distribution that
actually controls the strength, permeability, and volume
changes in a hardened cement paste.
 Pore size distributions are affected by water-cement ratio,
and the age (degree) of cement hydration.
 Large pores influence mostly the compressive strength and
permeability; small pore influence mostly the drying
shrinkage and creep.
Water in the hydrated cement
paste
Water in the hydrated cement
paste
1. Capillary water:- This is the water present in voids larger than about 50 Å. It may be pictured as
the bulk water that is free from the influence of the attractive forces exerted by the solid surface.
Two categories:
o The water in large voids of the order of >50 nm (0.05 μm), which may be called free water
(because its removal does not cause any volume change).
o The water held by capillary tension in small capillaries (5 to 50 nm), the removal of which may
cause shrinkage of the system.
2. Adsorbed water:- This is the water that is close to the solid surface. Under the influence of
attractive forces, water molecules are physically adsorbed onto the surface of solids in the hydrated
cement paste. The adsorbed water can be lost when hydrated cement paste is dried to 30 percent
relative humidity. The loss of adsorbed water is responsible for the shrinkage of the hydrated cement
paste.
Water in the hydrated cement paste
3. Interlayer water:- This is the water associated with
the C-S-H structure. It has been suggested that a
monomolecular water layer between the layers of C-S-
H is strongly held by hydrogen bonding. The
interlayer water is lost only on strong drying (i.e.,
below 11 percent relative humidity). The C-S-H
structure shrinks considerably when the interlayer
water is lost.
4. Chemically combined water:- This is the water
that is an integral part of the microstructure of various
cement hydration products. This water is not lost on
drying; it is evolved when the hydrates decompose on
heating.
 Microstructure-property relationships in the hydrated
cement paste
Case A,
 100 cm3 of the cement requires 200 cm3 of water;

this sums to 300 cm3 of paste volume or total

available space.
 Assuming that under the ASTM standard curing

conditions
 The volume of cement hydrated at 7, 28, and 365
days is 50, 75, and 100 percent.
 The calculated volume of solids (anhydrous
cement plus the hydration product) is 150, 175,
and 200 cm3.
 The volume of capillary voids can be found from

the difference between the total available space

and the total volume of solids.
 This turns out to be 50, 42, and 33 percent,
respectively, at 7, 28, and 365 days of hydration.
 Microstructure-property relationships in the hydrated cement
paste
Case B
 100 percent degree of hydration is assumed
 Water-cement ratios of 0.7, 0.6, 0.5, or 0.4.
 The paste with the largest amount of water will have the
greatest total volume of available space.
 The paste with the greatest total leads to larger volume of
capillary voids.
 Thus 100 cm3 of cement at full hydration would produce 200
cm3 of solid hydration.
 The total available space in the 0.7, 0.6, 0.5, or 0.4
 Water-cement-ratio pastes was 320, 288, 257, and 225 cm3.
 The calculated capillary voids are 37, 30, 22, and 11 percent,
respectively.
 Under the assumptions made here, with a 0.32 water-
cement-ratio paste, there would be no capillary porosity
when the cement had completely hydrated.
Dimensional stability
 A combination of water-cement ratio
and degree of hydration determines
the porosity of hydrated cement paste.
 The porosity and the opposite of
porosity (solid-space ratio) are
exponentially related to both the
strength and permeability of the
material.
 The shaded area shows the typical
capillary porosity range in hydrated
cement pastes.
Significance of Interfacial Transition Zone in
Concrete
Concrete behavior lie in the interfacial transition zone
that exists between large particles of aggregate and the
hydrated cement paste. Although composed of the same
elements as hydrated cement paste, the microstructure
and properties of the interfacial transition zone are
different from bulk hydrated cement paste. It is,
therefore, treated as a separate phase of the concrete
microstructure.
Microstructure- Interfacial transition zone
Information about the interfacial transition zone in concrete is scarce, based on a description given by
Maso, some understanding of its micro structural characteristics can be obtained by following the
sequence of its development from the time concrete is placed.

First, in freshly compacted concrete, water films form around the large aggregate particles. This
would account for a higher water-cement ratio closer to the larger aggregate than away from it
(i.e., in the bulk mortar).

The bulk paste, calcium, sulfate, hydroxyl, and aluminate ions, produced by the dissolution of
calcium sulfate and calcium aluminate compounds, combine to form ettringite and calcium
hydroxide.

Owing to the high water-cement ratio, these crystalline products in the vicinity of the coarse
aggregate consist of relatively larger crystals, and therefore form a more porous framework than
in the bulk cement paste or mortar matrix.
Microstructure- Interfacial transition zone
Finally, with the progress of hydration, poorly crystalline C-S-H and a
second generation of smaller crystals of ettringite and calcium
hydroxide start filling the empty space that exists between the
framework created by the large ettringite and calcium hydroxide
crystals. This helps to improve the density and hence the strength of the
interfacial transition zone.

At early ages, especially when a considerable internal bleeding has

occurred, the volume and size of voids in the transition zone are larger
than in the bulk cement paste or mortar. The size and concentration of
crystalline compounds such as calcium hydroxide
and ettringite are also larger in interfacial transition zone. The cracks
are formed easily in the direction perpendicular to the c-axis. Such
effects account for the lower strength of the transition zone than the
bulk cement paste in concrete.
 Influence of the interfacial transition zone
on properties of concrete
The interfacial transition zone, generally the weakest link of the chain, is considered as the strength-
limiting phase in concrete.

It is because of the presence of the interfacial transition zone that concrete fails at a considerably
lower stress level than the strength of either of the two main components.

It does not take very high energy levels to extend the cracks already existing in the interfacial
transition zone, even at 50 percent of the ultimate strength, higher incremental strains may be
obtained per unit of applied stress.
This explains the phenomenon that the components of concrete (i.e., aggregate and hydrated cement
paste or mortar) usually remain elastic until fracture in a un-iaxial compression test, whereas
concrete itself shows inelastic behavior.
 Influence of the interfacial transition zone
on properties of concrete
Typical cracking maps for normal (medium-
strength) concrete:

(a) After drying shrinkage.

(b) After short-term loading.

(c) For sustained loading for 60 days at 65
percent of the 28-day compressive strength.
End of Lecture