MICROSTRUCTURE

OF CONCRETE
By: Dr. Hana Aljewifi
 Cement hydratation
Period I: Pre-induction period
This is the initial phase that occurs at the time of mixing and only lasts a few
minutes. In contact with water, the cement grains begin to react immediately. The
initial dissolution of the anhydrous cement is marked by an important release of
heat, due to the dissolution of the aluminate phase and the alite. From the first
minutes, hydrated calcium silicate (CSH) and ettringite (TSA) are formed. During this
period, the portlandite (CH or Ca(OH)2) is not formed yet and the C3S and C3A
phases are more active.

Period II: Dormant period or induction period

This period is marked by the decrease of the heat flux related to the drop in the
dissolution rate of the anhydrous phases. The rapid rise in pH due to the increase
in the concentration of hydroxyl ions (OH-) and the accumulation of calcium ions
Ca2+ in the solution slows down this dissolution. This phase lasts a few hours and
depends on the composition. The aqueous phase is oversaturated with portlandite,
which begins to crystallize.
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 Cement hydratation
Period III: acceleration period or setting period.
The saturation of the aqueous phase with Ca²+ and OH- ions causes the precipitation of
portlandite Ca (OH)2. after ≈ 5 hours, this precipitation of portlandite will consume the ions
Ca²+ and OH- and accelerate again the dissolution of the constituents of anhydrous cement.
C-H-S that form on the periphery of anhydrous grains grow and interpenetrate while stiffening
the contacts between the grains of cement. A rapid increase in viscosity is observed and a
viscous consistency is increased to a rigid consistency. The mechanical strength of the
material begins to develop.

The setting phenomenon results from this precipitation and depends mainly on three major
conditions [Nonat and Mutin 1991]:

Coagulation of particles, under the action of Van deer Waals forces, forces electrostatic and
solvation.

Connectivity of the coagulated structure.

Rigidification of the connected structure and solidification of the resulting contacts of the
coagulation of C-S-H. 3
 Cement hydratation
Period IV: Period of slowdown or hardening
 The hydrate layers on the surface of the anhydrous grains become thicker, slowing down
the diffusion of water towards the grain surface.

 This results in a decrease in the chemical activity of the medium, and therefore the heat
flux.

 The proportion of hydration products increases and fills the porosity.

 Precipitation of hydrates occurs mainly during the acceleration and deceleration period
Hardening then follows the end of the setting.

 The exhaustion of the gypsum, visible with the fall of the sulphate concentration. The
formation of the monosulfoaluminate by reaction of Ettringite with excess aluminate is very
exothermic and rapid.

 Alkalis contained in the network crystalline C3A are then released into the aqueous phase.

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 Cement hydratation
Period IV: Period of slowdown or hardening

 The hydrates formed during these two periods are morphologically distinct.

 During the acceleration phase, the external products precipitate in the intergrain space,
initially occupied by mixing water.

 The internal precipitation products develop during the deceleration period, replacing the
anhydrous solid phase.

 The structuring of the pulp and development take place essentially during these two
periods.

 The imbrications of the multiple kinds produced contributes to the development of the
macroscopic properties (voluminal stability, mechanical resistance of the material).

 Hydration reactions continue for months or years while anhydrous cement and available
water remain, but with slower kinetics.
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 Cement hydratation
Period V: Period of slowdown (diffusion)

 This period manifests itself for several months, even several years after taking.

 The porosity of the material decreases continuously and the network hydrated products
becomes more and more dense.

 The structure of the material itself evolves by "recrystallization" and polymerization of the
previously formed products.

 In addition this last period follows the exhaustion of monosulfoaluminate and the formation
of hydrated aluminate.

 Hydrates continue to form in capillary pores, enrich themselves in alkalis, and by the play of
the solubility equilibrium of portlandite, become more and more poor in calcium.

 After 30 days, the hydrates do not contain almost more than NaOH and KOH.

 So, the solid part of the matrix is characterized by a porous network of cement grains,
bound by needles of calcium silicates. 6
Typical hydration process of cement (Mindess 2003)

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 Hydration of cement, temporal evolution
1 hr of hydration 2 hr of hydration

1: water; 2: clinker; 3: gypsum; 4: bubble;

5: sand; 6: hydrate

Mixing start period (left), dormant period (right) low ratio mortar
Microstructure: evolution during hydration. (low W/C) , simulation [Vernet*_1992].

*Vernet, C. et Cadoret, G., (1992), "Suivi en continu de l'évolution chimique et mécanique des BHP pendant les premiers jours" dans
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Les Bétons à Hautes Performances - Caractérisation, durabilité, applications, Presses de l'Ecole Nationale des Ponts et Chaussées.
 Hydration of cement, temporal evolution
4 hr of hydration 24 hr of hydration

Setting stars
P: portlandite
Setting period
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 Hydration of cement, temporal evolution
3 days of hydration 1 month of hydration

After gypsum exhaustion

Slowing down period
Dissolution of ettringite.
hardend period .
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Hydration of cement, topology

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 The hydration characteristics of cement compounds

 The rate of hydration for a cement compound can be found by evaluating the
individual compound and its percentage in the cement. The order of the rate of
hydration during the first few days is approximately C3A > C3S > C4AF > C2S .

Aluminate (C3A) and Alite (C3S) are the most reactive compounds, whereas belite (C2S) reacts much
more slowly. 12
Hydration rate of the cement
compound in a Type I cement
paste (Mindess and Young
2003 )

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 Microstructure-property relationships in the hydrated
cement paste
 It should be noted that the principal source of strength in the solid products of the
hydrated cement paste is the existence of the van der Waals forces of attraction.
 Adhesion between two solid surfaces can be attributed to these physical forces, the
degree of the adhesive action being dependent on the extent and the nature of the
surfaces involved.
 The small crystals of C-S-H, calcium sulfoaluminate hydrates, and hexagonal
calcium aluminate hydrates possess enormous surface areas and adhesive capability.
These hydration products of portland cement tend to adhere strongly not only to
each other, but also to low surface-area solids, such as calcium hydroxide, anhydrous
clinker grains, and fine and coarse aggregate particles. It is a well-known fact that
there is an inverse relationship between porosity and strength in solids.
 As stated earlier, the volume of capillary voids in a hydrated cement paste depends
on the amount of water mixed with the cement at the start of hydration and the degree
of cement hydration. When the paste sets, it acquires a stable volume that is
approximately equal to the volume of the cement plus the volume of the water.
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 Optimum Gypsum Content O.G.C
 The potential impact of excessive gypsum has thus been known for some
time, and is the reason ASTM C 150, Standard Specification for Portland
Cement contains provisions for control of sulfates in portland cement.
 Using requirements of ASTM C 150, one can optimize:
 the level of sulfates in cements to maximize strength
 and/or minimize shrinkage, without excessive expansion potential.
Cements are optimized prior to production by testing at various sulfate
levels to achieve maximum strengths in mortar cubes (and/or minimum
shrinkage of mortar prisms).
 ASTM C 150 contains numerical limits on sulfate levels that are a function of
cement type. In cases where the optimum sulfate level exceeds table limits,
the standard includes an option for a performance test that measures
expansion of mortar bars stored in water. This provides the opportunity to
optimize cements for sulfates, while protecting against the potential for
deleterious expansions.
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Optimum Gypsum Content O.G.C
 Optimum Gypsum Content O.G.C is a percentage
of gypsum that give:
 higher compressive strength.
 low drying shrinkage.
 and no excessive expansion in concrete volume
when immersed in water.

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 Factors affecting on O.G.C.

Using The Optimum Percentage of Gypsum is Very Important Because:

 It regulates the speed of the chemical reactions in the early ages.
 Prevent the local concentration of the hydration products.
 C3A content: Increase C3A content need to increase O.G.C because higher percentage will
react in short time.
 Cement fineness: Increase in cement fineness promote to increase O.G.C.
 Alkali content: Increase in alkali content means increase reaction of gypsum that leads to
increase O.G.C.
 Curing temperature: Increase in temperature of curing cause increase the reacrion of C 3A
with gypsum that means increase O.G.C.
 Curing time: Increase in curing time promote to increase O.G.C because of (Autogenously
Healing).
 Free CaO and MgO: Increase of these oxides lead to decraese in O.G.C.
 Clorides: Increase of clorides lead to decrease in O.G.C.
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 Evolution hydration of cement
The progress of hydration of cement can be determined by different means:
 The measurement of the amount of Ca(OH)2 in the paste resulted from the
hydration of the silicates.
 The heat evolved by hydration.
 The specific gravity of the paste.
 The amount of chemically combined water.
 The amount of unhydrated cement present (using X-ray quantitative analysis).
 Also indirectly from the strength of the hydrated paste.

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