Advanced Concrete

Technology
Lecture notes
By
Dr. B.K. Vendhan
Asst. Professor
Dept. of Civil Engineering
SVNIT, Surat
Course Outcomes (COs):
At the end of the course the students can able to:
1. Demonstrate cement hydration and its microstructure development.
2. Understand the concepts of special concrete and its mix design procedure.

3. Apply the Rheometers and corrosion analyzer systems for measurements in

fresh and hardened concrete properties.
4. Analyze the various durability related problems in reinforced concrete and its
mitigation.
5. Create the relation of various concrete deterioration issues with microstructural
features.
 HYDRATION OF CEMENT AND ADVANCE CHARACTERIZATION TECHNIQUES
Hydration of Cements and Microstructural development, Mineral additives, Chemical admixtures,
Cracking and Volume stability, Deterioration processes, Special concretes, Advanced Characterization
Techniques, Sustainability issues in concreting, Modelling properties of concrete

 ADVANCE MIX DESIGN AND RHEOLOGY OF CONCRETE

Advanced Mixture Design, Design Philosophy - Particle Packing & Rheology - Discrete and Continuous
approach, Packing density of powders and aggregates - Experimental tests and Models, Ternary Packing
Diagram, Mixture Design of Self - Compacting Concrete (SCC); pervious concrete, Aerated concrete, Ultra
high performance fibre reinforced concrete (UHFRC), Fresh Concrete Properties, Empirical test for SCC –
Rheology, Basics, Parameters, Models, Rheometers, Rheology of Paste and concrete – Pumping, Setting,
Curing, Plastic shrinkage, Strength Development, Maturity Method; Hardened Concrete Properties,
Factors influencing strength, Interfacial Transition Zone, Stress strain relationship –Localization, End
effects, Loading Conditions; Dimensional Stability, Creep and Shrinkage
•
DURABILITY OF CONCRETE
Durability, Permeability and Porosity, Chemical attack (Sulphate attack, Delayed
Ettringite Formation, Chloride attack, Acid Attack, Sea Water attack, Carbonation,
Freezing and Thawing, Alkali aggregate reaction, Alkali carbonate reaction Corrosion,
Mode of action, failure, Tests& Protection methods.

 REBAR CORROSION AND ITS EFFECTS

Rebar Corrosion, Factors inducing rebar corrosion, electrochemical process, role of
chloride in corrosion, role of carbon-di-oxide in corrosion, onset of corrosion,
corrosion propagation, and service life prediction of concrete structures.
BOOKS RECOMMENDED:

1. Neville, A.M., 'Properties of concrete', 4th ed., Pearson Education Limited, London, 2000.
2. P. Kumar Metha and P. J. M. Monterio, Concrete- Microstructures, Properties and Materials, Indian
Edition, Indian Concrete Institute, Chennai, 1999.
3. Lea, F.M., Chemistry of cement and concrete, 3rd ed, Edward Arnold, London, 1970.
4. De Larrard, F, Concrete Mixture proportioning, A scientific Approach, E&FN Spon, London, 1999.
5. Aitcin, P. C., High Performance Concrete, E&FN Spon, London, 1998.
6. Santhakumar, A. R., Concrete Technology, Oxford University Press, New Delhi, 2007.
7. Neville, A.M., and Brooks, J. J., Concrete Technology, Pearson Education Ltd., 2012.
8. Kalliopi K. Aligizaki., Pore Structure of Cement-Based Materials: Testing, Interpretation
and Requirements, CRC Press, 2005.
COs PO1 PO2 PO3 PSO1 PSO2 PSO3

CO1 3 3 3 3 1 2

CO2 3 3 3 3 2 3

CO3 3 2 3 3 2 3

CO4 3 3 2 2 3 3

CO5 3 2 3 3 2 3
 Hydration of Cement
Hydration of Cement in Civil Engineering is basically the chemical reaction taking place
when water is added to the cement. The products formed as a result of the hydration of
cement play an important role in the strength gaining of concrete.
Importance of Hydration of Cement

• The primary function of cement in concrete is that it acts as a binding material. Hence, it binds the
aggregates together.

• Anhydrous cement (unhydrated cement) does not bind with fine or coarse aggregates. Adhesive
property is gained by cement only after hydration. Hydration products discussed later on in this
presentation possess this adhesive property.

• Thus, the hydration of cement is of prime importance in concrete technology.

 Hydration of Portland Cement

Cement consists of the following major compounds:

• Tricalcium silicate, C3S
• Dicalcium silicate, C2S
• Tricalcium aluminate, C3A
• Tetracalcium aluminoferrite, C4AF
• Gypsum, CSH2
Tricalcium aluminate + gypsum + water ® ettringite + heat
C3A + 3CSH2 + 26H ® C6AS3H32, D H = 207 cal/g

Tricalcium silicate + water ® calcium silicate hydrate + lime + heat

2C3S + 6H ® C3S2H3 + 3CH, D H = 120 cal/g

Dicalcium silicates + water ® calcium silicate hydrate + lime • Ref:(26)

C2S + 4H ® C3S2H3 + CH, D H = 62 cal/g
9
Microstructure of CBM
(i) C-S-H
(ii) C-H
(iii) Ettringite
(iv) Monosulfate
(v) Pores & Porosity

(a) Gel pores

(b) Capillary pores
(c) Air Voids

10
11
12
Hydration Process of Cement
Hydration starts in about one hour, and then hydrated products can be found too in
the cement paste. With time, the proportion of hydration products increases while
cement paste decreases.

Hydration of Major Products of Cement

As we know, cement constitutes two types of constituents, minor and major
components. Major Compounds of Cement / Bogue’s Compounds are
responsible for strength gain as only they undergo hydration.

All four major compounds of cement do not hydrate at the same rate. The rate of
hydration of aluminates is much more as compared to silicates. The stiffening of
cement paste is determined by the hydration of aluminates. The hardening of
cement paste is determined by the hydration of silicates.
Hydration of C3S, C2S, C3A, and C4AF is discussed in detail
Mechanism of Hydration of Cement

There are two mechanisms postulated explaining the process of hydration

of cement as follows:
1. Through solution mechanism of cement hydration
2. Solid state mechanism of cement hydration

1. Through solution mechanism of cement hydration

o According to through solution mechanism theory, the cement compounds
dissolve when water is added to form ionic constituents.
o Hydrates are thus formed in the solution making the solution supersaturated.
o From this supersaturated solution, products of hydration of cement are
precipitated on account of the low solubility of the hydrates.
o Complete reorganization of original constituents takes place in through solution
mechanism during hydration
2. Solid state mechanism of cement hydration [Topochemical]
• As per solid state mechanism theory, the cement compounds are in the solid state
instead of the solution form. Water attacks these compounds in solid state and
converts them into hydrated products.
• Hydration starts from the surface of the compounds. As time goes by, hydration
continues to the interior of the compounds.

Both the above mechanisms occur in the cement hydration reaction.

 Through mechanism can be presumed to be taking place during the early stages of
hydration when plenty of water is available.
 Solid state mechanism continues in the later phase of hydration when the mobility
of ions in the solution is restricted.
Complete hydration of cement particles is almost impossible. For achieving complete
hydration,
•Cement particles should be very finely ground
•It should be reground with excess water so that fresh surface is exposed to water again

Hydration of Cement Chemical Reaction

Following observations can be made from the above reactions:
C3S hydration produces 61% C-S-H and 39% Ca(OH)2. C2S hydration produces 82% C-S-H and 18% Ca(OH)2
With the large amount of C-S-H produced by C2S, it can be concluded that the ultimate strength of C2S
will be higher as compared to that of C3S.
Ca(OH)2 reduces the durability of concrete by decreasing its resistance to sulphate attack and acid attack.
With the large amount of Ca(OH)2 produced by C3S, it can be concluded that the durability of C3S will be
higher as compared to that of C3S.
From the durability point of view, either of the following measures is taken-
C3S content is limited
Pozzolana is added to remove the excess Ca(OH)2
C3S requires more water content for complete hydration as compared to that of C2S.
Products of Cement Hydration
The products of hydration of cement are:
•calcium silicate hydrates
•calcium hydroxide
•calcium aluminate hydrates
When water is mixed with anhydrous cement compounds, they form hydration compounds.
Products formed by hydration have low solubility.

Calcium Silicate Hydrates (C-S-H gel)

Calcium silicate hydrate (C-S-H gel) and calcium hydroxide (Ca(OH)2) are formed during the reaction of
C3S and C2S with water.
Calcium silicate hydrate (C-S-H gel) is the most important hydration product of Portland cement.
Structure: The hyphen between C-S-H represents the non-defined product of calcium silicate hydrate.
It is a poorly crystalline fibrous mass.
As properties in concrete are determined by the structure, the difference in composition in terms
of calcium and silica proportion is not of much significance.

Tobermorite gel: C-S-H gel is also called tobermorite gel as its structure is similar to the naturally
occurring mineral tobermorite.
C-S-H gel is the most important product formed during the hydration reaction as it determines the
favorable properties of concrete.
Initially, there was no surety that the product of both C 3S and C2S is the same, but later on, it was
proved true.

2. Calcium Hydroxide
Structure: Distinct hexagonal prism morphology
20-25 % of the volume of solids in fully hydrated cement paste comprises Ca(OH) 2.
Sulphate Attack due to Ca(OH)2: Ca(OH)2 reacts with the sulfur present in soils or water and
calcium sulfate is produced. Calcium sulfate reacts with C3A, a major compound of cement, and
results in the deterioration of concrete.
Ca(OH)2 is not advantageous owing to the following reasons-

•It is soluble in water

•It undergoes leaching making concrete porous (especially in hydraulic structures)
•It decreases the durability of concrete
•It causes the deterioration of concrete
•It promotes sulfur attack on concrete
As seen above, Ca(OH)2 is disadvantageous to concrete. The harmful effects are overcome by
the use of blending materials like fly ash, silica fume, and other pozzolanic materials.

Advantage: Ca(OH)2 is of alkaline nature so the pH is maintained around 13, hence it can
provide corrosion resistance.
3. Calcium Aluminate Hydrates

 Hydration of C3A: Calcium aluminate system (CaO-Al2O3-H2O) is formed upon the hydration of
aluminates. C3AH6 is a stable cubic hydrate formed during hydration, which can remain the same till
225 °C. Other crystalline hydrates formed are C4AH19 and C2AH8.

 C3A reacts with water immediately causing a flash set. However, gypsum added during the
manufacture of portland cement acts as a retarder to slow down its reaction. If this step is not done,
portland cement cannot be used for most of the applications.

 Hence, not hydration of C3A, but hydration of C3A in presence of gypsum is of significance. Gypsum
dissolves in water forming calcium sulphoaluminate, which is insoluble. It forms a colloidal
membrane around C3A by depositing on its surface, and its hydration is retarded .
Hydrated aluminates give no contribution to the strength of cement. Rapid hydration of
C3A may help in contributing little to the early strength of cement.

However, the hydration of aluminates makes the concrete prone to sulphate attack.
Thus, it affects the durability of concrete and is rather not desirable.

Hydration of C4AF: Hydration of C4AF forms a system of (CaO-Fe2O3-H2O). C3FH6 is

a hydrated product, which is comparatively more stable.

Even this does not contribute to the strength. But, hydrates of C3AH6 show more
resistance to sulphate attack as compared to the hydrates of C3A.

Gypsum and alkalies decrease the solubility of C3A.

Either of the following precipitates is obtained-

•Ettringite: calcium aluminate trisulphate hydrate (C6AS3H22)

•Monosulphate: calcium aluminate monosulphate hydrate (C4ASH18)

Ettringite
•Ettringite hydrates and crystallises first owing to the high sulphate/aluminate ratio in the solution
phase, i.e. during the first hour of hydration.

•When sulphate concentration is reduced, aluminate concentration increases owing to the hydration of
C3A and C4AF. Now, ettringite becomes unstable.

•Gradually, ettringite forms monosulphate when sulphate concentration declines and that of aluminate
rises.

•Cement containing >5 % C4A will have the final product of monosulphate.
Importance of Products of Hydration of Cement

Adhesive or cementing property in cement is attributed to the products of hydration only.

Following aspects of hydration products of cement are important-

•Quality

•Quantity

•continuity of formation

•Stability

•rate of formation
Is it Correct to Call Hydration Products as Gel?

Not exactly.

Le Chatelier gave crystalline theory in which he stated that the hydration products are precipitates
resembling crystals interlocked with each other.

Michaelis gave colloidal theory in which he mentioned precipitates as a colloidal mass of gelatinous
nature.

Now, it is accepted that the products of hydration are more like gel in which poorly formed thin
fibrous crystals of infinitely small size are present.

Gel makes the concrete porous. Its porosity is 28%. The gel pores are filled with water.
Structure of Hydrated Cement
To understand the behaviour of concrete, the study of the structure of hydrated cement becomes
important.

At the macro-phase level, concrete is a 2-phase material comprising –

•paste phase
•aggregate phase
Aggregate particles are dispersed in cement paste. Paste structure is more important as it governs the
following properties of concrete –
•strength
•permeability
•durability
•drying shrinkage
•elastic properties
•creep
•volume change properties

At the microscopic level, 3rd phase is also seen – the transition zone .
Transition Zone
•It is visible only at a microscopic level, presumably the third phase of concrete.

•It is the region between the particles of coarse aggregates and hardened cement paste observed in the
vicinity of large aggregate particles.

•Water accumulates below the elongated and flaky aggregates due to internal bleeding. This reduces
the bond strength in this region.

•Transition zone is important, as it is a plane of weakness in concrete. Internal bleeding and such factors
make the quality of cement paste poor in this region.

•Even before loading, micro-cracks develop in this region because of drying shrinkage or temperature
variation. When the structure is loaded, these cracks propagate into bigger cracks.

Thus, the transition zone is the strength limiting phase in concrete. This is because concrete may fail at
lower stress than that resisted by bulk paste or aggregates .
Unhydrated Core
In cement grains, the hydration of cement compounds adheres firmly to its unhydrated core.

However, the unhydrated portion left in the cement grain does not affect the strength gain of the
cement mortar or concrete.

The only condition being the mortar or concrete should be well compacted.
To prove this, Abrams obtained strength of 280 MPa at only a 0.08 w/c ratio. At such a low w/c ratio,
hydration will occur only at the surface and most of the cement particles at the core would remain
unhydrated.

Still, high strength could be obtained.

Present day high performance concrete is obtained at a w/c ratio of 0.25. In this too, the core remains
unhydrated.

The unhydrated cement core works like fine aggregates in the system.
Water Requirement for Hydration of Cement

 Minimum water cement ratio for full hydration of cement is 38 %.

 Out of this, 23% is bound water while 15% is gel water.
 Water participating in the hydration reaction is not available and is called bound water. Water
filling up the gel pores is called gel water.
 Both bound water and gel water are complementary to each other.
 If enough water is not available to fill the gel pores, then the formation of the gel will be stopped.
 With a w/c ratio of 0.38, complete hydration will take place with no excess water.
 Excess water, if present, forms the capillary cavities in the concrete. The capillary cavities
increase porosity and are undesirable.
 Full hydration with a 0.38 w/c ratio is based on the assumption that hydration takes place in an
airtight system, where the exchange of moisture is not possible.
In general practice, complete hydration of cement is never achieved, hence w/c
ratio less than 0.38 is also used. Especially for high performance concrete, a w/c
ratio < 0.38 is used to avoid capillary activities.

Now, the volume of gel is twice the volume of unhydrated products. Production of
gel increases with the hydration of cement. The gel fills up the space occupied by
water earlier.

However, at a w/c ratio above 0.7, the gel will never be enough to fill up the space
occupied by water. Hence, the concrete will remain a porous mass.

Excess water in the concrete is undesirable. Effects of Excess Water in

Concrete are described HERE.
Heat of Hydration of Cement

Hydration of cement is an exothermic reaction. Hence, heat is liberated during the process. This heat
is termed as the heat of hydration.

Heat of hydration can be defined as the quantity of heat evolved in joules per gram of cement upon
complete hydration at a particular temperature.

(Heat of hydration can be proved by the following- Take freshly mixed concrete in a vacuum flask and
note its temperature at different intervals. Note the rise in temperature.)

The heat of hydration reaction is not an instantaneous reaction. The reaction is faster in the earlier
stage and it continues indefinitely at a decreased rate.

The depth of hydration at 28 days is only 4 μ.

 Heat of Hydration of Different Cement
Components

Compound Heat of Hydration

(J/g) (cal/g)

C 3S 502 120

C 2S 260 62

C 3A 867 217

C4AF 419 100

Heat of hydration of OPC cement at different time intervals is
tabulated below:

3-Days 90-Days 13-Years

Compound Heat of Heat of Heat of Hydration
Hydration Hydration

C3 S 58 cal/g 104 cal/g 122 cal/g

C2 S 12 cal/g 42 cal/g 59 cal/g

C3 A 212 cal/g 311 cal/g 324 cal/g

C4AF 69 cal/g 98 cal/g 102 cal/g

It can be noted from the above table that C3A gives the highest heat of hydration. The major
compounds in the sequence of the liberation of the heat of hydration are as follows:
C3A > C3S > C4AF > C2S
Importance of Heat of Hydration

In Mass Concreting:

•Control of heat of hydration is particularly important in mass concreting as in concrete dam

construction.
•The temperature at the inside of the concrete mass is 50 times more than that of the original
temperature at the time of placing of concrete. it continues to remain so for a prolonged time.
•This temperature rise is due to the fact that the mass concrete cools only from the surfaces
exposed to the atmosphere.
•The interior parts remain heated as the heat is released during the hydration of cement is trapped
inside.
•If this heat is not allowed to escape, a rapid increase in the strength of interior concrete will be
observed.
•Cooling of outer surfaces, while the inner concrete remains heated, induces stresses in concrete
resulting in shrinkage cracks.
•Hence, the study of the heat of hydration and its control measures is important .
In Cold Weather Concreting:
•Heat of hydration is desirable in cold weather concreting when the ambient
temperature is too low to activate the hydration reactions.
Early heat of hydration is attributed to the hydration of C3S. As hydration of
C3A is controlled by the retarders added to the cement for the purpose of
preventing the flash setting of cement.

Heat of hydration Time

50% 1 & 3 days
90% 6 months
Total Heat of Hydration in cement depends on the relative quantity of the
major compounds of cement.

Total heat of hydration of cement is independent of the fineness of the cement.

Heat of Hydration Test of Cement

The nature of hydration can be deduced by measuring the heat evolved during
the hydration reaction.

Almost half of the total heat is liberated in the first 3 days.

Rate of Hydration of Cement
Different compounds are present in cement hydrate at different rates.
The heat of hydration liberated by different compounds varies too.
Heat liberation after the setting of cement is described in the graph
below:
Ascending Peak A
A rapid heat evolution takes place when water is added to cement, which is shown by the ascending peak A.
This instant heat evolution is because of the reaction of the solution of aluminates and sulphates.
However, the peak does not last long as gypsum present in cement decreases the solubility of aluminates.

Ascending Peak B
Ettringite formation in cement results in the ascending peak B after 4-8 hours of hydration. This heat is liberated
by the reaction of C3S (ettringite).
Fineness of cement affects the rate of hydration of cement; but not the total heat of hydration.
Rate of Hydration of Pure Cement Compounds
Rate of hydration is the fastest in C4AF as seen from the above graph. The sequence of
Bogue’s compounds in ascending order of rate of hydration is: C 4AF > C3A > C3S > C2S.
Rate of Hydration v/s Time Graph
 Remarks (wrt
Reaction Stage Rate of Reaction Chemical Process
concrete)

Stage 1 rapid dissolution of ions

continued dissolution
Stage 2 slow determines initial set
of ions

formation of determines: final set

Stage 3 rapid
hydration products & initial hardening

continued formation determines rate of

Stage 4 slow
of hydration products early strength gain

gradual formation of determines rate of

Stage 5 slow
hydration products ultimate strength gain
Key Take Away
The chemical reaction of the cement powder with water is termed as hydration
of cement.
The useful binding property of cement is because of the hydrated products of
cement, unhydrated cement does not possess it.
Mechanism of Cement Hydration
Through solution mechanism– Cement compounds dissolve in water forming
supersaturated solution. From this solution, precipitates of hydrates are
obtained.
Solid state mechanism– Water reacts with the solid constituents forming
hydrated products.
Important observations from cement hydration:
•Ultimate strength of C2S will be higher as compared to that of C3S.
•Durability of C3S will be higher compared to that of C3S.
•C3S requires more water content
Products of Cement Hydration:
1.calcium silicate hydrates (C-S-H gel)
2.calcium hydroxide (Ca(OH)2)
3.calcium aluminate hydrates (CaO-Al2O3-H2O)
Hydrated Product Structure % by Vol Use Remarks

– Determines properties of
Silicates (C-S-H gel) Non-defined; poorly defined 50-60 % hardened concrete
crystalline mass
– Contributes to strength gain

– Increases porosity
Ca(OH)2 Distinct hexagonal prism Maintains alkaline pH reducing – Decreases durability
morphology 20-25 % corrosion risk – Increases risk of sulphur
attack

– Flash setting can be caused if

Early strength of concrete (little gypsum
is not there
Aluminates (Ettringite &
Crystalline – Decreases durability
Monosulphate) amount)
– Increases risk of sulphur
attack
Structure of Hydrated Cement:

3 phase cement structure is observed at a microscopic level-

•paste phase
•aggregate phase
•transition zone – strength limiting phase

Heat of hydration Definition: The amount of heat liberated in joules per gram of cement during
the process of complete hydration at the specified temperature.
Heat of hydration is useful in cold weather concreting while undesirable in mass concreting.

Total Heat of Hydration in cement depends on the relative quantity of the major compounds of
cement and not on the fineness of the cement.

Rate of heat of hydration depends on the fineness of the cement.

Water required for the hydration of cement is 38%. (23% as bound water and 15% as gel
water).

For complete hydration of cement, the w/c ratio needed is 0.38.