Introduction

 Hydration is the collective term describing the chemical and physical

processes that take place between cement and water
 Hydration of cement is very important as it is responsible for setting
and hardening of concrete
 The chemical reaction is typically called hydration and it transforms
the cement from a powder into a cohesive matrix of significant
strength that binds the aggregate particles together.
 An exothermic chemical reaction occurs between the Portland cement
and the water
 The hydrated cement is generally called the hydrated cement paste
or hydrated cement products(hcp) for brevity.
 Generally, the water causes the hardening of concrete
through a process called hydration.

Hydration of cement Hydration of product

 Oxide Composition of cement
Major =CaO (C), SiO2 (S), Al2O3 (A), Fe2O3 (F)
Minor=MgO, SO3, Na2O, K2O and Other minor oxides
How is composition determined?
Chemical analysis
 X-ray diffraction, Optical microscopy, Scanning electron microscopy
with energy dispersive X-ray analysis, Electron microprobe analysis,
Selective dissolution and Thermal analysis
Type of Portland Chemical composition, %
Cement SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2Oeq
I (mean) 20.5 5.4 2.6 63.9 2.1 3.0 0.61

II (mean) 21.2 4.6 3.5 63.8 2.1 2.7 0.51

III (mean) 20.6 4.9 2.8 63.4 2.2 3.5 0.56

IV (mean) 22.2 4.6 5.0 62.5 1.9 2.2 0.36
V (mean) 21.9 3.9 4.2 63.8 2.2 2.3 0.48
White (mean) 22.7 4.1 0.3 66.7 0.9 2.7 0.18
The five main cement types:
CEM I Portland cement
CEM II Portland Composite cement
CEM III Blast Furnace cement
CEM IV Pozzolanic cement
CEM V Composite cement
 Portland cement is a hydraulic cement, hence it derives its
strength from chemical reactions between the cement and
water.
 Cement consists of the following major compounds
 Tricalcium silicate (Alite)= C3S

 Dicalcium silicate(Belite)= C2S

 Tricalcium aluminate(Aluminate phase)= C3A

 Tetracalcium aluminoferrite(Ferrite phase)= C4AF

 Gypsum= CSH2 (CaO .SO3.2H2O)

Towards compound composition
 Using Bogue equations, oxide compositions are converted into
approximate compound compositions
 % C3S = 4.071C – 7.700S – 6.718A – 1.430F – 2.852SO3
 % C2S = 2.867S – 0.7544(% C3S)
 % C3A = 2.650A – 1.692F
 % C4AF = 3.043F
C3S C2S C3A C4AF
48.2 22.7 8.6 13.6
Under estimate the C3S content ( and overestimates C2S) because other oxides replace some of
the CaO in C3S
Common Sources for Raw Materials
 Lime (CaO)
- Limestone, shale
 Silica (SiO2)

-Clay, sand, shale

 Alumina (Al2O3)

- Clay, fly ash, shale

 Iron (Fe2O3)

- Clay, iron ore

Portland Cement Production
 5/8 CaO Limestone or calcareous rock
 1/5 SiO2 Clay or argillaceous rock
 1/10 Al2O3 Clay or Ore
 1/20 Fe2O3 Clay or Ore
 1/20 CaSO4*2H2O Gypsum
 Type of
Potential compound composition,% Blaine fineness
portland
m2/kg
cement C3S C2S C3A C4AF
I (mean) 54 18 10 8 369
II (mean) 55 19 6 11 377
III (mean) 55 17 9 8 548
IV (mean) 42 32 4 15 340
V (mean) 54 22 4 13 373
White (mean) 63 18 10 1 482
 Chemical reactions during hydration
 When water is added to cement, the following

series of reactions occur:

 The tricalcium silicate (alite) is hydrated to produce calcium
silicate hydrates, lime and heat:
 Tricalcium silicate + water= calcium silicate hydrate + lime +
heat
2C3S + 6H=C3S2H3 + 3CH, = 120 cal/g
 The CSH has a short-networked fiber structure which
contributes greatly to the initial strength of the cement
glue.
 C-S-H is poorly crystalline material which forms
extremely small particles in the size range of
colloidal matter (< 1µm)
 CH (calcium hydroxide) is the secondary hydration

product
 Unlike the C-S-H, CH is a crystalline material with a

fixed composition
  The tricalcium aluminate react with water to produce C-A-H
C3A + H = Calcium-aluminate-hydrates (C-A-H)
 The tricalcium aluminate reacts with the gypsum in the
presence of water to produce ettringite and heat:
 Tricalcium aluminate + gypsum + water= ettringite
+ heat
C3A + 3CSH2 + 26H= C6AS3H32, = 207 cal/g
 Ettringite consists of long crystals that are only stable in a solution
with gypsum.
 The compound does not contribute to the strength of the cement glue.
 Once all the gypsum is used up as per reaction
 The ettringite becomes unstable and reacts with any

remaining tricalcium aluminate to form monosulfate

aluminate hydrate crystals:
Tricalcium aluminate + ettringite + water= monosulfate
aluminate hydrate
2C3A + 3C6AS3H32 + 22H=3C4ASH18
 The monosulfate crystals are only stable in a sulfate deficient solution.
 In the presence of sulfates, the crystals resort back into ettringite,
whose crystals are 2.5 times the size of the monosulfate.
 This increase in size that causes cracking when cement is subjected to
sulfate attack.
 The belite (dicalcium silicate) also hydrates to form calcium silicate
hydrates and heat:
 Dicalcium silicates + water=calcium silicate hydrate + lime
C2S + 4H= C3S2H3 + CH, = 62 cal/g
 This reaction generates less heat and proceeds at a slower rate,
meaning that the contribution of C2S to the strength of the cement
paste will be slow initially.
 This compound is however responsible for the long-term strength of
portland cement concrete.
 The ferrite undergoes two progressive reactions with the gypsum:
 in the first of the reactions, the Ferrite reacts with the gypsum and
water to form ettringite, lime and alumina hydroxides, i.e.
 Ferrite + gypsum + water= ettringite + ferric aluminum
hydroxide + lime
 C4AF + 3CSH2 + 3H= C6(A,F)S3H32 + (A,F)H3 + CH
 the ferrite further reacts with the ettringite formed above to produce
garnets, i.e.
 Ferrite + ettringite + lime + water=garnets
 C4AF + C6(A,F)S3H32 + 2CH +23H=3C4(A,F)SH18 + (A,F)H3
 The garnets only take up space and do not in any way contribute to
the strength of the cement paste.
 Hardened paste consists of the following:
 Ettringite - 15 to 20%
 Calcium silicate hydrates, CSH - 50 to 60%
 Calcium hydroxide (lime) - 20 to 25%
 Voids - 5 to 6% (in the form of capillary voids and entrapped and
entrained air)
 3 times as much CH produced by C3S hydration compared to C2S
 C-S-H does not have a well-defined composition
 Aluminates (C3A and C4AF), in the absence of gypsum, hydrate rapidly
to produce Calcium-aluminate-hydrates (C-A-H)
 In the presence of gypsum, ettringite (AFt) and monosulphate (AFm)
are produced (depending on the C3A to SO3 ratio)
 Why do we add gypsum to cement?
 During the cement manufacturing process, upon the
cooling of clinker, a small amount of gypsum is
introduced during the final grinding process.
 Gypsum is added to control the “setting of cement”.
 It plays a very important role in controlling the rate of
hardening of the cement.
 Portland Cement Compound Hydration Reactions (Oxide Notation)

2 (3CaO•SiO2) + 11 H2O = 3CaO•2SiO2•8H2O + 3 (CaO•H2O)

Tricalcium silicate Water Calcium silicate Calcium hydroxide
hydrate (C-S-H)

2 (2CaO•SiO2) + 9 H2O =3CaO•2SiO2•8H2O + CaO•H2O

Dicalcium silicate Water Calcium silicate Calcium hydroxide
hydrate (C-S-H)
3CaO•Al2O3 + 3 (CaO•SO3•2H2O) + 26 H2O = 6CaO•Al2O3•3SO3•32H2O
Tricalcium aluminate Gypsum Water Ettringite
2 (3CaO•Al2O3) + 6CaO•Al2O3•3SO3•32H2O + 4 H2O =3(4CaO•Al2O3•SO3•12H2O)
Tricalcium aluminate Ettringite Water Calcium mono sulfoaluminate

3CaO•Al2O3 + CaO•H2O + 12 H2O = 4CaO•Al2O3•13H2O

Tricalcium aluminate Calcium hydroxide Water Tetracalcium aluminate hydrate
4CaO• Al2O3•Fe2O3 + 10 H2O + 2 (CaO•H2O) = 6CaO•Al2O3•Fe2O3•12H2O
Tetracalcium Water Calcium hydroxide Calcium aluminoferrite
aluminoferrite hydrate
Reactivity of Cement Compounds
Non evaporable Water Contents

Non evaporable
Hydrated cement (combined) water content
compound (g water/g cement compound)
C3S hydrate 0.24
C2S hydrate 0.21
C3A hydrate 0.40
C4AF hydrate 0.37
Free lime (CaO) 0.33
 Cement hydration
 Reaction of cement with water is exothermic and heat released is called ‘Heat of
Hydration’
 Rate of heat evolution is faster if the reaction is quicker
 Heat evolved depends on heat of hydration of individual compounds
 Heat of hydration of pure cement compounds
Compound HOH (J/g)
C3S 502
C2S 260
C3A 867
C4AF 419
Bogue: ½ or (50%) of total heat is evolved between 1 and 3 days, about 75% in 7
days, and 83 – 91% in 6 months
 Heat of Hydration
 When water is added, the reactions which occur are mostly
exothermic, that is, the reactions generate heat. An illustrative
example of the heat evolution curve produced is shown in figure

 The period of maximum heat evolution occurs typically between

about 10 and 20 hours after mixing and then gradually tails off.
 In a mix containing PC only, most of the strength gain has
occurred within about a month.
 Enthalpy (H) is a measure of the total energy of a system and often
expresses and simplifies energy transfer between systems.
Exothermic Reactions Endothermic Reactions
 Exothermic reactions are reactions or  The products are higher in energy
processes that release energy, usually in than the reactants.
the form of heat or light.  Therefore, the change in enthalpy is
 In an exothermic reaction, energy is positive, and heat is absorbed from
released because the total energy of the the surroundings by the reaction.
products is less than the total energy of the  Endothermic reactions are reactions
reactants. that require external energy, usually
 For this reason, the change in enthalpy, for in the form of heat, for the reaction
an exothermic reaction will always be to proceed.
negative.
 Stages of hydration of C3S
 There are five important stages of the C3S hydration, as
described by the following calorimetric curve (i.e. time
versus rate of heat evolution curve):
 Stage-1 corresponds to a period of rapid evolution of heat, which
ceases within about 15 min.
 Stage-2 corresponds to a dormant period which lasts for several
hours during which the hydration is almost at halt. This is the reason
why the concrete remains in plastic state for several hours.
 Stage-3 corresponds to acceleration period starting at the end of
dormant period and lasting till the rate of heat evolution reaches a
maximum value. By this time (4 to 8 h) final set has been passed and
early hardening has begun
 Stage-4 corresponds to deceleration period during which the rate of
heat evolution reduces from its maximum value to a very low steady
state rate (Stage-5)
Heat evolution pattern explanation
 Peak I: ‘Heat of wetting’ + some early C-S-H formation
 Dormant period: Very slow rate of heat evolution
 Peak II: Main peak; associated with the rapid dissolution of C3S to
form CSH, CH and formation of ettringite (AFt) from C3A.
 A slowdown of the hydration process beyond the main peak leads to
lower rates of heat evolution. A broader peak (III) is associated with
the conversion of ettringite to monosulphate (AFm).

Typical heat evolution pattern

Why dormant period?
 Several theories proposed

 These theories basically point to the fact that a layer is created on

the surface of cement particles

 Further wetting of the cement particle is possible only by diffusion
across this layer
 Therefore rate slows down

End of dormant period

 Weakening of barrier by aging

 Increased rates of diffusion

 Weakening of ionic strength around the hydrating particle

 Factors affecting hydration rate
1. The phase composition of cement
2. The amount and form of gypsum in the cement:
3. Fineness of cement: Higher the fineness, higher the rate of
reaction due to availability of a larger surface area.
4. w/c of mix: At high w/c, hydration may progress till all of the
cement is consumed, while at low w/c the reaction may stop
altogether due to lack of water.
5. Curing conditions: The relative humidity can have major effects
on the progress of hydration.
6. Hydration temperature: Increase in temperature generally
causes an increase in the rate of the reaction.
7. Presence of chemical admixtures: For example, set controllers,
and plasticizers.
Effect of Temperature on C3S Hydration

 The hydration of C3S is sensitive

to temperature (i.e. there is
increase in the rate of hydration
with increase in temperature)
but only when the reaction is
chemically controlled (e.g.
stage3)
 Once hydration is completely
diffusion-controlled in stage 5, it
is much less temperature-
sensitive, although the diffusion
coefficient of the hydrate barrier
varies with temperature.
 The overall effect of temperature
on the hydration of C3S is shown
in the figure.
 Gel-like C-S-H observed Bright particles: Unhydrated cement;
Gray regions: C-S-H; white rim around
aggregates: CH

C3S mortar showing white unhydrated cement Porosity of paste in concrete

particles and gray C-S-H, along with white rims is visible in this picture
 PRODUCTS OF HYDRATION

 If one looks closely at hydrated cement paste, typically see all of the
following:
1. Capillary pores ranging from microns to millimeters in size containing
mix water that did not participate in the hydration reaction;
2. Gel products which are the hydrated calcium silicates, the hydrated
aluminates, and the hydrated ferrites. Water molecules are bonded to
these foil-like particles via hydrogen-bonding. The gel products also
have some pores, but these typically are much smaller than the
capillary pores, ranging from nanometers to microns in size.
3. Un hydrated cement particles may remain in the hydrated cement
paste (hcp) if not all of the cement in the mix hydrated.
4. Calcium hydroxide crystals may also reside in the hydrated cement
products (hcp) as an additional hydration product.
 In hydrated cement paste, microstructure showing the gel and
capillary pores, the unhydrated cement, the calcium hydroxide, and
the hydrated silicates, aluminates, and ferrites.
 Alkali-Aggregate Reaction
 Some aggregates react with the alkali hydroxides in
concrete, causing expansion and cracking over a period
of many years.
 It is a reaction between the active mineral constituents
of some aggregates and the sodium, potassium alkali
hydroxides and calcium hydroxide in the concrete.
 Alkali-aggregate reactivity normally causes expansion
and cracking of concrete. The crack pattern is commonly
identified as "map-cracking".
 Cracking of the concrete and the resultant deterioration
is generally slow, although some extremely reactive
aggregates can produce cracks within a few years.
 With time, alkali-aggregate reactivity can cause
significant expansion, severe cracking, and differential
movements in concrete components.
 The risk of sudden structural failure in concrete
components affected by AAR is almost non- existent, but
can occur in rare cases
 Concrete affected by alkali-aggregate reactivity may
pose serviceability problems
 If severe enough, result in high maintenance and
rehabilitation costs and/or the need to replace the
structure “before the end” of the anticipated service life.
 Cracking, can allow rapid increase of moisture and/or
salts, which may result in the acceleration of
deterioration due to other mechanisms.
 In making decisions about the repair and replacement of
deteriorated concrete, it is important to know the reason
for the deterioration, so that the correct repair
methodology can be adopted and safety is not
compromised.
 There are many cases in which incorrect repair
techniques have actually increased the subsequent
damage to the concrete.
 For example, when structures are affected by AAR, it is
sometimes important to provide room for subsequent
continued expansion of the concrete by cutting expansion
relief slots.
 Failure to accommodate strain caused by AAR can result
in both small concrete elements, such as sidewalks and
curbs, and in large projects, such as bridges & dams.
Two Forms of alkali-aggregate reaction:
1. Alkali-silica reaction (ASR)
2. Alkali-carbonate reaction (ACR).
 It is generally agreed that the chemical reaction

between the alkali hydroxides and reactive silica is

essentially a dissolution reaction.
 This occurs as a result of the increased solubility of

amorphous, disordered or poorly-crystallized forms of

silica minerals in high Ph -solutions.
 Alkali-silica reaction (ASR)
 Cancer of concrete
 Alkali-silica reaction (ASR) in concrete is a reaction between certain
silicious constituents in the aggregate and the alkali-sodium and
potassium hydroxide which are released during the hydration of
Portland cement.
 A gelatinous product is formed which imbibes pore fluid and in so
doing expands, inducing and internal stress within the concrete.
 The gel will cause damage to the concrete only when the following
three conditions occur simultaneously.
 a reactive form of silica is present in the aggregate in significant quantities.
 sodium, potassium and hydroxyl ions are present in the pore solution within
the concrete.
 water is available from an external source
 Alkalis + Reactive silica+ moisture= ASR gel which
expand= concrete cracking
 Alkalis= mainly Na+, K+ (sources are cement, sea
water)
 Reactive silica=Aggregate from opal, cherts, quartzite,

strained quartz crystals

(Silica tetrahedron are both amorphous and crystalline)
Amorphous are=reactive silica
ASR Mechanism
 Alkali-silica reaction (ASR) needs more concern
because aggregates containing reactive silica
materials are more common.
 In ASR, it forms a gel that swells as it adsorbs water
from the surrounding cement paste or the
environment.
 These gels can induce enough expansive pressure to
damage concrete.
• Visual Symptoms
– Network of cracks

– Closed or spalled joints

– Relative displacements
Alkali-Silica Reaction (ASR)
• Visual Symptoms (cont.)
– Fragments breaking out of
the surface (popouts)

 Mechanism
1. Alkali hydroxide +
reactive silica gel 
reaction product (alkali-
silica gel)
2. Gel reaction product +
moisture  expansion
Alkali-Silica Reaction (ASR)

• Influencing
Factors
– Reactive forms of
silica in the
aggregate,
– High-alkali (pH) pore
solution
– Sufficient moisture

If one of these conditions is absent

― ASR cannot occur.
 Controlling ASR
The problem of alkali-silica reaction can be overcome by,
 Use of non-reactive aggregates
 Use of low-alkali cement, namely cement with an equivalent sodium
oxide (Na2O) content of 0.6% by mass or less.
 Limiting the cement content to 500 kg/m3
 Use of pozzolana, slag and other substitutes for part replacement
of cement (Supplementary cementing materials or blended cements)
 Use of ASR Inhibiting salts
 Lithium-based admixtures
 Controls on service conditions, namely preventing contact between
concrete and any external source of moisture.
 Typical indicators of ASR are:
a) Random map cracking and,
b) In advanced cases, closed joints and spalled concrete.
 Cracking usually appears in areas with a frequent supply

of moisture, such as:

a. Close to the waterline in piers,
b. Near the ground behind retaining walls,
c. Near joints and free edges in pavements,
d. Or in piers or columns subject to wicking action.
Test: Petrographic examination can conclusively identify ASR.
 Petrographic analysis
 Exam the aggregate in hardened concrete
 Toidentify aggregate size, shape and amount
to determine if it is within the design
specification
The mineral varieties and rock types
responsible for ASR.
 Alkali-reactive silica- bearing rocks and minerals are
common and are found in all regions of world.
 The test methods for recognizing and evaluating the
reactive aggregates took from 3 months to 1 year.
 As a result, testing was rarely done on specific construction
jobs.
 It is hoped, with the use of new test methods and increased
awareness of AAR, that potentially reactive aggregates
will cease to be used unless adequate preventive measures
are taken.
 Figure shows Concrete thin-section, viewed with a
Petrographic microscope, showing a chert aggregate
particle (at the right of the image) from which alkali-
silica gel has extruded into adjacent cracks.
 Figure shows polished section of concrete, viewed with a
scanning electron microscope, showing a chert aggregate
particle with extensive internal cracks due to ASR. The
cracks extend from the aggregate into the nearby
concrete .
 Figure shows detail of the chert particle in the previous
image and adjacent cement paste, showing alkali-silica
gel extruded into cracks within the concrete.
 Sample of ASR in Old Concrete
 Generally, the conditions required for ASR to occur are:
 A sufficiently high alkali content of the cement (or alkali
from other sources)
 A reactive aggregate, such as CHERT
 Water - ASR will not occur if there is no available water
in the concrete, since alkali-silica gel formation requires
water
 The use of pozzolans in the concrete mix as a partial
cement replacement can reduce the likelihood of ASR
occurring as they reduce the alkalinity of the pore fluid.
 The process of ASR is believed to be in many respects
similar to the Pozzolanic Reaction, such as occurs normally
in concrete containing Pulverized Fly Ash (PFA).
Difference between Pozzolanic & ASR Reaction
 In the Pozzolanic reaction small pozzolanic particles are
reacting in a Ca-rich environment, while ASR occurs in
mature concrete and involves larger particles of
aggregate.
 Alkali- Carbonate Reaction
 The Alkali-Carbonate Reaction is a chemical reaction
between hydroxyl ions associated with the alkalis sodium
and potassium in the cement and certain dolomitic
textures in the aggregate resulting in expansion and
eventually cracking of the hardened concrete
 ACR is relatively rare because the aggregate
susceptible to this reaction is “unsuitable for concrete.”
 Dolomitic lime which contains calcite and dolomite are
common aggregate which contain small amount of
reactive carbon
 Ca(Mg)CO3+ 2(Na,K)OH = Mg(OH)2+ CaCO3+ (Na,K)2CO3
Dolomite + Alkali Brucite + Calcite + Alkali Carbonate

 LiOH also causes expansion but not at the rate that NaOH and KOH does
 Influencing factors for ACR
 Aggregates have potential for expansive ACR if the
following lithological characteristics exist
1. Clay content, or insoluble residue content, in the range
of 5% to 25%;
2. Calcite-to-dolomite ratio of approximately 1:1
3. Increase in the dolomite volume up to a point at which
interlocking texture becomes a restraining factor; and
4. Small size of the discrete dolomite crystals (rhombs)
suspended in a clay matrix.
 Materials and Methods to Control ACR.
 ACR-susceptible aggregate has a specific composition
that is readily identified by petrographic testing.
 If a rock indicates ACR susceptibility, one of the
following preventive measures should be taken:
1. Selective quarrying to completely avoid reactive
aggregate;
2. Blend aggregates according to Appendix in
ASTM C 1105
3. Limit aggregate size to smallest practical.
4. Low-alkali cement and pozzolans