MCE 541 – CEMENT REPLACEMENT MATERIALS

Hydration of Portland Cement

 Contents
• History of Calcerous cements
• Manufacture of Portland cement (PC)
• Basic chemistry of cement
• Hydration, setting and hardening of cement
• Strength
• Soundness
• Classification of PC
 History of Calcerous cements
• Cements may be defined as adhesive
substances capable of uniting fragments or
masses of solid matter to a compact whole.

• The term 'cements' in this restricted sense

then becomes equivalent to 'calcareous
cements', but it may be allowed to include
certain allied compounds of magnesium.
• Hydraulic cement: a material which hardens under water.

• The investigations of L.J. Vicat on hydraulic lime led him to

prepare an artificial hydraulic lime by calcining an intimate
mixture of limestone (chalk) and clay, ground together in a
wet mill. This process may be regarded as the principal
forerunner of the manufacture of Portland cement.

• 21 October 1824 by Joseph Aspdin. Aspdin was a Leeds

builder or bricklayer who was conversant with building
stones, and in his patent he described his material as
'Portland Cement'
• Portland cement is the name given to a cement obtained by
intimately mixing together calcaerous and argillaceous, or
other-silica, alumina and iron oxide bearing materials, burning
them at a clinkering temperature, and grinding the results
clinker.
 Manufacture of PC
• PC is made initially from a combination of a calcerous material
(limestone or chalk) and of silica and alumina found as clay or
shale.

• Process requires grinding of raw materials to a very fine

powder size, and mixing and burning them at around 1400 °C.
Then material sinters and fuses into clinker.

• Clinker then cooled and grinded to a fine powder (with

gypsum addition) and final PC is formed.
• Environmental concerns?
 Basic chemistry of cement
There are 4 basic compounds of PC

• Tricalcium silicate (C3S): 3CaO.SiO2 = Ca3SiO5

• Dicalcium silicate (C2S): 2CaO.SiO2 = Ca2SiO4
• Tricalcium aluminate (C3A): 3CaO.Al2O3 =
Ca3Al2O5
• Tetracalcium alumina-ferrite (C4AF): 4CaO
Al2O3Fe2O3
• Ferrite phase, Fess = solid solution in the range of C2F and C6A2F.

• C4AF is the average formula for Fess.

• C3S : Alite is used.

• Alite: Mg and Al ions replace Ca ions at random points.

• Betite: C2S with different forms. There are 5 different polymorphic forms of C2S (crystal
structures are different)

• Among those, only - C2S (belite) is cementitious.

• Hydration of Portland cement is much more complex than the simple attachment of
H2O molecules or (OH)- to cement particles.

• C3A: Reaction of C3A with water is immediate and with high heat evolution. First
hexagonal plate crystals form.
• PC consists of lime, silica, alumina and iron oxide. These compounds interact with each other to form a series
of complex products and uncombined lime which does not have sufficient time to react.

• These consist of C4AH19 and C2AH8. They are not stable at ordinary temperatures and transform into C3AH6.

• Some of lime (CaO) in C3A may be replaced by alkali oxides (Na2O, K2O) to form a compound NC8A3.

• The presence of alkalis tend to accelerate the formation of C3AH6 .

• These reactions are so rapid that without the addition of gypsum, Flash Set would occur.

• Abbreviations used for oxides:

CaO: C
SiO2: S
Al2O3: A
Fe2O3: F
Na2O: N
K2O: K
SO3: 𝑆ሶ
H2O: H
• Gypsum reacts with C3A in alkaline environment to form calcium sulfoaluminate hydrates.

• Calcium sulfoaluminate hydrates are: C6AS3H30-32 (ettringite) and C4ASH12 (monosulfate form).

• Formation of ettringite is favoured by high SO3 concentration.

• Ferrite phase (C4AF): It is not well understood.

• Products of hydration are sulfoferrites, hydrated calcium ferrites, calcium aluminates, calcium
alumino silicates, etc.

• C4AF hydration is analogous to C3A hydration, but slower.

• Hydration products are analogs of those of C3A hydration.

• C3S & C2S: The main products of hydration are C-S-H (calcium silicate hydrates) with c/s between
1.5-1.8.
• Tobermorite gel: C3S2H3

• C-S-H covers about 60% of the total volume of a hydrated cement and it
governs most of the cementitious properties.

• The composition of C-S-H changes during hydration. It varies with;

water/solids, temperature, rate of reaction.

• C3S: When C3S is mixed with water, hydration starts quickly and both lime
and silica pass into solution initially in the same molecular ratio (3/1). As
time passes, the concentration of lime increases steadily while that of
silica decreases rapidly. Crystals of CH (calcium hydroxide) and nearly
amorphous C-S-H forms. At complete hydration:
2C3S + 6H →C3S2H3 + 3CH

(tobermorite gel)
• The immediate product of hydration has c/s  3.

• This product forms a thin and almost impervious film on C3S grain.

• The film retards further reaction.

• After few hours, dissolution, precipitation, etc of this initial product results
in the acceleration of hydration and formation of C-S-H (I) with c/s  1.5 or
lower.
• Final product is C3S2H3 (tobermorite gel)

• C2S: , , ’ and  forms of C2S may be present in Portland cement.

• Among these all the -C2S is cementitious.

• The hydration products of C2S are similar to those of C3S. However the
initial product has c/s=2. Within 12 hours this converts into C-S-H(I). C-S-
H(I) in this case has c/s=1.2. C-S-H(I) is produced gradually and c/s ratio of
1.6-1.8 is attained in a year or two. Upon complete hydration;

• 2C2S + 4H →C3S2H3 + CH
(gel)
Total 93 18
 Hydration, setting and hardening of
cement
• Hydration is a reaction of an unhydrous compound with
water, yielding a new compound of hydrate.

• Non-hydrated cement + water = hydrate

• (Fresh) Paste sets and hardens.

• Setting means a rather sudden loss of plasticity of the

original paste.

• Hardening means the development of hardness and

strength that follows the setting of the paste.
Factors affecting hydration and its kinetics:
• Phase composition of the cement and the presence of foreign ions
within crystalline lattices

• Fineness of cement (particle size distribution and specific surface)

• w/c ratio

• curing temperature

• presence of chemical admixtures

• presence of additives
Hydration of pure clinker materials

• Tricalcium silicate (3CaO.SiO2, abbreviated as C3S)

• Dicalcium silicate (2CaO.SiO2, abbreviated as C2S)
• Tricalcium aluminate (3CaOAl203 abbreviated as C3A)
• Calcium aluminoferrite
 Setting
• Setting is the term used to describe the stiffening of the
cement paste.

• It refers to a change from a fluid to rigid state.

• Setting is mainly caused by a selective hydration C3A and C3S

and is accompanied by temperature rises in the cement paste;
- Initial set corresponds to a rapid rise
- Final set corresponds to the peak temperature.
• A process in which a 'fresh' cement paste of freely flowing
or plastic consistency is converted into a set material which
has lost its unlimited deformability and crumbles under the
effect of a sufficiently great external force.

• Followed by the 'hardening' of the paste in which the

hardness, strength and modulus of elasticity increase until
an ultimate value of these parameters is attained.

• Setting is a spontaneous process characteristic of all

inorganic binders. It is preceded by a 'stiffening' of the
paste.
• After mixing a Portland cement with adequate amounts of water
the cement grains are initially evenly distributed in the liquid phase.
A fresh cement paste is formed whose rheological properties (called
also 'consistency') depend on the water/cement ratio, the fineness
of the cement and its composition.

• Prior to setting, i.e. during the dormant period and at the beginning
of the acceleratory stage, the flocculation of the paste is reversible.

• In the acceleratory stage of hydration the amount of hydrated

material increases rapidly and along with it the volume of the liquid
phase declines. Chemical bonds develop at the points of contact
between the individual cement particles covered with the hydrated
material.
• The latter contacts are stronger than the ones due to van
der Waals and electrostatic forces which are responsible for
flocculation, and are not restored if broken down.

• As the amount of hydrated material increases, the number

of contacts between particles also increases and eventually
a continuous, three-dimensional network of solids develops
within the paste

• As the hydration progresses and the amount of hydrated

material increases at the expense of the water-filled pore
space, the bonds between solid particles strengthen,
resulting in a gradual increase of strength of the set paste.
• The 'normal' setting of Portland cement appears to be the
consequence of both C3S and C3A hydration and the formation
of the C-S-H and AFt phases.

• To produce a cement with acceptable setting characteristics,

calcium sulfate acting as 'set regulator' has to be added or
interground with the clinker in most instances.
 Strength
• Cement sand mortar and concrete of prescribed proportions,
made with specified materials under strictly controlled
conditions, are used for the purpose of determining the
strength of cement.

• Compression test has been the main test to characterize the

cement.
• EN 196-1 specifies cement characteristics through a mortar
prism test. The cements are described by strength classes,
with N denoting normal, and R rapid hardening properties.

• ASTM C 109-05 presribes a cement-sand mix with proportions

of 1:2.75 and a water/cement ratio of 0.485, under ASTM C
778-06 standards for making 51 mm (2inch) cubes. The mixing
and casting procedure is similar to EN 196 but cubes are cured
in saturated lime water at 23 °C.
 Soundness
• It is of high importance that the cement paste (after
setting) does not undergo a large volume change.

• There is a restriction for appreaciable expansion

otherwise, it would distrupt hardened cement paste

• This expansion could be due to reactions of free lime,

magnesia and calcium sulfate and cements exhibiting
this type of expansion are classified as unsound.
• Free lime is present in the clinker and intercrystallized with
each other compounds, it hydrates very slowly occupying a
larger volume than the original free calcium oxide.

• Free lime cannot be determined by chemical analysis of

cement because it is not possible to distinguish between CaO
and Ca(OH)2 produced by a partial hydration of the silicates
when the cement is exposed to the atmosphere.
• Magnesia reacts with water in a manner similar to CaO, but
only the crystalline form is deleteriously reactive so that
unsoundness occurs.

• Calcium sulfate is the third compound liable to cause

expansion through the formation of calcium sulfoaluminate
(ettringite) from excess gypsum (not used up by C3A during
setting).
 Classification of PC
• Two approaches are normally used to classify cements - the first is in
respect of;
- their composition,
- their performance-related properties.

• The European Prestandard ENV 197-1 and the ASTM Standards C 150-95 C
219-94 and C 595M-95 define in more detail cement and the nature of the
component materials in the following ways.
ENV 197-1 states that:
• Cement is a hydraulic binder, i.e. a finely ground inorganic material
which, when mixed with water, forms a paste which sets and
hardens by means of hydration reactions and processes and which,
after hardening, retains its strength and stability even under water.
Cement conforming to this European Prestandard, termed CEM
cement, shall, when appropriately batched and mixed with
aggregate and water, be capable of producing concrete or mortar
which retains its workability for a suflficient time and shall after
defined periods attain specified strength levels and also long-term
volume stability.
• Hydraulic hardening of CEM cement is primarily due to the hydration of calcium
silicates but other chemical compounds may participate in the hardening process,
e.g. aluminates. The sum of the proportions of reactive calcium oxide (CaO) and
reactive silicon dioxide (SiO2) in CEM cement shall be at least 50% by mass.

• ASTM Standard C 219-94 defines Portland cement as 'a hydraulic cement produced
by pulverizing portland-cement clinker, and usually containing calcium sulfate' and
blended hydraulic cement as 'a hydraulic cement consisting of two or more
inorganic constituents (at least one of which is not portland cement or portland-
cement chnker) which separately or in combination contribute to the strength-
gaining properties of the cement, (made with or without other constituents,
processing additions and functional additions, by intergrinding or other blending).
• In addition to having requirements in respect of the secondary
components which are permitted to be incorporated into the cement,
there are also chemical constraints on the cements themselves.

• ENV 197-1 also places a restriction on the amount of chloride present

since this can have an adverse effect upon the corrosion of steel
reinforcement.