LECTURE # 04

Chemistry of
Cement
Manufacturing

Dr Tehmina Ayub
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Dr Tehmina Ayub
CONCRETE CONSTITUENT BY VOLUME
PEERCENTAGE

Dr Tehmina Ayub
Sources:

Dr Tehmina Ayub
 Cement Manufacturing Process

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Basically, clay is an alumina silicate and the formula is Al2O3 2SiO2 2H2O, but
it is never found in pure form. There are several different clay minerals; for
example: Kaolinite - a clay mineral with the chemical
composition Al2Si2O5(OH)4.
Dr Tehmina Ayub
The composition of sand varies, depending on the local rock sources and
conditions, but the most common constituent of sand in inland continental
settings and non-tropical coastal settings is silica (silicon dioxide, or SiO2),
usually in the form of quartz.
 Cement Manufacturing Process

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Dr Tehmina Ayub
Metakaolin
 Cement Manufacturing Process

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Dr Tehmina Ayub
Metakaolin

C
A

CEMENT
 C

S A F H

C3S
C2S
C3A
C4AF

Dr Tehmina Ayub
 Cement Manufacturing Process

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 Cement Manufacturing Process

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Dr Tehmina Ayub
Dr Tehmina Ayub
 Chemical shorthand
Because of the complex chemical nature of cement, a shorthand
form is used to denote the chemical compounds. The shorthand
for the basic compounds is:

Dr Tehmina Ayub
XRF (X-ray fluorescence) is a non-destructive analytical
technique used to determine the elemental composition of
materials. XRF analyzers determine the chemistry of a sample
by measuring the fluorescent (or secondary) X-ray emitted
from a sample when it is excited by a primary X-ray source.

Dr Tehmina Ayub
 Cement - Raw Materials
(1) Limestone :- Contains predominantly calcium carbonate (CaCO3) and
to use in cement manufacture, it should have 42-43% lime (CaO)
minimum. In cement manufacture, it is prime raw material and its usage
would be 90- 93%.
(2) Clay :- It contains more of silica (SiO2) and its usage should be 2 to 3%
in cement manufacture.
(3) Bauxite :- It contains alumina (Al2O3) and it’s usage should be 2 to 3%
in cement manufacture.
(4) Iron Ore :- It contains mainly iron oxide (Fe2O3) and it’s usage should
be 1 to 2% in cement manufacture.
The raw materials mix composition would be 90-93% limestone, 2- 3%
clay, 2-3% Bauxite, 1-2% Iron ore in cement making.
Fuel: Coal is used for burning the raw mix in powdered form. Normally
both imported and indigenous coal are used, coal is being imported
from mainly South Africa, Australia etc. because of low ash content. Pet
coke is also used as alternate fuel while manufacturing of cement.
Dr Tehmina Ayub
VIEW OF CEMENT PLANT

Dr Tehmina Ayub
 Chemical Name Chemical Formula Shorthand Notation Percent by Weight
Tricalcium Silicate 3CaO×SiO2 C3S (Alite) 50
Dicalcium Silicate 2CaO×SiO2 C2S (Belite) 25
Tricalcium Aluminate 3CaO×Al2O3 C3 A 12
Tetracalcium Aluminoferrite 4CaO×Al2O3×Fe2O3 C4AF (Ferrite) 8
Gypsum CaSO4×H2O CSH2 3.5

http://python.rice.edu/~arb/Courses/360_04_cement.pdf
 Gypsum
(3.5%) Other
(1.5%)

Tetracalcium Aluminoferrite
(8%)

Tricalcium Aluminate
(12%)
Tricalcium Silicate
(50%)

Dicalcium Silicate
(25%)
 CC33SS
C2S
C2S
C4AF

C3A
C3A
 (Belite)
C2S
(Alite) (Belite)

C3S
(Alite)
(Ferrite)
C3A

C4AF
(Ferrite)
 (Belite)
C2S
(Alite) (Belite)

C3S
(Alite)
(Ferrite)
C3A

C4AF
(Ferrite)
• C3S and C3A are mainly responsible for the strength of the cement.
• High percentage of C3S (low C2S) results in high early strength but also high heat
generation as the concrete sets.
• The reverse combination of low C3S and high C2S develops strengths more slowly
(over 52 rather than 28 days) and generates less heat.
• C3A causes undesirable heat and rapid reacting properties, which can be prevented
by adding CaSO4 to the final product.
• C3A can be converted to the more desirable C4AF by the addition of Fe2O3 before
heating, but this also inhibits the formation of C3S. C4AF makes the cement more
resistant to seawater and results in a somewhat slower reaction which evolves less
heat.
HYDRATION PRODUCTS - 𝑪𝟑 𝑨 𝒂𝒏𝒅 𝑪𝟒 𝑨𝑭

1. 𝑪𝟑 𝑨 hydrates are prone to sulphate attack.

2. 𝑪𝟑 𝑨 hydrates very quickly so gypsum is added. (how
gypsum slows down hydration?)
3. 𝑪𝟒 𝑨𝑭 hydrates are relatively more stable and thus, less
prone to sulphate attack.
Since mostly, gypsum is added in the cement, hydrates
formed in the presence of gypsum are of more interest for
𝑪𝟑 𝑨 𝒂𝒏𝒅 𝑪𝟒 𝑨𝑭.
1. Gypsum and alkalis go into solution together and solubility
of the 𝑪𝟑 𝑨 is decreased.
2. Depending on the sulphates present following products
are formed.
• 𝑪𝟑 𝑨 + 𝑯 → 𝑪𝑨𝑺𝟑 𝑯 -> ettringite (prone to sulphate attack)
• 𝑪𝟒 𝑨𝑭 → 𝑪𝑨𝑺𝑯 -> (stable compound than ettringite)
 TYPES OF CEMENT – ASTM

type description composition uses

TYPE I General Purpose High 𝐶3 𝑆 General purpose
TYPE II Moderate Sulphate Low 𝐶3 𝐴 Hydraulic, underground structures
Resistance
TYPE III High Early Strength High 𝐶3 𝑆 Rapid formwork removal
TYPE IV Low Heat (Slow Low 𝐶3 𝑆 (more 𝐶2 𝑆) Mass concrete
Hardening)
TYPE V Very High Sulphate Even lower 𝐶3 𝐴 Hydraulic, underground structures
Resistance
 LECTURE # 05
Cement Hydration Process

Dr Tehmina Ayub
 Overview of the Hydration Process

Removal of Formwork
after 24 hrs

Reaction
due to water
sprinkling

Reaction due
to water
added during
concrete
mixing

Hydration Reaction
Wet Concrete of Cement Paste Hardened Concrete

Dr Tehmina Ayub
 Overview of the Hydration Process
• The hydration of cement is a two-step process.
• In the first step, called “dissolution”, the cement dissolves,
releasing ions into the mix water.
• The mix water is thus no longer pure H2O, but an aqueous solution containing a
variety of ionic species, called the pore solution.
• The gypsum and the cement minerals C3S and C3A are all highly soluble,
meaning that they dissolve quickly.
• Therefore, the concentrations of ionic species in the pore solution increase
rapidly as soon as the cement and water are combined.

• The concentrations increase to the point that the pore

solution is supersaturated, meaning that it is energetically
favorable for some of the ions to combine (Ettringite)
into new solid
phases rather than remain dissolved. This second step of
the hydration process is called “precipitation”.
 Overview of the Hydration Process
• The hydration of cement is a two-step process.
• In the first step, called “dissolution”, the cement dissolves,
releasing ions into the mix water.
• The mix water is thus no longer pure H2O, but an aqueous solution containing a
variety of ionic species, called the pore solution.
• The gypsum and the cement minerals C3S and C3A are all highly soluble,
meaning that they dissolve quickly.
• Therefore, the concentrations of ionic species in the pore solution increase
rapidly as soon as the cement and water are combined.

• The concentrations increase to the point that the pore

solution is supersaturated, meaning that it is energetically
favorable for some of the ions to combine into new solid
phases rather than remain dissolved. This second step of
the hydration process is called “precipitation”.
Microscopic Image of Cement paste
 Overview of the Hydration Process
• These new precipitated solid phases, called “hydration products”,
are different from the starting cement minerals.
• Precipitation relieves the supersaturation of the pore solution
and allows dissolution of the cement minerals (C3S, C3A) to
continue. Thus, cement hydration is a continuous process by
which the cement minerals are replaced by new hydration
products, with the pore solution acting as a necessary transition
zone between the two solid states.
• The reactions between Portland cement and water have been
studied for more than a hundred years, and the fact that hydration
proceeds by a dissolution-precipitation process was first
elaborated by the famous chemist Le Chatelier [1].
 Overview of the Hydration Process
Stage I: Rapid evolution of
According to the figure, the rate of
heat, lasts about
cement hydration over time, with the 15 minutes.
hydration process divided into four
somewhat arbitrary stages.
Stage 1
when cement and water are first
combined there is a short period of fast
reaction and heat output as the cement
dissolves, lasting for less than one
minute.
Stage 1 is brief because of the rapid Schematic of the rate of hydration or heat
formation of an amorphous layer of evolution as a function of time.
hydration product around the cement After 24 hrs. of mixing
particles, which separates them from
the pore solution and prevents further
rapid dissolution.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
 Overview of the Hydration Process
Stage 2

Stage 1 is followed by the “induction

period”, during which almost no
reaction occurs.

The precise nature of the induction

period, and in particular the reason for
its end, is not fully known, or perhaps
it should be stated that it is not fully
agreed upon, as there are strongly
held but differing opinions among Schematic of the rate of hydration or heat
cement chemists. The induction evolution as a function of time.
period will be discussed later.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
 Overview of the Hydration Process
Stage 2

Stage 1 is followed by the “induction

period”, during which almost no
reaction occurs.

The precise nature of the induction

period, and in particular the reason for
its end, is not fully known, or perhaps
it should be stated that it is not fully
agreed upon, as there are strongly
held but differing opinions among Schematic of the rate of hydration or heat
cement chemists. The induction evolution as a function of time.
period will be discussed later.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
 Overview of the Hydration Process
Stage 3

Stage 3 is a rapid reaction period.

During this period, the rate of reaction
increases rapidly, reaching a maximum
at a time that is usually less than 24
hours after initial mixing, and then
decreases rapidly again to less than
half of its maximum value.

This behavior is due almost entirely to

the hydration of the C3S, and the rate of Schematic of the rate of hydration or heat
hydration is controlled by the rate at evolution as a function of time.
which the hydration products nucleate
and grow.
Both the maximum reaction rate and the time at which it occurs depend strongly on
the temperature and on the average particle size of the cement. This reaction
period is sometimes divided into two stages (before and after the maximum rate)
but as the rate-controlling mechanism is the same throughout (nucleation and
growth) it is preferable to treat this as single stage.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
 Overview of the Hydration Process
Stage 3
At the end of Stage 3, about 30% of the
initial cement has hydrated, and the
paste has undergone both initial and final
set.
Stage 3 is characterized by a continuous
and relatively rapid deposition of hydration
products (primarily C-S-H gel and CH) into
the capillary porosity, which is the space
originally occupied by the mix water.

This causes a large decrease in the total Schematic of the rate of hydration or heat
pore volume and a concurrent increase in evolution as a function of time.
strength. After 24 hrs. of mixing

The microstructure of the paste at this point

consists of unreacted cores of the cement
particles surrounded by a continuous
layer of hydration product, which has a
very fine internal porosity filled with pore Black=water (pores), Red = C3S, Blue = C2S
solution, and larger pores called capillary
pores.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
Dr Tehmina Ayub
Dr Tehmina Ayub
Dr Tehmina Ayub
 The Hydration Reactions
Hydration of the calcium silicate minerals (C3S and C2S)

Tricalcium silicate (C3S) is the most abundant and important cement mineral in
Portland cements, contributing most of the early strength development. The
hydration of C3S can be written as:

2C3S + 6 H  C3S2H3 +3 CH (1)

where C3S2H3 is the calcium silicate hydrate (C-S-H) gel phase and CH is calcium
hydroxide, which has the mineral name portlandite.

The kinetics of hydration of C3S are substantially similar to those of Portland

cement as a whole (see Figure). Much of the reaction occurs during the first few
days, leading to substantial strength gains and reduction in capillary porosity.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.html
 The Hydration Reactions
Hydration of the calcium silicate minerals (C3S and C2S)

The dicalcium silicate phase (C2S) reacts according to:

2C2S + 6 H  C3S2H3 + CH (2)

The hydration products are the same as those of C3S, but the relative amount
of CH formed is less. C2S is much less soluble than C3S, so the rate of
hydration is much slower. C2S hydration contributes little to the early strength
of cement, but makes substantial contributions to the strength of mature
cement paste and concrete.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.html
 Hydration of Cement
Formation of Calcium Silicate Hydrate (C-S-H)

2C3S + 6H → C3S2H3 + 3CH (ΔH = -500 J/g)

Moderate reaction rate, gives high strength and heat

liberation

2C2S + 4H → C3S2H3 + CH (ΔH = -250 J/g)

Slow reaction rate, gives low initial but high later strength,
and low heat liberation

Overall reaction:
Calcium silicates (C3S + C2S) + water → C-S-H + Ca(OH)2

Young et al.
 Hydration of Cement
Formation of Calcium Silicate Hydrate (C-S-H)

Young et al.
 HYDRATION PRODUCTS - 𝑪𝟑 𝑺 𝒂𝒏𝒅 𝑪𝟐 𝑺

•𝑪𝟑 𝑺 produces less 𝑪 − 𝑺 − 𝑯 and higher

𝑪𝒂(𝑶𝑯)𝟐
•𝑪𝟑 𝑺 produces more heat of hydration
(contribution to early or late strength?)
•C-S-H produced by 𝑪𝟑 𝑺 is less dense

•Vice versa for 𝑪𝟐 𝑺

 Chemical shorthand
Because of the complex chemical nature of cement, a shorthand
form is used to denote the chemical compounds. The shorthand
for the basic compounds is:

Dr Tehmina Ayub
 LECTURE # 06
Cement Hydration Process

Dr Tehmina Ayub
 The Hydration Reactions
Hydration of the calcium aluminate (C3A)
The hydration of the aluminate and ferrite minerals is somewhat more complex than that of the
calcium silicate minerals, and the reactions that take place depend on whether sulfate ions are
present in the pore solution. C3A is highly soluble, even more so than C3S. If C3A is hydrated in
pure water, calcium aluminate hydrates form. The reaction sequence is:

2C3A + 21H  C4AH19 + C2AH8  2C3AH6 + 9H (3)

where the first reaction is very rapid and the second reaction occurs more slowly. The final
reaction product, C3AH6, is called hydro garnet.

The initial reaction is so rapid that if it is allowed to occur in a Portland cement paste it would
release large amounts of heat and could cause the paste to set within a few minutes after
mixing, an undesirable condition known as flash set.
The purpose of adding gypsum (C S ഥ H ) to Portland cement is to prevent this from
2
happening. The gypsum is also highly soluble, rapidly releasing calcium and sulfate ions into
the pore solution. The presence of the sulfate ions causes the C3A to undergo a different
hydration reaction. The reaction of C3A and gypsum together is:

ഥ + 26H
C3A + 3CSH  ഥ H (Mineral Ettrengite)
C6AS (4)
2 3 32

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_2.html
The Hydration Reactions
Hydration of the calcium aluminate (C3A)

Dr Tehmina Ayub
 HYDRATION PRODUCTS - 𝑪𝟑 𝑨 𝒂𝒏𝒅 𝑪𝟒 𝑨𝑭
1. 𝑪𝟑 𝑨 hydrates are prone to sulphate attack.
2. 𝑪𝟑 𝑨 hydrates very quickly so gypsum is added. (how gypsum slows
down hydration?)
3. 𝑪𝟒 𝑨𝑭 hydrates are relatively more stable and thus, less prone to
sulphate attack.
Since mostly, gypsum is added in the cement, hydrates formed in the
presence of gypsum are of more interest for 𝑪𝟑 𝑨 𝒂𝒏𝒅 𝑪𝟒 𝑨𝑭.
1. Gypsum and alkalis go into solution together and solubility of the
𝑪𝟑 𝑨 is decreased.
2. Depending on the sulphates present following products are formed.
• 𝑪𝟑 𝑨 + 𝑯 → 𝑪𝑨𝑺𝟑 𝑯 -> ettringite (prone to sulphate attack)
• 𝑪𝟒 𝑨𝑭 → 𝑪𝑨𝑺𝑯 -> (stable compound than ettringite)
 The Hydration Reactions
Hydration of the calcium aluminate (C3A)
Since all Portland cements contain gypsum, eq. (4) is the main hydration reaction for C3A.
Small amounts of hydrogarnet formed by eq. (3) can sometimes be found in cement
pastes, however. If the gypsum in the cement reacts completely before the C3A, then the
concentration of sulfate ions in the pore solution decreases drastically and the
ettringite becomes unstable and converts to a different solid phase with less sulfate:

ഥ H + 4H
2C3A + C6AS  ഥ
3C4ASH (5)
3 32 12

where the new reaction product, 3C4ASH ഥ

12, is called monosulfoaluminate. Most cements
do not contain enough gypsum to react with all of the C3A, and as a result most or
all of the ettringite is converted to monosulfoaluminate within the first day or two of
hydration via the reaction of eq. (5).

Reactions eq. (4) and eq. (5) are both exothermic and contribute to the heat of hydration of
cement. The early hydration of C3A to form ettringite via eq. (4) is quite rapid; this is a
major contributor to the stage 1 kinetics shown in Figure. As with the early C-S-H
formation, this separates the C3A particles from the pore solution, slowing their
dissolution.

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_2.html
 Hydration of Cement
Formation of calcium sulphoaluminates
(CASH)
Ettringite (AFt) formation:
C3A + 3CSH2 + 26H → C6AS3H32 (ΔH = -1672 J/g)

Fast reaction rate, gives low strength and very high heat
liberation

Ettringite, in the absence of gypsum, reacts further

to become monosulfoaluminate (AFm) :
C6AS3H32 + 2C3A + 4H → 3C4ASH12

Overall reaction:
C3A + CSH2 + 10H → C4ASH12 (ΔH = -1144 J/g)
 Cement Composition
Chemical formula Notation Name Typical
The difference between
weight %
CaO C Lime, calciumalumina
oxide and aluminate. is60-67that
SiO2 S alumina is aluminum17-25
Silica, silicon dioxide
H 2O H Water oxide used especially in--
Al2O3 A mining,
Alumina, aluminum material sciences 3-8
oxide and
Fe2O3 F Iron or ferric oxide
ceramics while aluminate 1-6
MgO M Magnesia, magnesium oxide a compound,
is (chemistry) 1-4
K2O, Na2O K, N Alkalis, Potassium & sodium
containing aluminium 0.5-1.2
and
SO3 S oxides 2-3.5
oxygen with more
CO2 C Sulphur trioxide --
Carbon dioxide
electropositive elements,
that is a salt of the
3CaO·SiO2 C 3S Tricalcium silicate, Alite 45-60
hypothetical aluminic acid.
2CaO·SiO2 C 2S Dicalcium silicate, Belite 15-30
3CaO·Al2O3 C 3A Tricalcium Aluminate 6-12
4CaO·Al2O3·Fe2O3 C4AF Tetracalcium Aluminoferrite 6-8
CaSO4·2H2O CSH2 Gypsum, Calcium sulphate 3-4
dihydrate
M. Santhanam
Evolution of Hydration

Young et al.
 Overview of the Hydration Process

Figure
The shows figure
following the microstructure
is a result ofofaa realistic
cement digital
paste
at it of
model hydrates. The yellow
cement hydration. phase
Phases are is thecoded:
color main
hydration product,
Black=water C-S-H
(pores), Redgel.= C3S, Blue = C2S, Yellow
AtC-S-H
= the endgel. of Stage 3, the yellow rims if hydration
product have become interconnected, causing final End of
set Cement
a) and givingparticles
paste some minimalinstrength.
dispersed water just after Stage 3
By mixing.
28 days the image
(Stage 1). is dominated by C-S-H gel
and30%
b) the porosity has
hydration, ~1noticeably
day (end decreased.
of Stage 3).The final
amount
c) 70%ofhydration,
porosity will depends
~ 28 days strongly
(Stage 4).on the initial
(Images
w/c courtesy
of the paste.
of NIST).

After 24 hrs. of mixing After 28 days of mixing

Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
 Overview of the Hydration Process
• The overall progress of hydration reactions is described by the
degree of hydration, which is simply the fraction of the cement that
has reacted. Complete hydration of all the cement gives = 1.

• From figure, it can be seen that the degree of hydration and the
strength track together, particularly at later times.
• This is because the strength of cement paste
depends primarily on the amount of capillary
porosity. The amount of capillary
porosity decreases in proportion to the Complete
Hydration
amount of hydration that has
taken place. This decrease
occurs because the C-S-H gel
phase (including its internal gel
pores) occupies significantly
more volume than the cement
minerals it forms from. Typical development of the degree of hydration and
compressive strength of a Type I Portland cement over time.
 Overview of the Hydration Process

In the following figure, alpha

has reached a value of 1
(complete hydration) after one
year.

But this will not always be the

case, as many cement pastes
will never reach full hydration.
Depending on why hydration
terminates?
Typical development of the degree of
hydration and compressive strength of a
Type I Portland cement over time.

The final degree of hydration will depend on

• the w/c of paste,
• the cement particle size, and
• the curing conditions.
Summary of the Rate of Heat Evolution During Hydration

Stage I: Rapid evolution of heat, lasts about 15 minutes.

Stage II: Dormant period, lasts until initial set occurs in 2 to 4 hours
Stage III: Rapid reaction of C3S during the acceleration period, with the peak
being reached at about 8-10 hours, much after final set at 4-8 hours
and hardening has begun
Stage IV: Rate of reaction slows down until steady state is reached in 12-24
hours
Stage V: Steady state
Dr Tehmina Ayub
Dr Tehmina Ayub
 LECTURE # 07

Morphology & Microstructure

of Hydrated Cement Paste
 Course Outline
• Electrochemistry: Laws of electrolysis, E.M.F Series,
Corrosion (Theories, Inhibition & Protection)
• Cement & Aggregates: chemical composition,
Hydration, Structure of hydrated cement, Influence of
the compound composition on the properties of
cement, Alkali-silica reaction in aggregates, Alkali-
carbonate reaction, Tests for aggregate reactivity
• Durability of concrete: Diffusion and absorption,
Carbonation, Acid attack on concrete, Sulfate attack
on concrete, Effect of sea water on concrete
• Water-related Chemistry: pH, Chloride, TDS, Hardness
• Soil-related Chemistry: Chemical formation of soil, pH,
Organic content, Salt content, Mica content

Dr Tehmina Ayub
 Morphology of the Main Hydration
Products
• The morphology of a solid phase can be defined as
its shape, form, or structure at the microscopic
scale, that is, the scale of nanometers and microns.

• The morphology of a material often has a greater impact

on its macroscopic properties (mechanical properties
(e.g. compressive, tensile and flexure) and durability)
than its chemical composition; this is certainly true of
cement paste and concrete.

• The combined morphology of the solid phases in a

porous material such as cement paste is one of the
major components of its microstructure, with the other
being the pore system itself.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
Dr Tehmina Ayub
Morphology of the Main Hydration Products
• One of the major reasons that the science of
cement and concrete is so complex is that the
morphology of the hydration products are both
complex and highly variable. The standard
approach for studying a complex material or
process is to break it down into individual phases
or steps and to study each of these in isolation.
Lets study

• Calcium-Silicate-Hydrate (C-S-H) gel

• Calcium Hydroxide (CH) or Porlandite
• Calcium Sulfoaluminate Phases
• Other Phases
Source:
http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Microstructure of cement grain showing
CSH and Ca(OH)2

Source: http://file.scirp.org/Html/4-7701198_41386.htm
 Morphology of the Main Hydration Products
Calcium-Silicate-Hydrate (C-S-H) gel

• The C-S-H gel is not only the

most abundant reaction product,
occupying about 50% of the
paste volume, but it is also
responsible for most of the
engineering properties of cement
paste.
• This is not because it is an intrinsically strong or stable
phase but because it forms a continuous layer that binds
75/124
together the original cement particles intox100 = 60% whole.
a cohesive
• The ability of the C-S-H gel to act as a binding phase arises
from its nanometer-level structure. Because of its importance
and complexity. 99/121 x100 = 82%
Source:
http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Morphology of the Main Hydration Products
Calcium-Silicate-Hydrate (C-S-H) gel

• The C-S-H gel is not only the

most abundant reaction
product, occupying about 50%
of the paste volume, but it is
also responsible for most of the
engineering properties of
cement paste.
• This is not because it is an intrinsically strong or stable
phase but because it forms a continuous layer that binds
together the original cement particles into a cohesive whole.
• The ability of the C-S-H gel to act as a binding phase arises
from its nanometer-level structure. Because of its importance
and complexity.
Source:
http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Morphology of the Main Hydration Products
Calcium-Silicate-Hydrate (C-S-H) gel
The most important general features of C-S-H gel are:

1. The internal pore system, and Unhydrated Cement

2. The two morphologies. C-S-H Gel

Rate of hydration vs. time, showing when the

low-density and high-density morphologies form

Source:
http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Morphology of the Main Hydration Products
Calcium Hydroxide (CH) or Portlandite
• Calcium hydroxide, also known by its mineral name
portlandite, forms from C3S and, to a lesser extent, C2S via
reactions (1) and (2). It occupies about 15% of the volume of a
normal Portland cement paste (not 20-25%, as is reported in
some texts).

• Calcium hydroxide forms as crystals with a wide range of

shapes and sizes, depending primarily on the amount of room
available for growth.

• Crystals that nucleate (form initially) in the capillary pores tend

to form irregular hexagonal plate-shaped crystals several
microns across, large enough to be seen in an optical
microscope (see Figure). These crystals can completely
engulf a small cement particle next to it.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Morphology of the Main Hydration Products
Calcium Hydroxide (CH) or Portlandite

• Calcium hydroxide contributes slightly to the strength and

impermeability of the paste, because it reduces the total
pore volume by converting some of the liquid water into
solid form. In this respect it is much less important than
the C-S-H.
• CH is the most soluble of the hydration products, and
thus is a weak link in cement and concrete from a
durability point of view. If the paste is exposed to fresh
water, the CH will leach out (dissolve), increasing the
porosity and thus making the paste more vulnerable to
further leaching and chemical attack.
Source:
http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
 Morphology of the Main Hydration Products
Calcium Sulfoaluminate Phases

• The hydration products that form from the C3A and

C4AF minerals occupy about 15-25% of the volume of
a mature portland cement paste.
• Similar to CH, they do not contribute much to the
engineering properties of concrete, except in a
negative sense when a cement paste undergoes
sulfate attack.

• The main calcium sulfoaluminate phases have very

different morphologies. Ettringite forms as distinctive
clusters of prismatic needles (see Figure 5-7), whereas
monosulfate forms as hexagonal-plate crystals similar
to CH, but smaller.
 Hydration of Cement
Formation of calcium sulphoaluminates
(CASH)
Ettringite (AFt) formation:
C3A + 3CSH2 + 26H → C6AS3H32 (ΔH = -1672 J/g)

Fast reaction rate, gives low strength and very high heat
liberation

Ettringite, in the absence of gypsum, reacts further

to become monosulfoaluminate (AFm) :
C6AS3H32 + 2C3A + 4H → 3C4ASH12

Overall reaction:
C3A + CSH2 + 10H → C4ASH12 (ΔH = -1144 J/g)
 The microstructure of Hydrated Cement paste
The interfacial transition zone (ITZ)

• This is actually a general phenomenon associated with

particle packing, known as the "wall effect."

• In the case of concrete, this is effect is magnified by the

shearing stresses exerted on the cement paste by the
aggregate particles during mixing, which tend to cause the
water to separate from the cement particles.

• The result is a narrow region around the aggregate particles

with fewer cement particles, and thus more water. This is
called the interfacial transition zone, abbreviated as ITZ.
 The microstructure of Hydrated Cement paste
The interfacial transition zone (ITZ)
• The ITZ is a region with a higher w/c, and thus a higher
porosity, than the bulk paste. It is not uniform, but varies
from point to point along each aggregate particle, with
an average thickness of 20-40 £gm.
• Because of the larger pores, the ITZ is characterized by
the presence of larger crystals, particularly of calcium
hydroxide, than are found in the bulk paste (see Figure).
The ITZ tends to be larger around larger aggregate
particles.
• The ITZ has important effects on the properties of
concrete, because it tends to act as the "weak link in the
chain" when compared to the bulk cement paste and the
aggregate particles.
 Ettringite

ITZ

Aggregate
Ettringite