Lecture # 04: Chemistry of Cement Manufacturin G

LECTURE #
04
Chemistry of
Cement
Manufacturin
g
Dr Tehmina Ayub
1
Dr Tehmina Ayub
CONCRETE CONSTITUENT BY VOLUME
PEERCENTAGE
Dr Tehmina Ayub
Sources:
Example of hydraulic cement:

portland cement and of non
hydraulic is gypsum plaster or
ordinary lime
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.
Process
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Metakaolin
Process
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Metakaolin
C
A
CEMENT
C
S A F H
C3S
C2S
C3A
C4AF
Dr Tehmina Ayub
Process
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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
CementRaw Materials
(1)-Limestone :- Contains predominantly calcium carbonate (CaCO ) 3
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.
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VIEW OF CEMENT PLANT
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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.
Clinker Grain Structure
Micrograph of alite-surfaced
cement grains. Etch colours: alite C 3S (Alite) C 3A
= brown, belite = blue, aluminate
and ferrite = white. C2S (Belite) C4AF (Ferrite)
Silicates are approximately 80% of total material

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
• 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”.
Microscopic Image of Cement paste
• 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].
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
Stage 2
Process
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 cement chemists. Schematic of the rate of hydration or heat
The induction period will be evolution as a function of time.
discussed later.
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.
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.
Dr Tehmina Ayub
Dr Tehmina Ayub
Dr Tehmina Ayub
In order for further hydration to take place, the dissolved ions
from the cement must diffuse outward and precipitate into the
capillary pores,
or
water must diffuse inward to reach the unreacted cement cores.
These diffusion processes become slower and slower as the
layer of hydration product around the cement particles becomes
thicker and thicker. This final period (Stage 4) is called the
“diffusion-limited reaction period”.
After 24 hrs. of mixing
The Hydration Reactions
Each of the four main cement minerals (C2S, C3S, C3A, C4AF)
reacts at a different rate and tends to form different solid phases
when it hydrates.
The behavior of each of these minerals is studied by

synthesizing it in its pure form and hydrating it under controlled
conditions.
It should be noted that during the actual cement hydration

process, all minerals dissolve into the same pore solution. Thus,
the solid hydration products are associated with the pore
solution as a whole rather than a particular cement mineral.
However, the individual reactions provide a good approximation

of the overall hydration behavior of cement.
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
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.
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.
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
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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
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Dr Tehmina Ayub
where C6A S ഥ H is mineral ettringite. Since all Portland cements contain
3 32
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:
2C3A + C6AS ഥ H + 4H  3C ASH ഥ (5)
3 32 4 12
where the new reaction product, 3C4ASHഥ

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.
3 32
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:
2C3A + C6AS ഥ H + 4H  3C ASH ഥ (5)
3 32 4 12
where the new reaction product, 3C4ASH ഥ

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).
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.
After a period of several hours the early-forming ettringite converts to
monosulfoaluminate via eq. (4) , allowing the C3A to undergo renewed rapid
hydration, with kinetics that are roughly similar to the main hydration peak of C3S
(stages 3 and 4).
When C3A is hydrating within a cement paste, this second period of reaction often
creates a shoulder in the decelerating (Stage 4) rate period just after the main peak
(not shown in the Figure).
The ferrite phase (C4AF) reacts in a similar fashion to the C3A (eqs. (1)-(5)), but
more slowly. One important difference is that some of the aluminum in the reaction
products is substituted for iron. The amount of substitution depends on many
factors including the composition of the C4AF and the local conditions in the
paste. A convenient way to represent these reactions is as follows:
ഥ + 21H
C4AF + 3CSH  ഥ H
C6(A,F)S + (F,A)H3 (6)
2 3 32
ഥ H + 7H
C4AF + C6(A,F)S  ഥ H
3C4(A,F)S + (F,A)H3 (7)
3 32 3 12
3 32
the concentration of sulfate ions in the pore solution decreases drastically and
the ettringite becomes unstable and converts C3to a different solid phase with less
A Hydration
sulfate:
2C3A + C6AS ഥ H + 4H  3C ASH ഥ (5)
3 32 4 12
where the new reaction product, 3C4ASH ഥ

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).
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.
where (A,F) indicates aluminum with variable substitution of iron, and
(F,A) indicates iron with variable substitution of aluminum. The (F,A)H3 is
an amorphous phase that forms in small amounts to maintain the correct
reaction stoichiometry.
Because of the substituted iron, the main reaction products are not pure
ettringite and monosulfoaluminate, although they have the same crystal
structure. Instead, cement chemists have given them the names AFt and
AFm, respectively, where the m indicates monosulfate (one sulfate ion)
and the t indicates trisulfate.
In Portland cement paste where the C3A and C4AF are intimately mixed
together, it can be safely assumed that the aluminum-bearing reaction
products are never completely free of iron, and so the terms AFm and AFt
are more correct. However, as with the terms alite (impure C3S) and belite
(impure C2S), this is a bit more confusion than many people are willing to
deal with, and thus the terms ettringite and monosulfoaluminate are
commonly used to refer to these phases in cement pastes.
Reaction with additional sulfate ions
As noted, most Portland cements do not contain enough added gypsum

to fully hydrate the C3A and C4AF via reactions (4) and (6) to form
ettringite. Once the gypsum is consumed, the ettringite reacts with the
remaining C3A and C4AF to form a new lower-sulfate phase called
monosulfate (reactions (5) and (7)). Thus in a mature Portland cement
paste it is normal to find monosulfate and little or no ettringite.
However, if a new source of sulfate ions becomes available in the pore

solution, then it becomes thermodynamically favorable to form ettringite
again, just as it was initially. This will occur at the expense of the existing
monosulfate:
ഥ 12 + 2CSH
C4ASH ഥ 2 + 16H  ഥ 3H32
C6AS (8)
where it is understood that the A sites will contain some F. The gypsum
on the left side of eq. (8) represents the equivalent amount of dissolved
ion, as no solid gypsum need form in the paste.
Evolution of Hydration
Young et al.
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
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
Dr Tehmina Ayub
Dr Tehmina Ayub
Dr Tehmina Ayub
• 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.
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 Typical development of the degree of
terminates? 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.
Hydration will continue at a slow rate during

Figure 1
Stage 4 (Refer to Figure 1) until one of the
three following criteria is met:
1) All of the cement reacts. This is the
situation shown in Figure 2. This indicates
that the paste has a moderate or high w/c
and was cured correctly. While it is the best
possible outcome for the given mix design, it
does not guarantee high quality concrete as
the w/c may have been too high. If the
cement contains some large particles, full
hydration of these particles may not occur for
years. However this is generally not the case
with modern cements.
2) There is no more liquid water available Figure 2

for hydration. If the cement has a w/c less
than about 0.4, there will not be enough
Typical development of the degree of hydration and
original mix water to fully hydrate the cement. compressive strength of a Type I Portland cement over time.
If additional water is supplied by moist curing
or from rainfall, hydration may be able to-
continue. However, it is difficult to supply

additional water to the interior of large Figure 1
concrete sections. If the cement is
improperly cured so that it dries out,
hydration will terminate prematurely
regardless of the w/c. This is the worst-case
scenario, as the strength will be lower
(perhaps significantly) than the value
anticipated from the mix design.
3) There is no more space available for

new reaction product to form. When the
capillary porosity is reduced to a certain
minimal level, hydration will stop even if
there is unreacted cement and a source of
water. This is the best possible outcome,
and it is only possible if the w/c is less than
about 0.4. Not only will the cement paste or Figure 2
concrete have a high strength, but it will
also have a low permeability and thus be Typical development of the degree of hydration and
durable. compressive strength of a Type I Portland cement over time.
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
The Hydration
Reactions
LECTURE #
07
Morphology of the
Main Hydration
Products
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 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:
The morphology of a particular solid phase will depend
on many factors, including the crystal structure, the
mechanism of formation, the temperature, and the space
available for the phase to form, to name just a few that are
particularly relevant to cement paste. In addition, the
morphology of a solid phase can change over time in
response to changes in its surrounding environment.
Source:
Dr Tehmina Ayub
Dr Tehmina Ayub
• 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:
Microstructure of cement grain showing CSH and Ca(OH)2
Source: http://file.scirp.org/Html/4-7701198_41386.htm
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:
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:
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:
• A significant proportion of the calcium hydroxide forms as
an intimate mixture with the C-S-H gel, particularly the
low-density C-S-H.
• These crystals tend to be much smaller, with many under
1 £gm in diameter, because their growth is impeded by the
surrounding solid.
• There is some evidence of nanometer-scale CH in cement
pastes as well. This is logical considering the fact that C-
S-H, which has a nanometer-level morphology, forms in
conjunction with CH.
• At such a small length scale, which is on the order of
hundreds of atoms, it is difficult to clearly distinguish
between CH and C-S-H, since the latter contains a
significant proportion of Ca-OH bonds.
Source:
• 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,
however.
• 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:
• Calcium hydroxide is believed to play a role in limiting the
amount of shrinkage that occurs when a cement paste is
dried.
• As water is removed from the pore system, the C-S-H gel
phase collapses causing an overall shrinkage, while other
crystalline phases such as CH are unaffected.
• As the C-S-H starts to shrink the CH that is in contact with
it acts as a restraint, so that the overall shrinkage is less
than it would be if the CH were not present.
• Blended cement pastes, which have little or no CH, as
the CH that forms from cement hydration is consumed
along with the mineral admixtures to form additional C-S-H
gel. This has beneficial effects on the strength and
permeability, but tends to increase the tendency for drying
shrinkage for the reasons mentioned above.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_4_1.html
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.
• As with 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. In most cases, the individual crystals of
both phases are too small to be seen with optical
microscopy.

Lecture # 04: Chemistry of Cement Manufacturin G

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Lecture # 04: Chemistry of Cement Manufacturin G

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LECTURE #

Example of hydraulic cement:

Silicates are approximately 80% of total material

• The concentrations increase to the point that the pore

The precise nature of the

Stage 3 is a rapid reaction period.

This behavior is due almost entirely to

The microstructure of the paste at this point

After 24 hrs. of mixing

The behavior of each of these minerals is studied by

It should be noted that during the actual cement hydration

However, the individual reactions provide a good approximation

2C3S + 6 H  C3S2H3 +3 CH (1)

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

The dicalcium silicate phase (C2S) reacts according to:

2C2S + 6 H  C3S2H3 + CH (2)

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

Moderate reaction rate, gives high strength and heat

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

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

where the new reaction product, 3C4ASHഥ

where the new reaction product, 3C4ASH ഥ

where the new reaction product, 3C4ASH ഥ

As noted, most Portland cements do not contain enough added gypsum

However, if a new source of sulfate ions becomes available in the pore

Ettringite, in the absence of gypsum, reacts further

After 24 hrs. of mixing After 28 days of mixing

In the following figure, alpha

But this will not always be the

The final degree of hydration will depend on

Hydration will continue at a slow rate during

2) There is no more liquid water available Figure 2

continue. However, it is difficult to supply

3) There is no more space available for

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

• The morphology of a solid phase can be defined as its

• The morphology of a material often has a greater impact

• The combined morphology of the solid phases in a

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

1. The internal pore system, and Unhydrated Cement

Rate of hydration vs. time, showing when the

• Calcium hydroxide forms as crystals with a wide range of

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

• The main calcium sulfoaluminate phases have very

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