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Lecture # 04: Chemistry of Cement Manufacturin G
Lecture # 04: Chemistry of Cement Manufacturin G
04
Chemistry of
Cement
Manufacturin
g
Dr Tehmina Ayub
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Dr Tehmina Ayub
CONCRETE CONSTITUENT BY VOLUME
PEERCENTAGE
Dr Tehmina Ayub
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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
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Dr Tehmina Ayub
Metakaolin
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Dr Tehmina Ayub
Metakaolin
C
A
CEMENT
C
S A F H
C3S
C2S
C3A
C4AF
Dr Tehmina Ayub
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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.
Dr Tehmina Ayub
Dr Tehmina Ayub
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.
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)
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.
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.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
Overview of the Hydration Process
Stage 3
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
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
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.
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:
where C3S2H3 is the calcium silicate hydrate (C-S-H) gel phase and CH is calcium
hydroxide, which has the mineral name portlandite.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.html
The Hydration Reactions
Hydration of the calcium silicate minerals (C3S and C2S)
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)
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
The Hydration Reactions
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:
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/ferrite minerals (C3A and C4AF)
Dr Tehmina Ayub
Dr Tehmina Ayub
The Hydration Reactions
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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
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
The Hydration Reactions
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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
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
The Hydration Reactions
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_2.html
The Hydration Reactions
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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 C3to a different solid phase with less
A Hydration
sulfate:
2C3A + C6AS ഥ H + 4H 3C ASH ഥ (5)
3 32 4 12
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
The Hydration Reactions
Hydration of the calcium aluminate/ferrite minerals (C3A and C4AF)
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.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_2.html
The Hydration Reactions
Reaction with additional sulfate ions
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.
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_3.html
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
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
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).
Source: http://iti.northwestern.edu/cement/monograph/Monograph5_1.htmlc
Dr Tehmina Ayub
Dr Tehmina Ayub
Dr Tehmina Ayub
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
Source:
Morphology of the Main Hydration Products
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
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
Source:
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
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:
Morphology of the Main Hydration Products
Calcium-Silicate-Hydrate (C-S-H) gel
The most important general features of C-S-H gel are:
Source:
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).
Source:
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,
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:
Morphology of the Main Hydration Products
Calcium Hydroxide (CH) or Portlandite
• 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
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.
• 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.