Lecture # 05 Cement: LT Col Md. Jahidul Islam, PHD, Engrs

CE6110: Advanced Concrete Technology 1/6/2021
Lecture # 05
Cement
Lt Col Md. Jahidul Islam, PhD, Engrs

e-mail: [email protected]
 Hydraulic or water-resisting cements consist essentially of

Portland cement and its several modifications
 To understand the properties of Portland cement, it is
helpful to acquire some familiarity with its manufacturing
process, chemical and mineralogical composition, and
reactivity of the constituent compounds such as calcium
silicates and calcium aluminates.
 Furthermore, properties of concrete containing Portland
cement develop as a result of chemical reactions between
the Portland cement compounds and water, because the
hydration reactions are accompanied by changes in matter
and energy
CE6110: Dr M. Jahidul Islam 2
by Dr. M. Jahidul Islam 1

 The cements derived from the calcination of gypsum or

calcium carbonates are non-hydraulic because their
products of hydration are not resistant to water
 Lime mortars that were used in ancient structures built
by Greeks and Romans were rendered hydraulic by the
addition of pozzolanic materials, which reacted with lime
to produce a water-resistant, cementitious product
 Compared to gypsum and lime cements, Portland cement
and its various modifications are the principal cements
used today for making structural concrete
 Portland cement and modified Portland cements are
hydraulic cements because they do not require the
addition of a pozzolanic material to develop water-
resisting properties

 Definition:
 “ASTM C 150 defines Portland cement as a hydraulic cement
produced by pulverizing clinkers consisting essentially of
hydraulic calcium silicates, and a small amount of one or
more forms of calcium sulfate as an interground addition.
Clinkers are 5- to 25- mm-diameter nodules of a sintered
material that is produced when a raw mixture of
predetermined composition is heated to high temperatures”
 Since calcium silicates are the primary constituents of

portland cement, the raw material for the production of
cement must provide calcium and silica in suitable forms
and proportions
 Raw materials
 CaO: found in limestone, chalks, shell deposits
 SiO2: iron-bearing aluminosilicates, e.g. clays, silts, shale
and other argillaceous rocks

 Clay minerals contain alumina (Al2O3), iron oxide (Fe2O3),

and alkalies
 contribute little to Portland cement as regards to strength
 can cause durability problem and abnormal setting
 act as fluxing agents, lowering the production temperature of
cement clinker
 Therefore, when sufficient amounts of iron and alumina
minerals are not present in the primary raw materials,
these are purposely incorporated into the raw mix through
addition of secondary materials such as bauxite and iron
ore
 As a result, besides the calcium silicate compounds, the
portland cement clinker also contains aluminates and
aluminoferrites of calcium
 The objective of processing raw materials is to ensure that

the raw feed entering the kiln is of constant composition
and in a thoroughly pulverized and blended state.
 Wet process
 Raw material is crushed and stockpiled separately
 Blending may take place during fine grinding or after
each material has been ground separately
 Clay can be broken down to finely divided slurry by
mechanical agitation
 Evaporation of water consumes heat, high cost
 Dry process (used in modern cement plants)
 If source of silica is an argillaceous rock, grinding is
required
 Improvements in grinding mills have made the wet
process uneconomic and obsolete

 In cement kiln, partial melting takes place; only about

¼ of the charge is in liquid state at any time, but it is
in this fraction that the necessary chemical reaction
proceeds
 Four processes take place in the kiln

 Evaporation
 Calcination
 Clinkering
 Cooling
(3) Clinkering
-Final chemical
combination occurs
to form calcium
silicates
-1400 to 1600 oC
-15 to 45 min.
(4) Cooling
-Liquid phase
solidify to produce
hard clinker
-Exit temp 1000-
(1) Evaporation: free water lost 1200 oC
(2) Calcination
 Water from Argillaceous materials lost at ~600 C
 CO2 from limestone lost at ~900 C (CaCO3  CaO + CO2)
 Calcium aluminates and ferrites form at ~1200 C, act as fluxes,
melting at ~1350 C to begin the clinkering zone

 Grinding
 A small amount of gypsum is interground with the clinker
nodules (6-50 mm)
 to control the early reactions of calcium aluminate
 to avoid flash setting
 Economic consideration
 Environment consideration, CO2
 Although portland cement consists essentially of

various compounds of calcium, the results of routine
chemical analysis are reported in terms of oxides of
the elements present

 Since properties of portland cement are related to the

compound composition, it is difficult to draw any
conclusions from the cement oxide analyses.
 It is a common practice in the cement industry to compute
the compound composition of portland cement from the
oxide analysis by using a set of equations which were
originally developed by R.H. Bogue.

 The Bogue equations for estimating the theoretical or

the potential compound composition of portland cement
are as follows:
* C4AF has a different composition from that in Case A. C 2F

may also present.
 Some can be of considerable significance with regard to

cement performance
 Unsoundness problem
 MgO
 Slow hydration of crystalline MgO (periclase) may cause

expansion and cracking
 Limit is specified in ASTM standard
 Free lime
 Content is not limited in ASTM standard

 Typically < 0.5%, >1.5% indicates poor control of burning
process
 High gypsum level
 Alkalis (Na2O, K2O)

 Generally does not cause problem except when certain
aggregates are used that can participate alkali-aggregate
reaction

 Hydration - reaction with water

 Reaction products formed – hydration products
 All the compounds, however, do not hydrate at the same

rate
 The aluminates are known to hydrate at a much faster rate
than the silicates
 In fact, the stiffening (loss of consistency) and setting
(solidification) characteristics of a portland cement paste,
are largely determined by the hydration reactions
involving the aluminates
 The silicates, which make up about 75 percent of ordinary
portland cement, play a dominant role in determining the
hardening (rate of strength development) characteristics

 The reaction of C3A with water is immediate

 Crystalline hydrates, such as C3AH6, C4AH19, and
C2AH8, are formed quickly, with liberation of a large
amount of heat of hydration
 Unless the rapid hydration of C3A is slowed down by
some method, portland cement cannot be used for
most construction applications
 This task is generally accomplished by the addition of
gypsum
 Therefore, for practical purposes, it is not the
hydration reactions of C3A alone but the hydration
reactions of C3A in the presence of gypsum which are
important

 Several theories have been postulated to explain the

mechanism of retardation of C3A by gypsum
 According to one theory, since gypsum and alkalies go into
solution quickly, the solubility of C3A is depressed in the
presence of hydroxyl, alkali, and sulfate ions
 Depending on the concentration of aluminate and sulfate
ions in the solution, the precipitating crystalline product is
either calcium aluminate trisulfate hydrate or the calcium
aluminate monosulfate hydrate
 In solutions saturated with calcium and hydroxyl ions, the
former crystallizes as short prismatic needles and is also
referred to as high-sulfate or by its mineralogical name,
ettringite
 The monosulfate is also called low-sulfate and crystallizes
as thin hexagonal plates
 The relevant chemical reactions may be expressed as

follows
 Ettringite is usually the first hydrate to crystallize because

of the high sulfate/ aluminate ratio in the solution phase
during the first hour of hydration
 In normally retarded portland cements, which contain 5 to
6 percent gypsum, the precipitation of ettringite
contributes to stiffening (loss of consistency), setting
(solidification of the paste), and early strength
development

 Later, after the depletion of sulfate when the

concentration of aluminate ions in the solution goes
up again due to renewed hydration of C3A and C4AF,
ettringite becomes unstable and is gradually
converted into the monosulfate phase, which is the
final product of hydration of portland cements
containing more than 5 percent C3A

 Case I
 When the rates of availability of the aluminate ions and the
sulfate ions to the solution phase are low, the cement paste will
remain workable for about 45 min; thereafter it will start
stiffening as the water-filled space begins to get filled with
ettringite crystals. Most so-called normal-setting portland
cements belong to this category. The paste becomes less
workable between 1 and 2 h after the addition of water, and
may begin to solidify within 2 to 3 h
 Case II
 When the rates of availability of the aluminate ions and the
sulfate ions to the solution phase are high, large amount of
ettringite form rapidly and cause a considerable loss of
consistency in 10 to 45 min, with solidification of the paste
between 1 and 2 h. Freshly produced high-C3A cements
containing more than normal amounts of alkali sulfates or
calcium sulfate hemihydrate are generally characterized by this
type of behavior
 Case III
 When the amount of reactive C3A is high but the soluble
sulfate present is less than required for normal
retardation, hexagonal-plate crystals of monosulfate and
calcium aluminate hydrates form quickly and in large
amounts causing the cement paste to set in less than 45
min after the addition of water. This phenomenon is
known as quick set
 Case IV
 When little or no gypsum has been added to a ground
portland cement clinker, the hydration of C3A is rapid and
the hexagonal-plate calcium aluminate hydrates start
forming in large amounts soon after the addition of water,
causing almost an instantaneous set. This phenomenon,
known as flash set, is associated with large heat evolution
and poor ultimate strength

 Case V
 When the C3A in cement is of low reactivity, as is the case
in partially hydrated or carbonated cements which have
been improperly stored, and at the same time a large
amount of calcium sulfate hemihydrate is present in the
cement, the solution phase will contain a low
concentration of aluminate ions but will quickly become
supersaturated with respect to calcium and sulfate ions.
This situation will lead to the rapid formation of large
crystals of gypsum with a corresponding loss of
consistency. The phenomenon, called false set, is not
associated with large heat evolution and can be remedied
by vigorous mixing of the cement paste with or without
additional water
 Although gypsum is added to cement to serve as a

retarder, what is known as the optimum gypsum content
of cement is generally determined from standard tests
which show maximum cement strength and minimum
shrinkage at given ages of hydration
 The sulfate ions contributed to the solution phase by
gypsum have a retarding effect on the hydration of the
aluminate compounds but an accelerating effect on the
hydration of the silicates that are the principal
compounds in portland cement
 Therefore, depending on the composition of a cement, a
specific gypsum content is indicated for optimum
performance of the cement

 C 3S provides
most of the
early strength
(in the first 3-4
weeks)
 Both C3S and

C2S contributes
to ultimate
strength
 The hydration of C3S and C2S in portland cement produces

a family of calcium silicate hydrates which are structurally
similar but vary widely in calcium/silica ratio and the
content of chemically combined water
 Since the structure determines the properties, the
compositional differences among the calcium silicate
hydrates have a little effect on their physical
characteristics
 In general, the material is poorly crystalline and forms a
porous solid which exhibits characteristics of a rigid gel
 Since the chemical composition of the calcium silicate
hydrates in hydrating portland cement pastes varies with
the water-cement ratio, temperature, and age of
hydration, it has become rather customary to refer to
these hydrates simply as C-S-H, a notation that does not
imply a fixed chemical composition

 On complete hydration the approximate composition of

the material may be assumed as C3S2H3; this composition is
therefore used for stoichiometric calculations
 The stoichiometric reactions for fully hydrated C 3S and C2S
pastes can therefore be expressed as
 Similar reaction products are formed on hydration of both

the tricalcium silicate and the dicalcium silicate present in
portland cement
 Stoichiometric calculations show that the C3S

hydration would produce 61 percent C3S2H3 and 39
percent calcium hydroxide, whereas the C2S hydration
would produce 82 percent C3S2H3 and 18 percent
calcium hydroxide
 As the high specific surface area and, consequently,
the adhesive property of the hydrated cement paste
are essentially due to the formation of the calcium
silicate hydrate, it is to be expected that the ultimate
strength of a high-C3S portland cement would be
lower than a high-C2S cement

 If the durability of a hardened cement paste to acidic

and sulfate waters is reduced due to the presence of
calcium hydroxide, it may be expected that a cement
containing a high proportion of C2S will be more
durable to acidic and sulfate environments compared
to a cement containing a high proportion of C3S
 From the standpoint of durability to chemical attacks,
some cement standards attempt to limit the maximum
permissible C3S in cement, others recommend the use
of pozzolans in order to remove the excess calcium
hydroxide from the hydrated cement paste
 It can be calculated from the stoichiometric equations
that C3S and C2S require 24 and 21 percent water,
respectively, for complete hydration
 From the standpoint of instability of the crystal

structure and the heat of hydration data given below,
it is apparent that C3S would hydrate at a faster rate
than C2S
 In the presence of gypsum, C3S in fine particles of
cement begins to hydrate within an hour of the
addition of water to cement, and thus contributes to
the final time of set and the early strength of a
hydrated cement paste
 The relatively quicker rate of C3S hydration in finely
ground portland cements has become an important
factor in the production of high-early-strength
portland cements

 Type I – ordinary Portland cement (OPC)

 Most commonly used in construction
 Type II – Modified cement
 Moderate sulphate resistance
 Moderate heat of hydration
 Type III – Rapid hardening Portland cement (RHPC)
 Used for obtaining high early strength, cold weather
concreting, precast concrete
 Type IV – Low heat Portland cement (LHPC)
 Used for mass concrete, hot weather concreting
 Type V – Sulphate resisting portland cement (SRPC)
 Used in situation where ground water or soil have high
sulphate contents

 Rate of heat evolution measured as temperature rise of

mass concrete stored under adiabatic conditions
 The compounds of portland cement are non-

equilibrium products of high temperature reactions
and are therefore in a high-energy state
 When a cement is hydrated, the compounds react with
water to acquire stable, low-energy states and the
process is accompanied by the release of energy in the
form of heat
 In other words, the hydration reactions of portland
cement compounds are exothermic
 The significance of heat of cement hydration in
concrete technology is manifold

 The heat of hydration can sometimes be a hindrance (e.g.,

mass concrete structures), and at other times a help (e.g.,
winter concreting when ambient temperatures may be too
low to provide the activation energy for hydration
reactions)
 The total amount of heat liberated and the rates of heat
liberation from hydration of the individual compounds can
be used as indices of their reactivity
 On mixing cement with water, a rapid heat evolution (ascending

portion of peak A) lasting a few minutes occurs
 This probably represents the heat of solution of aluminates and
sulfates
 This initial heat evolution ceases quickly (descending portion of peak
A) when the solubility of aluminates is depressed in the presence of
sulfate in the solution
 The next heat evolution cycle, culminating in the second peak after
about 4 to 8 h of hydration for most portland cements, represents the
heat of formation of ettringite (ascending portion of peak B).
 Researchers believe that the heat evolution period includes some
heat of solution due to C3S and heat of formation of C-S-H
 The paste of a properly retarded cement will retain much of its
plasticity before the commencement of this heat cycle and will
stiffen and show the initial set (beginning of solidification) before
reaching the apex at B, which corresponds to the final set (complete
solidification and beginning of hardening)

 From analysis of the heat of hydration data on a large

number of cements, Verbeck and Foster computed the
relative rates of heat evolution due to the four principal
compounds of portland cement
 Since the heat of hydration of cement is an additive
property, it can be predicted from an expression of the
type
 Where H represents the heat of hydration at a given age and under

given conditions; A, B, C, and D are the percentage contents of
C3S, C2S, C3A, and C4AF present in the cement; and a, b, c, and d
are coefficients representing the contribution of 1 percent of the
corresponding compound to the heat of hydration
 The values of the coefficients will be different for the various
ages of hydration
 For a typical portland cement, it appears that

approximately 50 percent of the potential heat is liberated
within the first 3 days, and 70 percent within the first 7
days of hydration
 Type I portland cements meeting ASTM C150 Standard
Specification generally produce 330 to 370 kJ/kg (80 to 90
cal/g) in 7 days

 ASTM C150 contains standard specifications for a low-heat

Portland cement (Type IV) and a moderate-heat portland
cement (modified Type II) with 7-day heat of hydration
limits of 250 kJ/kg (60 cal/g), and 290 kJ/kg (70 cal/g),
respectively
 Such Portland cements are no longer readily available
 Hydraulic cements meeting similar heat of hydration
requirements, that is, a Type LH (low-heat) cement and a
Type MH (moderate-heat) cement can now be marketed
under a performance specification (ASTM C 1157) that does
not restrict the composition or the constituents of the
cement
 Blended Portland cements containing large proportions of
pozzolans or slags can readily satisfy the performance
limits specified byASTM C 1157
(Concrete Manual, 8th ed. Bureau

of Reclamation, 1975)

0.658
 Fineness
 In addition to the compound composition, the fineness of
cement also affects its reactivity with water
 Generally, the finer the cement, the more rapidly it will
react
 For a given compound composition the rate of reactivity and
hence the strength development can be enhanced by finer
grinding of cement
 However, the cost of grinding and the heat evolved on hydration
set some limits on the fineness
 For quality control purposes in the cement industry, the
fineness is easily determined as the residue on standard
sieves such as No. 200 mesh (75 μm) and No. 325 mesh (45
μm)

 Fineness distribution
 It is generally agreed that
cement particles larger
than 45 μm are slow to
hydrate and those larger
than 75 μm may never
hydrate completely
 However, an estimate of
the relative rates of
reactivity of cements with
similar compound
composition cannot be
made without knowing the
complete particle size
 Stiffening is the loss of consistency by the plastic cement paste, and is

associated with the slump loss phenomenon in concrete
 It is the free water in a cement paste that is responsible for its plasticity
 The gradual loss of free water from the system as a result of the formation of
hydration products, surface adsorption by poorly crystalline products such as
ettringite and C-S-H, and evaporation causes the paste to stiffen and, finally,
to set and harden
 The term setting refers to the solidification of the plastic cement paste.
The beginning of solidification, called the initial set, marks the point in
time when the paste has become unworkable
 Accordingly, concrete placement, compaction, and finishing operations are
difficult beyond this stage
 The paste does not solidify suddenly; it requires considerable time to become
fully rigid
 The time taken to solidify completely marks the final set, which should not be
too long in order to avoid delays in the construction process

 At the final set, Portland cement paste has little or no

strength because it represents only the beginning of the
hydration of C3S, the principal compound present
 Once the C3S hydration starts, the reaction continues rapidly
for several weeks
 The progressive filling of void spaces in the paste with
reaction products results in a decrease of porosity and
permeability, and an increase in strength
 In concrete technology, the phenomenon of strength gain
with time is called hardening

 Since the rates of reactivity of individual Portland cement

compounds with water vary considerably, it is possible to
change the strength development characteristics of cements
simply by altering the compound composition
 For instance, the early strengths at 3, 7, and 28 days would
be high if the cement contains relatively large amounts of
C3S and C3A; and the early strength would be low if the
cement contains a larger proportion of C2S
 Also, from theoretical considerations, the ultimate strength
of a high-C2S cement should be greater than that of a low-
C2S cement
 Also, as the compound composition of the cement affects

the heat of hydration, it is to be expected that cements
containing high C2S will not only exhibit slow hardening but
also less heat production
 The rates of strength development and heat evolution can
also be controlled by controlling the fineness of cement
 For instance, with a given compound composition, by making
a change in the surface area of the cement from 300 to 500
m2/kg Blaine, it was possible to increase the 1-, 3-, and 7-
day compressive strengths of the cement mortar by about 50
to 100 percent, 30 to 60 percent, and 15 to 40 percent ,
respectively

 Fineness
 Blaine air-permeability method (ASTM C 204): determine
specific surface
 Time of setting:
 Methods: ASTM C 191 by Vicat needle or ASTM C 266 by
Gillmore needle

 Unsoundness
 Autoclave expansion test (ASTM C 151)
 Excessive expansion indicates unsoundness (excess MgO or
excess free lime)
 Heat of hydration
 Defined as the amount of heat evolved during setting and
hardening of Portland cement at a given temperature
measured in J/g of unhydrated cement
 Heat of solution method (ASTM C 186)
 Limits: Type II and Type IV cements (Table 3-10)
 Compressive strength
 ASTM C 109, 50-mm mortar cubes, sand/cement ratio 2.75/1,
w/c=0.485 for all portland cements, w/c=0.460 for air-
entraining Portland cement
 EN 196: 40x40x160 mm prism

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CE6110: Advanced Concrete Technology 1/6/2021

Lt Col Md. Jahidul Islam, PhD, Engrs

 Hydraulic or water-resisting cements consist essentially of

CE6110: Dr M. Jahidul Islam 2

by Dr. M. Jahidul Islam 1

 The cements derived from the calcination of gypsum or

CE6110: Dr M. Jahidul Islam 4

by Dr. M. Jahidul Islam 2

CE6110: Dr M. Jahidul Islam 5

 Since calcium silicates are the primary constituents of

by Dr. M. Jahidul Islam 3

 Clay minerals contain alumina (Al2O3), iron oxide (Fe2O3),

 The objective of processing raw materials is to ensure that

by Dr. M. Jahidul Islam 4

 In cement kiln, partial melting takes place; only about

 Four processes take place in the kiln

by Dr. M. Jahidul Islam 5

 Environment consideration, CO2

 Although portland cement consists essentially of

by Dr. M. Jahidul Islam 6

 Since properties of portland cement are related to the

by Dr. M. Jahidul Islam 7

 The Bogue equations for estimating the theoretical or

* C4AF has a different composition from that in Case A. C 2F

 Some can be of considerable significance with regard to

 Slow hydration of crystalline MgO (periclase) may cause

 Content is not limited in ASTM standard

 Alkalis (Na2O, K2O)

by Dr. M. Jahidul Islam 8

 Hydration - reaction with water

 All the compounds, however, do not hydrate at the same

by Dr. M. Jahidul Islam 9

 The reaction of C3A with water is immediate

by Dr. M. Jahidul Islam 10

 Several theories have been postulated to explain the

 The relevant chemical reactions may be expressed as

 Ettringite is usually the first hydrate to crystallize because

by Dr. M. Jahidul Islam 11

 Later, after the depletion of sulfate when the

by Dr. M. Jahidul Islam 12

by Dr. M. Jahidul Islam 13

 Although gypsum is added to cement to serve as a

by Dr. M. Jahidul Islam 14

 Both C3S and

 The hydration of C3S and C2S in portland cement produces

by Dr. M. Jahidul Islam 15

 On complete hydration the approximate composition of

 Similar reaction products are formed on hydration of both

 Stoichiometric calculations show that the C3S

by Dr. M. Jahidul Islam 16

 If the durability of a hardened cement paste to acidic

 From the standpoint of instability of the crystal

by Dr. M. Jahidul Islam 17

 Type I – ordinary Portland cement (OPC)

by Dr. M. Jahidul Islam 18

 Rate of heat evolution measured as temperature rise of

 The compounds of portland cement are non-

by Dr. M. Jahidul Islam 19