Hydraulic Cements: Atce-I

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ATCE-I Advanced Topics in Civil Engineering
Admixtures in Concrete
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Advanced Topics in Civil Engineering
HYDRAULIC CEMENTS
AND THEIR PROPERTIES
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Concrete Basics
Portland cement, water, sand, and coarse

aggregate are proportioned and mixed to
produce concrete suited to the particular
job for which it is intended.
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Definitions
Cement → Powder
Cement + Water →Cement Paste
Cement Paste + Fine Aggregate (FA) → Mortar
Mortar + Coarse Aggregate (CA) → Concrete
Professor Kamran M. Nemati

First Semester 2006 1
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Definitions
Concrete is initially plastic, allows

one to mold into desired shape.
Chemical reaction (hydration) and

paste set of concrete - producing
strength and stiffness.
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Cement
Cement is a pulverized material that
develops binding forces due to a reaction
with water
Hydraulic Cement → Stable under water
Nonhydraulic Cement → Products of

hydration are not resistant to water (i.e.
limestone)
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Hydraulic Cements
Cements that harden by reaction with
water and form a water-resistant
product.
Portland Cement (P.C.)
Portland cement is a hydraulic cement
capable of setting, hardening and
remains stable under water. It is
composed of calcium silicates and some
amount of gypsum.

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Cement Chemistry
In cement chemistry, the individual oxides and clincker
compounds are expressed by their abbreviations
Short Hand Notation Reactive Compounds

C (CaO, calcium oxide) C3S (tricalcium silicate)
A (Al2O3, alumina) C2S (dicalcium silicate)
S (SiO2, silica) C3A (tricalcium aluminate)
S (SO3, sulfate) CSH2 (gypsm)
H (H20, water) C4AF (tetra-calcium
alumino ferrite)
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Compounds of Portland Cement

C3S 3CaO . SiO2
C2S 2CaO . SiO2
C3A 3CaO . Al2O3
C4AF 4CaO.Al2O3.Fe2O3
C4A3S 4CaO.3Al2O3.SO3
 C 3S = Tricalcium Silicate
 C S = Dicalcium Silicate
 2

 C3 A = Tricalcium aluminate
C 4 AF = Tetracacium aluminate ferrite
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Cement Chemistry
Hydration Reactions
2C3S + 6H C-S-H + 3CH (120 cal/g)
2C2S + 4H C-S-H + CH (62 cal/g)
C3A + 3CSH2 +26H C6AS3H32 (300 cal/g)
2C3A + C6AS3H32 + 4H 3C4ASH12
C4AF + 10H + 2CH C6AFH12
C3S2H3 (C-S-H gel)

CH (calcium hydroxide)
C6AS3H32 (ettringite)
C4ASH12 (monosulfate)
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Hydration of Portland Cement

Hydration: Reaction with water
2C3S + 6H → C − S − H + 3CH + 120 Cal/g
2C 2S + 4H → C − S − H + CH + 62 Cal/g
C 3 A, C 4 AF, C S H → C − A − S − H (Ettringit e)
Compound Composition Morphology Amount (% Vol.)
Variable Poorly crystalline

C-S-H C/S ≈ 1.5 to 2 High surface area: higher 50 – 60%
bonding energy
Large hexagonal crystals,
CH Ca(OH)2 low surface area, and poor 20 – 25%
bonding energy
C6AS3H32 Long, well crystallized
C-A-S-H Ettringite needles 15 – 20%
C4ASH12-18 Hexagonal – small
Monosulfate crystals
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Manufacturing Process
Calcium silicates are the primary constituents
of portland cement.
Raw material for P.C. Calcium & Silica
Calcium: Limestone, chalk, etc (CaO+CO2)
Silica: Clays and shales (SiO2+Al2O3+Fe2O3+H2O)
Raw mix should be well

2/3 Calcium 
 homogenized before the
 1/3 Clay  heat treatment

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Aerial Photo of a Cement Manufacturing Plant

(Colorado)
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Raw Mill Feed

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Kiln Line Overview

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Raw T = 1400°C
(Limestone Rotary Kiln Clinker+Gypsum
+Clay) Grind
Grind Mill Portland Cement
 3CaO.SiO 2 (C3S )
Limestone → CaO + CO 2  (C 2S)
  2CaO.SiO 2
→
Clay → SiO 2 + Al2O 3 + Fe 2 O 3 + H 2 O   3CaO.Al2 O 3 (C3A )
4CaO.Al2 O 3 .Fe 2 O 3 (C 4 AF)
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Fineness
Reactivity of cement with water is
a function of its fineness.
Generally, the finer a cement, the

more rapidly it will react, and the
strength development will be
enhanced (expensive).
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Types of Portland Cement

ASTM C 150, Standard Specifications for
Portland Cement
Type I: General purpose. For use when the special
properties specified for any other types are not required.
Type II: For general use, more specially when moderate
sulfate resistance or moderate heat of hydration is desired.
Type III: For use when high early strength is desired.
(limit the C3A content of the cement to maximum 15%)
Type IV: For use when low heat of hydration is desired.
Type V: For use when high sulfate resistance is desired.
(Maximum limit of 5% on C3A)
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Effects of Chemical Composition of Portland

Cements on Strength
In classic research from over seventy years
ago Bouge and Lerch* found that of the four
portland cement phases only C3S and C2S
developed appreciable compressive strength
when pure samples of each were hydrated.
The compressive strength found by Bogue and
Lerch** are plotted in the next Fig. as a
function of age. Compressive strengths of C3A
and C4AF, hydrated alone “A” and have not
been plotted explicitly.
* T.C. Powers, “The Non-Evaporable Water Content of Portland Cement Paste: Its Significance for
Concrete Research and Its Method of Determination,” ASTM Bulletin, No. 158, (May 1949) pp. 68-76.
** R H Bouge and W Lerch “Industrial Engineering, Chem. 26 873 (1934)
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Effects of Chemical Composition of Portland

Cements on Strength
The compressive strength found by Bouge and Lerch** for hydrated samples of the
pure cement phases C3S and C2S are plotted as a function of age. The compressive
strengths of C3A and C4AF, hydrated along and with gypsum, fall within the cross-
hatched region labeled “A” and have not been plotted explicitly. The time scale is
linear. The time scale is logarithmic, which has the effect of expanding the early
ages, and this shows the differences between strength gain of C3S and C2S pastes.
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The Structure of Concrete

The type, amount, size, shape & distribution of
phases present in a solid material constitute its
structure.
Concrete Consists of aggregates, paste and voids.
The macrostructure of concrete is shown below:
A polished section
of concrete
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The Microstructure of Portland Cement Concrete
The structure of the aggregates in

concrete is important but it can be
characterized as a macrostructure
which is visible to the human eye.
The limit of resolution of the unaided
human eye is approximately 1/5
millimeter which is 200 microns.
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The use of both light and electron

microscopes allows the study of the
microstructure of concrete at the
submicron level.
The microstructure of concrete can
be divided into regions:
Cement Paste
Transition Zone between Aggregate
and Cement paste
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Structure of “un-damaged” Concrete

Macrostructure
Aggregates (CA, FA)
Hydrated cement paste (hcp)
Entrapped air voids
Microstructure
Hydrated cement paste
(Hydration products:C-S-H, ettriginite;
monosulfate; porosity: gel, capillary pores

entrained/ entrapped air voids)
Transition zone (TZ)
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Microstructure of Concrete
(Hydration products)
CH C-S-H
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(Hydration products)
Ettringite
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(Transition Zone)
Characteristics of the TZ
Large crystals of Ettringite and
CH with preferred orientation
Porous Structure 26
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One way to view cement paste is to

consider the hydration of one grain of
cement.
The partial hydration of one grain of
cement is schematically represented in the
next slide.
There are many details in this process that
are not yet understood, but there is
sufficient information available to allow a
consistent mental picture to be considered.
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The hydration products
formed inside and outside
the cement grain are
schematically represented.
The multiple nature of the
cement grain is neglected
and assumed to be a
single phase that shows
two types of products.
P1 refers to the “primary”
portlandite which appears
early in the originally
water-filled space.
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The Microstructure of Portland

Cement Paste
The hydration of a number of cement grains
is schematically represented in the next slide
at different degrees of hydration.
The fresh paste (i.e., the initial combination
of water and cement grains) is drawn to
approximately represent the 0.4
water/cement ratio, and thus there are not
enough hydration products to fill the
originally-water-filled space and a capillary
porosity remains in the final microstructure.
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The Microstructure of Portland Cement Paste
A schematic representation of the hydration of a number of cement grains. The multiphase

nature the cement grains has been neglected as this is like the hydration of tricalcium
silicate alone. (a) Fresh paste of water-to cement ration of 0.4 is shown cement grains in
the originally water-filled space. (b) After 33% hydration, the cement grains now have
inner hydration regions and outer products which form a “columnar zone” around each
grain. (c) After 67% hydration, the un-hydrated cores are clearly surrounded by thick
“rims” of inner hydration products and the columnar zone of outer products is growing on
the surface of each grain. The primary portlandite, P1, is shown with the dendrite
morphology. (d) At 100% hydration, the un-hydrated cement has been consumed but the
shape of the original cement grains can be distinguished if the inner product differs from the
columnar zone of outer products. The intergrowth of the columnar zones from two different
grains is shown at several points, but this would be larger at low water/cement rations.
Originally water-filled space = clear, unhydrated cement = /// , inner hydration products = ,
outer hydration products = , & primary portlandite = P1.
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Capillary Porosity
The originally-water-filled space within the
cement paste becomes the capillary pores
which act as stress concentrations and
reduce the strength significantly.
The strength of most engineering materials is
increased with a decrease in porosity, and by
controlling the water/ cement ratio the
engineer is assured that the basic porosity of
the paste is also controlled. That is not to
say the other sources of porosity will not
occur, but at least the cement paste will
have a given porosity.
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Capillary Porosity
Figure below shows a graphical representation of the
relative volumes of hydration products during hydration.
Graphical representation of the relative volumes of hydration products

during hydration. The initial w/c is 0.5, and one unit of cement is shown to
produce two volumes of hydration products.
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Capillary Porosity Over a Range of W/C Ratios
If cement paste specimens are prepared

with a range of w/c ratios it is apparent
that the density of high w/c samples is
much lower than low w/c samples.
This is illustrated in the next slide in a
presentation originally given by T.C.
Powers*.
*T.C. Powers, “The Non-Evaporable Water Content of Portland Cement Paste: Its Significance for
Concrete Research and Its Method of Determination,” ASTM Bul., No. 158, (May 1949) pp. 68-76.
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Capillary Porosity Over a Range of W/C Ratios
Composition of Cement Paste at different stages of hydration. The

percentage indicated applied only to paste with enough water-filled space
to accommodate the products at the degree of hydration indicated.
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ATCE

Portland cement, water, sand, and coarse

Cement + Water →Cement Paste

Cement Paste + Fine Aggregate (FA) → Mortar

Mortar + Coarse Aggregate (CA) → Concrete

Professor Kamran M. Nemati

Concrete is initially plastic, allows

Chemical reaction (hydration) and

Hydraulic Cement → Stable under water

Nonhydraulic Cement → Products of

Professor Kamran M. Nemati

Short Hand Notation Reactive Compounds

Compounds of Portland Cement

C3S2H3 (C-S-H gel)

Professor Kamran M. Nemati

Hydration of Portland Cement

Variable Poorly crystalline

Raw mix should be well

Aerial Photo of a Cement Manufacturing Plant

Professor Kamran M. Nemati

Raw Mill Feed

Kiln Line Overview

Professor Kamran M. Nemati

Generally, the finer a cement, the

Types of Portland Cement

Effects of Chemical Composition of Portland

Professor Kamran M. Nemati

Effects of Chemical Composition of Portland

The Structure of Concrete

The Microstructure of Portland Cement Concrete

The structure of the aggregates in

Professor Kamran M. Nemati

The Microstructure of Portland Cement Concrete

The use of both light and electron

Structure of “un-damaged” Concrete

monosulfate; porosity: gel, capillary pores

Professor Kamran M. Nemati

The Microstructure of Portland Cement Concrete

One way to view cement paste is to

Professor Kamran M. Nemati

The Microstructure of Portland Cement Concrete

The Microstructure of Portland

The Microstructure of Portland Cement Paste

A schematic representation of the hydration of a number of cement grains. The multiphase

Professor Kamran M. Nemati

Graphical representation of the relative volumes of hydration products

Capillary Porosity Over a Range of W/C Ratios

If cement paste specimens are prepared

Professor Kamran M. Nemati

Capillary Porosity Over a Range of W/C Ratios

Composition of Cement Paste at different stages of hydration. The

Professor Kamran M. Nemati

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