Concrete Technology

Hydraulic Cements

Concrete Technology

HYDRAULIC CEMENTS
AND THEIR PROPERTIES

Concrete Technology

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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Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

Definitions
 Cement  Powder

 Cement + Water  Cement Paste

 Cement Paste + Fine Aggregate (FA)  Mortar

 Mortar + Coarse Aggregate (CA)  Concrete

Concrete Technology

Definitions

 Concrete is initially plastic, allows

one to mold into desired shape.

 Chemical reaction (hydration) and

paste set of concrete - producing
strength and stiffness.

Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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.

Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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)
 A (Al2O3, alumina)
 S (SiO2, silica)
 S (SO3, sulfate)
 H (H20, water)
 C3S (tricalcium silicate)
 C2S (dicalcium silicate)
 C3A (tricalcium aluminate)
 CSH2 (gypsm)
 C4AF (tetra-calcium
alumino ferrite)
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Concrete Technology

Compounds of Portland Cement

 C3S 3CaO . SiO2
 C2S 2CaO . SiO2
 C3A 3CaO . Al2O3
 C4AF 4CaO.Al2O3.Fe2O3
 C4A3S 4CaO.3Al2O3.SO3

 C3S  Tricalcium Silicate

 C S  Dicalcium Silicate
 2

 C3 A  Tricalcium aluminate
C 4 AF  Tetracacium aluminate ferrite
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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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 (Ettringite)
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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Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

Manufacturing Process

Aerial Photo of a Cement Manufacturing Plant

(Colorado)
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Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

Manufacturing Process

Raw Mill Feed

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Concrete Technology

Manufacturing Process
This image cannot currently be display ed.

Kiln Line Overview

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Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

Manufacturing Process
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  Al2 O 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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Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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.

Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

The Microstructure of Portland Cement Concrete

 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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

Microstructure of Concrete
(Hydration products)

CH C-S-H

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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

Microstructure of Concrete
(Hydration products)
 Ettringite

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Concrete Technology

Microstructure of Concrete
(Transition Zone)

 Characteristics of the TZ
 Large crystals of Ettringite and
CH with preferred orientation
 Porous Structure 26

Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

The Microstructure of Portland Cement Concrete

 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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Concrete Technology

The Microstructure of Portland Cement Concrete

 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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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 Concrete Technology
Hydraulic Cements

Concrete Technology

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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Concrete Technology

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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Professor Kamran M. Nemati

Winter Quarter 2015
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