CONTENTS

No. Content Page

Introduction 2
Chapter (1) Cement manufacture and blended cement 3
1.1 Ordinary Portland Cement composition, types 4
and manufacturing
1.2 Blended cement 6
Chapter (2) Characterization of pozzolana 8
2.1 Definition 9
2.2 Types and their composition 9
2.3 Difference between pozzolanic cement and 19
pozzolana cement
Chapter (3) Lime and pozzolana mixtures 20
3.1 Pozzolanic reactions 21
3.2 Thermal treatment of pozzolana 23
3.3 Reaction products 24
Chapter (4) Properties of pozzolana mixtures 27
4.1 Microstructure and porosity of pozzolana cement 28
4.2 Properties of pozzolana containing mortars 34
4.3 Effect of pozzolana on durability 37
Chapter (5) Experimental Results 49
5.1 Determination of free lime procedures 50
5.2 Results and discussion 51
List of tables 53
List of figures 45
References 55

1
 Introduction

Pozzolana is one of the mineral admixtures blended with the Portland cement
clinker in an attempt to improve mechanical and physical properties for
produced concrete. Pozzolana also reduces cost of cement manufacture where
it replaces a part of clinker which production cost is high.

Most importantly the role of pozzolana in improving durability of concrete

has provoked an increase in use of pozzolanic materials in cement
manufacture.
This research will include a simple characterization of pozzolana and a study
of its effect on properties of cement.

2
Cement Manufacture and Blended Cement

Ch. (1): Introduction

3
1-1. Ordinary Portland Cement
Portland cement is a hydraulic binding material most used in building and
structures.
1-Composition:
It is composed of clinker which is a ground burnt mixture of raw materials,
limestone and clay, and other additives that are used to improve quality and
properties of clinker such as gypsum which control setting time of cement,
mineral admixtures are added up till 15% of the total amount.
A] Chemical composition
Lime stone is composed of two oxides, CaO and CO2 , while clay is composed
of SiO2, Al2O3 and Fe2O3; CO2 is removed by burning and the remaining four
oxides are the main constituents of clinker in the following percentages:
CaO 62-68%
SiO2 21-24%
Al2O3 4-8%
Fe2O3 2-5%
There are also other minor oxides that can affect quality of the clinker such as;
MgO when it exist in percentage above 5% it is burned at 1500°c and slakes
very slowly causing cracks in hardened concrete. Alkali oxides like Na2O or
K2O in percentage above 1% cause failure in concrete.
These oxides are not free in clinker, they exist in form of combined materials,
and the main four compounds are:
3CaO.SiO2 (alite) 45-65%
2CaO.SiO2 (belite) 15-35%
3CaO.Al2O3 (celite) 4-14%
4CaO.Al2O3.Fe2O3 (celite) 10-18%
Free CaO are not supposed to exist in clinker because it has the same effect of
MgO but in wider range.
B] Mineral composition
Knowing the minerals in clinker allow us to pre determine its physical and
mechanical properties. Minerals in clinker are subdivided into
High alite C3S >60%
Low alite C3S >50-60%
Belite C2 S >35%
Aluminate C3A >12%
Aluminoferrate C4AF >18%
Varieties of OPC have altered percentages of each mineral according to the
cement type.

2- Types of OPC:

4
Different types of Portland cement are manufactured to meet different
physical and chemical requirements for specific purposes, such as durability
and high-early strength. Eight types of cement are covered in ASTM C 150.

More than 92% of Portland cement produced is Type I and II (or Type I/II);
Type III accounts for about 3.5% of cement production. Type IV cements is
only available on special request, and Type V may also be difficult to obtain
(less than 0.5% of production).

Although IA, IIA, and IIIA (air-entraining cements) are available as options,
concrete producers prefer to use an air-entraining admixture during concrete
manufacture, where they can get better control in obtaining the desired air
content. However, this kind of cements can be useful under conditions in
which quality control is poor, particularly when no means of measuring the air
content of fresh concrete is available. If a given type of cement is not
available, comparable results can frequently be obtained by using
modifications of available types. High-early strength concrete, for example,
can be made by using a higher content of Type I when Type III cement is not
available, or by using admixtures such as chemical accelerators or high-range
water reducers (HRWR). The common types of OPC are listed in the table
bellow. Table (1-1)
Cement
Use
type
General purpose cement, when there are no
I1
extenuating conditions
Aids in providing moderate resistance to sulfate
II2
attack
III When high-early strength is required
When a low heat of hydration is desired (in massive
IV3
structures)
4
V When high sulfate resistance is required
A type I cement containing an integral air-entraining
IA4
agent
A type II cement containing an integral air-entraining
IIA4
agent
A type III cement containing an integral air-
IIIA4
entraining
3- Manufacturing:
•Raw materials must contain 75-78% CaCO3 and 22-25% of clayed
materials, since there are no natural rocks with that composition, a mixture of
limestone and clay is used in addition to the correcting admixtures to
5
compensate for oxides not exist in raw materials. For example insufficient in
SiO2 calls for introduction of high silica materials such as (opoka or diatomite)
•Also there is wide use in cement industry for waste and by-products of
other industries such as blast furnace, slag or nepheline slime.
•The fuel used is pulverized coal, fuel oil and natural gas.
Steps of manufacturing flow sheet:
•Quarrying lime stone and clay
•Preparing raw materials and blending them
•Burning mixture
•Grinding with gypsum to fine powder with addition
Techniques of manufacturing:
•Dry method: raw materials are mixed, ground and burned dry with out
water
•Wet method: raw materials are mixed with water then ground and burned.
•Combined method: to acquire advantages of both methods, raw materials
are mixed with water, ground then dewatered before drying as granules.

1-2. Blended Portland Cements

Blended cement is a mixture of Portland cement and blast furnace slag (BFS)
or a mixture of Portland cement and a pozzolana. The use of blended cements
in concrete reduces mixing water and bleeding, improves finish ability and
workability, enhances sulfate resistance, inhibits the alkali-aggregate reaction,
and lessens heat evolution during hydration, thus moderating the chances for
thermal cracking on cooling. Blended cement types and blended ratios are
presented in table bellow. Table (1-2)

Type Blended Ingredients

IP 15-40% by weight of pozzolana (fly ash)
I(PM) 0-15% by weight of Pozzolana (fly ash)
(modified)
P 15-40% by weight of pozzolana (fly ash)
IS 25-70% by weight of blast furnace slag
I(SM) 0-25% by weight of blast furnace slag
(modified)
S 70-100% by weight of blast furnace slag

The advantages to using mineral admixtures added at the batch plant:

• Mineral admixture replacement levels can be modified on a day-to-

day and job-to-job basis to suit project specifications and needs.

6
 • Cost can be decreased substantially while performance is increased
(taking into consideration the fact that the price of blended cement is at
least 10% higher than that of Type I/II cement [U.S. Dept. Int. 1989]).
• GGBFS can be ground to its optimum fineness.
• Concrete producers can provide specialty concretes in the concrete
product markets.

Precautions must be considered when mineral admixtures are added at the

batch plant:

• Separate silos are required to store the different hydraulic materials

(cements, pozzolanas, and slags). This might slightly increase the initial
capital cost of the plant.
• There is a need to monitor variability in the properties of the
cementitious materials, often enough to enable operators to adjust
mixtures or obtain alternate materials if problems arise.
• Possibilities of cross-contamination or batching errors are
increased as the number of materials that must be stocked and controlled
is increased.

7
 Characterization of Pozzolana

Ch. (2): Characterization of Pozzolana

2-1. Definition

8
The term Pozzolana has two meanings; the first is that pyroclastic rocks
mainly glassy or zeolitised which occur near Pozzuoli (ancient Puteoli, Italy)
or near Rome.
The second meaning is those artificial or natural materials that harden when
mixed with water in presence of lime or any material that release calcium
hydroxide (Portland cement). The interest here will be of the latter definition
since it is more general.
For along time the interest in Pozzolana was restricted to Italy where natural
Pozzolana was found. In other countries that interest is rather recent, arises
from the need to reuse waste materials such as fly ash and silica fume. Many
studies have confirmed that pozzolanic cement yield concrete showing a high
ultimate strength and great resistance to aggressive attacks.
Establishing a classification for pozzolanic materials has proven difficult since
that name include materials of different composition and mineralogical and
geological origin. The more common classification is of the origin of
Pozzolana, a subdivision to natural and artificial pozzolanas. This division is
not very well defined since there are materials that originally pozzolanic but
contain other components which takes on clear pozzolanic action only by
firing.
Types & Their Composition .2-2

Volcanic origin Sedimentary Mixed -------------

Natural
Incoherent Tuffs origin origin -
Fly ash Burned clays Micro Other
Artificial
(Class (F (Class (C and shale silica materials
(Table (2-1
Natural pozzolana
(a) Volcanic origin:
Pyroclastic rocks result from explosive volcanic eruptions. Rapid pressure
decrease during eruption causes the gases dissolved in liquid magma to be
released forming microscopic bubbles in particles, forming a micro porous
structure. At the same time particles are subjected to quenching process
responsible for the glassy state. The material can be deposited on ground or in
water, ground deposits are loose and heterogeneous, they are composed of
ashes mixed with ducts fragments.
Non explosive eruptions produce weak quenching which is not sufficient to
prevent crystallization which give no or little pozzolanic effect.

9
 1- Incoherent materials; glassy volcanic pozzolanas. Most common example
is Italian pozzolana form Campania.
The following table shows the chemical composition of some incoherent
volcanic pozzolana by percentage.

Pozzolana SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 SO3 LOI
Bacoli 53.08 17.89 4.29 9.05 1.23 3.08 7.61 0.31 0.65 3.05
Barlie 44.07 19.18 9.81 12.25 6.66 1.64 1.12 0.79 .Tr 4.42
Salone 46.84 18.44 10.25 8.52 4.75 1.02 6.35 0.06 .Tr 3.82
Vizzini 50.48 16.44 11.59 4.86 5.24 0.87 0.17 0.08 0.15 9.68
Volvic 54.3 14.5 4.47 2.6
Santorin
65.1 19.53 5.5 3 1.1 3.5
earth
Rhine
58.91 15.89 2.85 2.48 1.33 6.12 4.53 2.21
tuffash
Rhyolite
65.74 14.56 2.54 3.35 4.97 1.92 3.43
Pumicite
Furue
69.34 14.56 1.02 2.61 1.33 3 2.39 0.25 1.85
shirasu
Higashi
71.77 11.46 1.14 1.1 0.54 1.53 2.55 0.14 6.5
Matsuyama
(Table (2-2
LOI: loss on ignition
The mineralogical composition of some in coherent volcanic pozzolanas is
.shown below in the table
Pozzolana Country Active Phase Inert Phase
Bacoli Italy Glass ,Quartz, feldspar, augite
Partially decomposed Pyroxene, olivine, mica,
Barlie Italy
glass analcime
Leucite, Pyroxene, alkali
Salone Italy Glass, analcime
feldspare, mica
Feldspare, quartz, olivine,
Vizzini Italy Glass
clay
Volvic France Glass Andesine, quartz, diopside
Quartz, anorthite,
Santorin earth Greece Glass
labradorite
Quartz(9%),
Rhine trass Germany (Glass (55-60%
(feldspar(15%
(Glass (62-67%
Quartz(19%),
Bavaria trass Germany (Chabasite(3%
(feldspar(15%
(Analcime(5%
10
 Rhyolite Clay(5%), calcite, quartz,
Pumicite
USA (Glass (80%
feldspar
Quartz(1%),
Furue shirasu Japan (Glass (95%
(anoethite(3%
Higashi Quartz(1%),
Matsuyama
Japan (Glass (97%
(anoethite(1%
(Table (2-3

(2) Compact materials (tuffs); the deposits of volcanic pozzolana could

contain compact layers as a result of weathering, which can cause zeolitisation
or agrillation. Zeolitisation increase pozzolanic activity and agrillation cause
decrease in it. Chemical composition of some tuffs is shown in the following
table.

Pozzolana SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 LOI
Bacoli 52.12 18.29 5.81 4.94 1.2 1.48 5.06 11.1
Barlie 62.45 16.47 4.41 3.39 0.94 1.91 2.06 7.41
Salone 55.69 15.18 6.43 2.83 1.01 0.26 16.33
Vizzini 73.01 12.28 2.71 2.76 0.41 0.1 6.34
Volvic 54.68 17.7 3.82 3.66 0.95 3.43 6.38 9.11
Santorin
67.7 11.32 2.66 3.73 1.64 0.18 7.27
earth
Rhine
40.9 12 14 14.6 1.45 12.06
tuffash
Rhyolite
71.63 10.03 4.01 1.93 1.22 2.35 3.05
Pumicite
Furue
71.65 11.77 0.81 0.88 0.52 1.8 3.44 0.34 9.04
shirasu
Higashi
71.11 11.79 2.57 2.07 0.15 1.66 1.66 0.27 9.5
Matsuyama
(Table (2-4
In some deposits transformation of pozzolana and incoherent glassy layers
into compact tuffs is evident. Pozzolana in common is separated from tuffs
with an intermediate layer. The composition of those three layers is shown in
the following table.
Pozzolana Intermediate layer Yellow tuffs
SiO2 56.04 54.3 51.36
TiO2 0.42 0.42 0.42
ZrO2 0.03 0.05 0.03
Al2O3 17.79 17.4 16.84
Fe2O3 2.07 2.65 3.9
11
 FeO 2.8 2.12 0.84
MnO 0.12 0.15 0.14
MgO 1.19 0.92 0.99
CaO 3.47 3.61 3.47
BaO 0.06 0.08 0.05
K2O 7.43 6.93 6.57
Na2O 4.17 3 2.57
Cl2 0.05 0.06 0.09
SO3 0.05 0.05 0.04
P2O5 0.1 0.08 0.13
CO2 0.44
-
H2O 0.6 2.65 4.96
+
H2O 3.79 5.7 7.55
Total 100.18 100.17 100.39
(Table(2-5
The relation between loose pozzolana layer and layer of tuffs is proved by
reproducing the (pozzolana → yellow tuffs) transition. Bucoli pozzolana
underwent hydrothermal treatment resulting in a material similar to yellow
tuffs. Chemical composition does not change but the original component was
transformed into zeolitic materials confirming the large capacity of pozzolana
for zeolitisation. Rate of transformation and type of mineral resulting depend
on autoclaving conditions and chemical activator used. The table shows the
mineral composition of transformed materials.
(%)Contents
Tokay Heulandite
Mineral
Zaloska tuffs Gorenje tuffs mountain form
tuffs theigarhorn
Clinoptilolite 62±3 68±3
Heulandite 18±1 11±1 100
Analcime 45±2
α-Quartz 19±1 28±2 15±1
Cristobalite 5±1
Montmorillonite Traces
Illite Traces
Andesine 24±1
Chlorite Traces
(Table (2-6

(b) Sedimentary origin:

12
Clays and diatomaceous earths are sedimentary rocks capable of combining
with lime. Clays originate from alternation of igneous rocks. Diatoms
originate from siliceous skeletons of microorganisms deposited in water.
Both clays and diatoms occur mixed together. Clay minerals alone can react
with lime but can not be used as pozzolana due to increased water demand and
lowering of strength. Diatomaceous earths, also called moler, consist of
mixture of montmorillonite and amorphous opal, used either as it is or
calcined to improve pozzolanic properties.
Chemical composition of some diatoms is shown in table:
Pozzolana SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 LOI
Moler 75.6 8.62 6.72 1.1 1.34 0.43 1.42 1.38 2.15
Diatomite 85.97 2.3 1.84 .Tr 0.61 0.21 0.21 8.29
Diatomite 60.04 6.3 5.8 1.92 2.29 11.93
(Table (2-7
:c) Mixed origin )
In north Rome there are some deposits composed of materials of different
origin.
Chemical composition of some of those materials is presented in the table
below:
Pozzolana SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O SO3 LOI
Sacrofano 85.5 3.02 0.44 1.22 0.58 0.16 0.26 0.77 7.94
White earth-
90 2.7 0.7 0.2 6.1
a
White earth-
84.25 4.5 1.55 2.4 8.4
b
Whit earth-c 78.4 12.2 1.5 1.55 8.6
White earth-
56.8 21.4 1.7 2.35 7.5
d
Beppu white
87.75 2.44 0.41 1.1 0.19 0.23 0.11 0.11
clay
Gaize 79.55 7.1 3.2 2.4 1.04 0.86 5.9
(Table (2-8
The presence of diatoms with fragments of volcanic rocks shows that these
deposits originate from deposition of materials of different origin in stagnant
water followed by acid attack.

Artificial pozzolana
:a)Fly ash )

13
It consists of finely divided ashes produced by burning of pulverized coal in
power plants.

Owing to high temperature reached in burning, most minerals of coal are

melted to small drops, sudden cooling transforms them into spherical glass
particles. Chemical composition of bituminous fly ash(class F), low lime, is
shown in table below:
Country SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 C LOI
France 51.68 27.01 6.25 1.72 1.88 0.54 4.49 4.7
France 48.1 24.68 6.5 1.41 1.82 0.56 4.06 11.7
Belgium 55.74 24.41 6.02 2.47 2.22 1.04 2.74
Taiwan 48.75 23.21 4.15 3.93 1 0.24 1.1 10.39
UK 50.09 28.1 11.7 1.62 1.54 0.28 0.62 1.27
Poland 50.8 23.9 8.6 3.6 2.8 0.8 2.9 0.8 2.9
Denmark 53.98 22.27 11.6 3.95 1.97 2.71 .Eq 0.73 2.13
Netherlands 50.46 25.74 6.53 4.32 2.24 2.04 4.43 3.95
Canada 47 17.7 25.3 2.1 1 0.7 2.3 0.3 2.4
Japan 57.5 26.1 4 5.1 1.3 1.5 1.35 0.4 1.6
UK 48 38.2 4.5 3.3 1.5 0.3 1.7 0.37 2.3
Japan 53.53 23.55 6.23 5.85 1.6 2.2 1.75 2.14 3.44
USA 52.24 19.01 15.71 4.48 0.89 0.82 2.05 1.34 0.92
Canada 43.8 22.1 16.2 3.5 0.8 4.4 .Eq 1.1 5
Germany 51.2 29.6 6.8 3.4 1.2 0.6 3.1 0.5 3.3
(Table (2-9
Class F fly ash has few mineral phases, beside the prevailing vitreous ground
mass, only four compounds are present: quartz, mullite, hematite and
magnetite.
The mineral composition of this class is presented in the following table:
Flay ash
Quartz Mullite Hematite Magnetite Carbon Glass Anhydrite
source
Dunston 4.5 11 2.7 1.4 3.1 77
Ferrybridge 2.8 6.5 1.6 1.9 1.5 86
Hams hall 3.5 10 2.1 1.2 0.6 83
Rye house 8.5 14 2.4 2.5 2.4 71
Skeleton
4.1 10 9 2.6 2.1 79
Grange
Northeast
7 28 7 7 4 45
P26
Northeast 2 9 7 3 70
14
 P27
EFA 1.8 2.1 0.7 95.4
LM 5.1 22.8 0.5 71.6
Lubbenan 17.1 10.4 2.7 75.8 11.4
Eophenhain 1.4 1.9 3.8 74.3 12.9
Swarze
2 5.7 1 74.3 16.9
Pumpe
Vackarode 2 6.2 2.2 80.2 9.4
Hagenwerder 0.3 5.1 6.1 85.1 3.3
Hershfeld 1.8 3.8 5.1 93.6 0.7
(Table (2-10
The microprobe analysis of types of class F fly ash show chemical
[(heterogeneity of particles. This is shown in the following table; [Table(2-11
.No SiO2 Al2O3 Fe2O3 CaO
1 58 36.1 3 2
2 53.1 33.1 6.3
3 51.1 42.9 5.1
4 43.5 24.2 9.6 18.4
5 42.5 30.2 12.9 7
6 42.1 29.3 17.9 4.6
7 42.1 24.2 26.8
8 42 29.5 20.8
Ash particles classification is shown in the following table:
Type shape colour texture Size comments
a- glassy, clear,
solid
b-glassy with
0-20
Spherical bubbles
1 Colorless
& round c-glassy with
trace crystalline
d-most
10-50
crystalline, solid
Spherical Light brown Light color are Deep color
2 5-30
& round to black glassy, all solid indicate iron
Bubbles give
10-
3 Rounded White Glassy, spongy foam or
200
cenospheres
Partially 10- Irregularity
4 Irregular Light brown
crystalline, solid 100 very marked
15
 Agglomerated
Partially 50- particles
5 Irregular Varicolored
crystalline, solid 500 contain red
areas
Partially burnt
20-
6 Irregular Black Solid or porous coal contain
200
some minerals
10-
7 Angular Colorless crystalline, solid May be quartz
100
May be
8 Angular Red crystalline, solid 5-50
hematite

(Table (2-12
There is another type of fly ash, Class (C) which has high lime content, this is
resultant from sub bituminous coal and lignite combustion. The chemical
composition of this class is shown in the table below:

Free
Country SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 LOI
lime
Saudi Arabia 52.3 25.2 4.6 10 2.2 0.6 0.4
Poland 44.4 16.4 6 22.1 1 0.1 0.5 4.6 3.9
Canada 38.67 18.56 5.89 22.96 4.99 1.74 0.41 1.87 6.26
Spain 49.8 17.3 8.7 24.9 1.9 0.3 1.7 4.3 2.3 11.4
Greece 26 10.6 6.59 42.1 1.84 0.17 0.8 5.57 4.55 10
b
USA 51.3 20.9 6 7.98 1.05 0.25 0.52 0.17
USA 44.6 15.5 7.7 20.9 0.89b 1.5 0.05
b
USA 32.8 22.9 5.1 27.4 4.82 1.56 2.21 0.53
Turkey 27.4 12.8 5.5 47 2.5 0.2 0.2 6.2 2.4 18.6
Turkey 40.6 9.1 7.7 19.9 8.1 0.9 0.7 10.6 1.4 5.5
Turkey 39.9 22.3 4.4 25.4 1.9 0.1 0.4 4.8 0.4 9.8
Italy 55.42 23.41 7.71 3.16a 3.82 0.9 2.87 0.18 1.06
Canada 47.9 21.9 4.91 13.3 2.92 6.05 0.96 1.16 0.14
(Table (2-13
a: Low-lime lignite b: Na2O equivalent
Unlike class F, class C has many mineralogical phases due to variable
chemical composition. By XRD analysis we can identify: quartz, lime,
periclase, anhydrite, ferrite, spinel, merwinite, alkali sulfate, melilite, sodalite
and hematite.
16
The mineralogical composition of this class is presented in the following table:

Mineral HL1 HL2 HL3

Quartz 4.5 5.6 5.1
Lime 18.6 5.5 9.8
Anhydrite 12.2 9.3 7.4
Plagioclase 28~ 15~ 20~
Hematite 4 6 2
Magnetite 0.8 2.5 0.6
Mullite 1 1.2 4.3
Amorphous and
30~ 50~ 50~
glass
(Table (2-14
The difference between class F and class C fly ash concerns the chemical and
mineral composition and the structure of the glass. These differences are
highlighted by the change in X-ray diffraction background induced by the
glass. The relation between content of CaO and the position of maximum of
X-ray in background is shown in the figure:

Figure (2-1)
(b) Burned clay and shale:
Clay gains a pozzolanic activity when burned at temperature between 600-
900°c. Theses artificial pozzolanas are composed mostly of silica and alumina.
The loss of combined water at burning cause the crystalline structure to be
destroyed, silica and alumina become in a messy and unstable amorphous
state.
Heating does not affect on anhydrous minerals, so the pozzolanic activity
depends on the clay minerals and the thermal treatment conditions.
The chemical composition varies according to the origin. Silica content can
vary between 22-42%, and lime can vary between 22-55%.

17
Burned shales have more complicated mineral composition than burned clays
depending on the chemical composition and temperature and duration of
burning. For example a burned shale at 750-840°c contain minerals already
exist in shale like: β-quartz, α-cristobalite, calcite, α-ferric oxide and
muscovite; and other minerals formed by burning like: gehlenite, anorthite,
wollastonite, orthoclase, anhydrite, β-C2S, CA and CaO.

(c) Micro silica or silica fumes:

The manufacturing process of silicon metal and ferrosilicon alloy in electrical
arc at temperature up to 2000°c generate fumes containing spherical micro
particles of amorphous silicon dioxide due to the reduction of quartz to silicon.
The gaseous silicon dioxide is transported by combustion gases to lower
temperature zones where it is condensed to tiny particles.
The main properties of micro silica are the high silica content, high specific
surface area and amorphous structure. The chemical composition of the micro
silica is shown in the table below:
Si metal manufacture FeSi 75%
SiO2 97-98 86-90
C 0.2-1.3 0.8-2.3
Fe2O3 0.02-0.15 0.3-1
Al2O3 0.1-0.4 0.2-0.6
CaO 0.08-0.3 0.2-0.6
MgO 0.3-0.9 1-3.5
Na2O 0.1-0.4 0.8-1.8
K2O 0.2-0.7 1.5-3.5
S 0.1-0.3 0.2-0.4
LOI 0.8-1.5 2-4
(Table (2-15
Micro silica particles are spherical and have average diameter of 0.1μm. The
specific surface area ranges from 15 to 25 m2/g. It may contain traces of
quartz, low-lime silica fume shows a high degree of condensation of silicate
ions since it is formed by polymeric species.

2-3. Difference between pozzolanic cement and pozzolana cement

When pozzolana is mixed with Portland cement and water, it reacts with
calcium hydroxide formed during hydration of calcium silicates. As a result
the final portlandite content in hydration products is always lower than it is in
18
Portland cement alone. The simultaneous existence of cement and pozzolana
modifies the hydration products. Pozzolanic cements are mixes of pozzolana
and cement that if dispersed in excess water under certain conditions give rise
to unsaturated calcium hydroxide solution. Pozzolana cement do not comply
with this requirements, as their pozzolana content is insufficient to combine all
portlandite formed during hydration of calcium silicates to give unsaturated
lime solution. Hardened pozzolanic cement lack for free lime, while pozzolana
cement does not. Portlandite content depends on the activity of pozzolana,
amount of lime released and pozzolana/cement ratio.
Pozzolana can be added at the plant or at the building site. In the first case,
pozzolana undergoes either grinding with clinker and gypsum or separate
grinding followed by mixing and homogenization.
In the latter case, pozzolana is introduced into concrete mixer along with
Portland cement. This procedure improves quality in term of strength and
stability, but it causes certain decline in properties of concrete when pozzolana
is added as partial replacement for Portland cement. Yet, this procedure is not
recommended for the following reasons:
•degree of homogenization reached is lower
•replacing large part of Portland cement with pozzolana reduces early strength
•building yards rarely have personnel, equipment and time required for
checking properties of pozzolana and mixes.

19
 Lime and Pozzolana Mixtures

Ch (3): Lime and Pozzolana mixtures

3-1. Pozzolanic reactions
Pozzolanic activity covers all reactions occurring between active constituents
of pozzolana, lime and water. There is great difficulty in evaluating
pozzolana's active phases so, the progress of reaction is followed in term of
20
diminution in free lime in system or the increase in silica+ alumina soluble in
acid using the Florentin attack method. The activity of pozzolana includes two
parameters, the maximum amount of lime that pozzolana can combine and the
rate at which this combination occur. The heterogeneity of pozzolana and the
complexity of hydration phenomena do not allow a model of pozzolanic
activity only enables a general trend identified.

Figure (3-1)
From the figure above, when water is in excess, amount of combined lime
vary according to type of pozzolana. After 180 days pozzolanas have
combined 45-75% of lime. In pastes, lime combination is lower than it is in
hardened mass.
The factors affecting amount of combined lime:
1- Different pozzolanas have different capabilities to combine lime, as shown
in the table below;
Free alkali Average
Mineral Lime Calculated lime
amount
component reaction Na2O K2O reaction
in trass
Rhenish
trass 43 1.5 0.4 13 5.5
Quartz
Feldspar 117 1.1 0.2 15 17.5
Leucite 90 1.3 1.8 6 5.4
Analcime 190 10.7 3 7 13.3
Kaolin 34 0.3 2.1 2 0.7
Glass phase 364 18 24 55 200
21
 Total ------- ------- ------- 98 242.5
Glass phase
272 6 6 66 179
Bavarian
Obsidian
176 3.7 3.1 ------- -------
glass
Table (3-1)
2- The larger the amount of combined lime, the higher the content in the active
phase and the lower the content in the inert phase.
3- The amount of combined lime is related to the SiO2 content in the active
phase which ranges between 45-75% in volcanic glass and fly ash but reach
95% in active amorphous micro silica.
4- Within certain limits the amount of combined lime increase as
lime/pozzolana ration increase, as shown in figure below;

Figure (3-2)
5- Combined lime also depends on curing time, but the rate varies between
types of pozzolana. The following figure illustrates effect of curing time on
the combination amount.

22
 Figure (3-3)
6- Short term activity depends on the specific surface area (BET) of
pozzolana, while long term activity better referred to the chemical and
mineralogical composition of pozzolana.
7- The larger the amount of water the higher the rate of combination, thus the
pozzolanic reaction is slower in paste.
8- The rate of pozzolanic reaction increase by the increase in temperature, as
seen from the following graph;

Figure (33-4)
3-2. Thermal treatment of pozzolanas
When heated, pozzolana undergoes chemical and structural transformation
that may change, to a positive or negative extend. The resulting effect, an
increased or decreased pozzolanic activity, depends on type of pozzolana,
temperature and duration of heating. The negative effect induced by
temperature explains the apparent contradiction that occurs in some materials.

23
If temperature is raised step by step, combined lime increase then decreases.
The following figure shows this effect, it also shows that heating is followed
by a decrease in specific area.

Figure (3-5)
This means that optimum thermal treatment must be defined for each
pozzolana by means of testing. For most pozzolanas the heating is done at 70-
800°c, higher temperature improve deverification, crystallization and
densification and formation of more stable phases. Micro structural changes
by calcinations are evident in natural pozzolana due to the variation in
refraction index.
3-3. Reaction products
Reaction of lime and pozzolana give similar products to those found in
hydration of Portland cement since the overall chemical composition of both
mixes falls in the same field. For the same reason different types of pozzolana
give the same products. The table below shows the difference between
hydration products in pastes and in hydration in excess water.
Dehydrate Neapolitan Rhine
Bacoli Sengi
d Kaolin yellow tuffs trass
a b a b a b a b a b
C-S-H + + + + + + + + + +
C2ASH8 + + + + + + + + + +
C4AH13 - - - - - - + - + +
C3A.CO3.H1
- + + + - - - + - -
2
C3AS3
- - + - - - - - - -
C3AH6
a: reaction time in water=90 days
b: w/s ratio=0.4 ; pastes cured for 5 years
Table (3-2)

24
Excess water accelerates final stage of reaction. The hydration products
formed in pastes are smaller in size and more irregular.
By extending reaction time between lime and pozzolana in solution, there are
some compounds are recognizable such as hex. Ca-aluminate, ca-silicate
hydrate, carboaluminate, gehlenite hydrate and hydrogarnet. The following
table shows nature and amount of hydrated compounds;
Curing Ag C- C3AH6 C3A.CaCO3.H12
Pozzolana C2ASH8
temp. e S-H C3AS2H2 C4AH13
20,40,6
Furue 7 + - + -
0
20,40,6 ++
Shirasu 180 (+) +++ (+)
0 +
20 7 - - (+) -
++
20 180 - + -
+
Higashi 40 7 (+) - (+) -
Matsuyam ++
40 180 - (+) -
a +
Tuff(G) 60 7 + - - -
++
60 180 - - -
+
20 7 - - +++ +
20 180 (+) (+) +++ +++
Kanto 40 7 (+) - + (+)
(Hachoiõji) 40 180 (+) +++ (+) (+)
Loam(R) 60 7 (+) +++++ (+) -
60 180 + ++++ - -
Beppu 20,40,6
7 + - - -
white 0
20,40,6 ++
Clay(V) 180 - - -
0 +
20 7 - (+) +++ -
20 180 - - ++ -
Tominaga 40 7 - (+) + -
Masa
40 180 - ++ + -
soil(M)
60 7 - + + -
60 180 (+) +++ (+) -
20,40,6
Takehara 7 + - - -
0
20,40,6
Fly ash (T) 180 ++ - + (+)
0
Table (3-3)
When gypsum occurs in the paste, ettringite can be formed, formation of
ettringite causes paste to crumple.
25
The C/S ratio in C-S-H is variable and depends on the type of pozzolana, time
and temperature of curing, the lime/pozzolana ratio and analytical method
used. The variability of C/S ratio is attributed to non-staichiometry of C-S-H,
depending on chemical composition of the pore solution. The progress of
pozzolanic reaction is marked by changes in distribution of silicate ions in the
reaction products.
SO4- in low lime fly ash dissolves in lime and water and cause ettringite and
gypsum to precipitate. The rate of ettringite formation depends on rate of
alumina dissolution.
If ash is washed with water the sulfate occur in soluble form and both
ettringite and gypsum are not formed. Low lime fly ash mixed with water and
lime form C-S-H, C4AH13 and C2SAH8 and some times ettringite. High lime
fly ash which contain high amount of free lime when mixed with water
transform to Ca(OH)2so it doesn't need any lime addition, so they corresponds
to artificial hydraulic limes. High lime fly ash may contain C2S, in this case
hardening occur due to pozzolanic reaction and hydration of hydraulic
components. In any case C-S-H, C4AH13, carboaluminate, gehlenite hydrate
and ettringite are formed. If lime combine with Al2O3 and SiO2 there will be
no pozzolanic action. The reaction of silica fumes and Ca(OH)2 is very rabid
and causes a phase to precipitate on silicon peroxide, this layer is unstable and
turns to C-S-H rabidly. In pastes, owing to high reactivity of silica fume, free
lime disappear generally between7 and 28 days. In all hydrations the product
C-S-H is more crystalline than that found in Portland cement.

26
 Properties of Pozzolana and Cement Mixture

Ch (4): Properties of pozzolana mixtures

4-1. Microstructure and porosity of pozzolana cement
Porosity of pozzolana-containing pastes;
27
It is an intrinsic property of cement which can be limited but not eliminated. It
influences the strength and permeability of paste, mortars and concretes.
All aspects of strength are related to total porosity where permeability depends
on structure and size distribution of the pores. Porosity depends on :
1- decrease by decrease in water ratio
2- decrease by increasing curing period
3- increase by increasing curing temperature
4- differs according to type of cement
Correct determination of porosity and pore size distribution is a difficult
target. Difficulties come from structure alternation that method of sample
preparation and determination induces. Determination involves preliminary
removal of water from pores of the paste and filling the same pores with a
suitable fluid. Water removal obtained by:
1- Oven drying
2- D-drying( under vacuum over a dry ice trap)
3- P-drying( under vacuum over magnesium per chlorate hydrate)
4- Sublimation
5- Solvent replacement
Methods of porosity determination are:
1- mercury intrusion under pressure
2- helium displacement at low pressure
3- methanol displacement at low pressure
4- water intrusion
5- nitrogen sorption
The relevant distribution curve allows calculation of:
1- Threshold diameter (TD): pore diameter at which continuous
mercury intrusion begins
2- Maximum continuous diameter (MCD): maximum pore diameter
corresponding to the main pore frequency
3- Main peak intensity (PI): frequency of pore corresponding to MCD
Influence of drying procedure on porosity and pore size distribution is
illustrated in the following figure:

28
 Figure(4-1)
These results show:
1- Oven drying result in partial distribution of pore structure due to
stresses induced by receding water meniscuses on drying.
2- Solvent replacement tends to preserve original pore structure.
The table below shows the effect of solvent type in solvent replacement
technique:
Pore
Heat Time of Pore
vol Total
Sample drying preheating TD vol At
solvent At pore
no. with vacuum (µm) 0.1
0.01 volume
vacuum treatment µm
µm
A 0 Methanol 0.5 16 37.5 51
B 5 Methanol 0.59 19 38.2 52
C 16 Methanol 0.59 16 36 50.5
D 24 Methanol 0.25 13.6 36 49
20h,100˚c
H 0 Isopropanol 0.35 12 35 49.8
J 5 Isopropanol 0.35 12 35 49.8
L 16 Isopropanol 0.35 12 35 49.8
M 24 Isopropanol 0.59 19 41.5 49.8
(For CEMI)
Table (4-1)
29
When Portland cement pastes are prepared with the same drying procedure,
the porosity values found by mercury intrusion or helium pycnometry are the
same. But this is different in case of pozzolana containing cement.
Since values of porosity obtained by helium are confirmed by using methanol
saturation, we can say that mercury can not occupy the entire space accessible
to helium and methanol.
When total porosity of pozzolanic cement is assessed by mercury intrusion, it
turns out to be higher than that of Portland cement. The table below shows
these results for natural pozzolana and containing cement:

Porosity
Portland Blending
sample 28 days curing 7 months curing
cement% component%
Rabid Slow Rabid Slow
CEM I 100 0 17 14.7 13.1 10.6
Filler 70 30 17.8 21.4 15.3 13.8
Fly ash 70 30 21.8 21.3 17.4 16.4
Vizzini
70 30 18.7 21.6 14.3 12.9
pozzolana
Qualiano
70 30 20 18.8 11.3 10.7
pozzolana
Casteggio
70 30 17.8 16.3 13.6 11.6
pozzolana
Barile
70 30 17.7 17.9 13.5 12.7
pozzolana
Sengi
70 30 17.5 19.3 13.4 34.2
pozzolana
Bacoli
70 30 17.8 18.7 13.3 11.4
pozzolana

Table (4-2)

30
As for silica fume and fly ash containing cement:

paste Age Total Av. Bulk Skeletal porosity Permeability

pore Pore density density
are diameter
Control 1 38.3 0.036 1.37 2.6 47.4 1.2×10-7
3 53.4 0.022 1.46 2.54 42.5 4.9×10-10
7 53.9 0.019 1.47 2.39 38.4 6.5×10-10
28 50.7 0.018 1.51 2.33 35 6.2×10-12
4515 1 28.8 0.045 1.43 2.65 46 1.1×10-7
3 48.4 0.026 1.4 2.48 43.6 2×10-8
7 50.4 0.023 1.4 2.32 39.7 1.3×10-8
28 50.7 0.02 1.5 2.39 37.4 1.3×10-11
4530 1 24.4 0.061 1.32 2.57 48.6 7.1×10-7
3 43.2 0.031 1.42 2.7 47.5 4.7×10-8
7 50.7 0.026 1.32 2.3 42.8 5.6×10-9
28 55.9 0.02 1.43 2.42 40.9 1×10-12
1015 1 32.9 0.041 1.37 2.54 46.3 6×10-8
3 43.3 0.028 1.41 2.46 42.7 6.4×10-9
7 53.9 0.022 1.42 2.43 42.1 6.1×10-10
28 55 0.019 1.47 2.36 37.9 2.9×10-12
1030 1 41 0.039 1.29 2.62 50.9 1.6×10-7
3 49 0.03 1.35 2.66 49.3 2.3×10-8
7 50 0.026 1.36 2.43 44.3 1.9×10-9
28 36.9 0.02 1.35 2.35 42.4 5.3×10-13
Table (4-3)
What ever was the type of pozzolana, porosity decrease with time but it still
higher than porosity of Portland cement. Porosity increases by increasing fly
ash but decrease by increasing rice husk.
Porosity of blended cement paste depends on method of determination through
all range of porosities. Porosity measured by methanol or helium pycnometry
appears to be lower than by mercury intrusion, as shown in figures below:

31
Figure (4-2)

Figure (4-3)

32
So, basically we can say that;
• Mercury porosity is higher than helium porosity
• Helium porosity is higher for oven dried samples than for solvent
replacement
The damage caused by mercury intrusion in fly ash containing pastes is
demonstrated by subjecting samples to two following intrusions. Repeated
intrusions showed that in Portland cements pores size distributions did not
change much except for an increase in threshold diameter, but blended cement
differs a lot.
The figure here shows that curve has changed from convex to convex.

Figure (4-4)

33
Since the two methods give comparable results with Portland cement pastes, it
can be assumed that the pore structure of pozzolana cement pasties different
and the pore system is more segmented.

4-2. Properties of pozzolana containing Mortars

Mechanical properties
1. Setting:
Setting time does not change greatly from Portland cement when using natural
pozzolana. As for fly ash, it delays initial and final setting times. Silica fumes
prolong setting times but, it is usually used with plasticizers which make it
difficult to differentiate the delay resultant by silica fume from the one of the
admixtures.
2. Strength:
Pozzolana starts reacting slowly with calcium hydroxide and initially behaves
as an inert material diluting the Portland cement. Pozzolana accelerates early
hydration of clinker after 8hours after mixing with water.
Partial replacement of pozzolana for Portland cement reduce initial rate of
hardening but at greater ages this situation is reversed and pozzolana cement
can attain the same or even higher strength than Portland cement.
The following figure shows that 30% replacement of fly ash can reduce
strength by 50%, difference in strength decrease by time till it disappears or
reverse sign.

Figure (4-5)
34
The moment of recovery depend on fineness of Portland cement and
pozzolana and activity of pozzolana. The effect of pozzolana on strength
depends on:
• Pozzolana content and type
The figure below shows an optimum level of replacement which is dependent
on type of pozzolana used.

Figure (4-6)
The strength of pozzolana cement depends on characteristics of pozzolana
used as shown in figure below.

35
 Figure (4-7)
• Particle size distribution of pozzolana
The figure below shows that the negative effect on strength increases with
particle size and decrease with time only for fine fractions.

Figure (4-8)
Grinding promotes activity of fly ash but if fineness exceeds certain limits
compressive strength decrease instead. That is due to decrease in combined
lime which is ascribed to decrease in permeability of paste which hinders
mobility of ions.

36
 • Properties of Portland cement
The influence of 8fly ashes and 4portland cements on relative compressive
strength.

Figure (4-9)
Difference in strength between blended and Portland mortars have been
attributed to different content of alkalis in Portland cements among other
factors.
Shrinkage
Normal percentage of pozzolana does not affect drying shrinkage or expansion
in water. The following table shows that shrinkage in air for Portland cement
and pozzolana cement is the same.
Curing period
Cement
7 28 90
CEM I 32.5 427 755 890
CEM I 42.5 396 733 873
CEM I 52.5 453 842 1043
CEM I 32.5 329 653 793
CEM I 42.5 381 725 904
CEM I 52.5 434 797 991
CEM I 42.5 430 685 810
CEM I 52.5 461 770 988
CEM IV 32.5 428 784 943
CEM IV 42.5 420 743 915
CEM IV A 393 737 889
CEM IV B 32.5 440 765 900
CEM IV A 42.5 425 706 890
Table (4-4)

37
The next table shows that shrinkage of mortars is affected by the fineness of
clinker more than by fineness of fly ashes.
Fineness(cm2/g) Fly ash Curing period
Clinker Fly ash content 7days 28days 90days 1year 5years
2540 0 430 500 650 750 750
2880 40 400 460 500 500 550
8200 40 400 500 560 600 630
3580 0 500 650 780 1000 1100
2880 40 400 530 590 680 720
8200 40 400 530 620 750 780
5130 0 700 870 1060 1340 1450
2880 40 460 590 720 840 870
8200 40 440 590 720 840 870
Table (4-5)

4-3. Effect of pozzolana on durability

Durability defines the suitability of concrete to preserve structural
performance, fixed by designer, over the time; it plays an important role in
.determining the service life of the structure
;Influence of environment
(1) H2O effect:
Water can decompose any hydrated compound in cement and leach lime
leaving a residue made of SiO2.xH2O,Al2O3.yH2O and Fe2O3.zH2O. The
residue acts as a protective layer against leaching on account of the gel-like
nature of its compounds.
The rate of leaching is high for porous concrete in excess presence of water or
its renewal. It slows down when concrete is compact and strong. Leaching
increases porosity and permeability which decreases strength and durability.
The methods for assessing resistance of leaching based on water percolation
through more or less porous concrete followed by determining leached lime or
loss of mass.
The amount of leached lime by distillated water from porous pozzolana
cement is less than released by Portland cement and decreases as
pozzolana/clinker ratio increase as shown in the following figure.

38
 Figure (4-10)
When compared to pozzolanic cement, Portland cement showed;
• Thicker corroded layer
• Diffuse porosity decreasing form the surface to the
inside
• Deposit on the surface of gel like layer crossed by
small channels
The mass loss of prism cured for28 days stored in soft water and brushed
increase by substituting 30-40%of fly ash for Portland cement.
That loss is related to the decrease in strength caused by partial replacement in
initial setting period. Acid water increase rate of leaching, but pozzolanic
cement shows better resistance than Portland cement as illustrated in the table
below:
Mix composition
Mix105 Mix109
OPC(kg/m3) 170 312
Fly ash(kg/m3) 170
Water/binder 0.35 0.6
28 days compressive
78.4 43.2
strength
Cumulative mass
loss(g/kg) 5.8 7.8
Brushed
39
 Un brushed 2.5 3.4
Table (4-6)
The reasons that hard pastes of pozzolanic cement are more resistant to
leaching more than Portland ones are:
• They contain 3-6%Ca(OH)2 compared to 20-22% of
Portland cement
• They contain more calcium silicate hydrates
• The C/S ratio of C-S-H is lower
• They have lower permeability

(2)SO4-2 effect:
Sulfate can be dangerous to concrete due to expansive nature of them or the
products of their reaction with cement. CaSO4 reacts on calcium aluminates
hydrates forming expansive ettringite (3CaO.Al2O3.3CaSO4.32H2O)
Na2SO4 react on calcium hydroxide forming gypsum which in presence of
aluminates gives ettringite.
MgSO4 react on all cement compounds forming Mg(OH)2 (brucite) and
gypsum.
Conditions enhancing formation of expansive compounds are:
• Occurrence of both aluminates hydrates and
calcium hydroxide, the following figures illustrate the positive effect of
natural pozzolana

Figure (4-11)
40
 Figure (4-12)
• Characteristics of mortar and concrete
(strength, porosity and permeability)
The figure below shows the expansion of Portland cement mortars by
increasing w/c ratio, i.e. by increasing porosity and permeability.

Figure (4-13)
• PH range, the range between 6-11.5 is less aggressive
41
 • Volume/surface area ratio of concrete. In the figure below we can
see that positive effect by pozzolana is enhanced by increasing the size
of the sample.

Figure (4-14)
Na2SO4 attack; natural pozzolana increase the sulfate attack resistance of
cement.
Also artificial pozzolana improves sulfate resistance to the attack by sodium
sulfate. The sulfate resistance of pozzolana increases as curing time increases.
Pozzolana only delays the performance failure but not eliminate it. They can
prolong the life expectancy of concrete as shown in the figure below.

42
 Figure (4-15)
The next figure shows the improvement in resistance to sulfate attack caused
by increase cement dosage.

Figure (4-16)
Silica fumes increase resistance to sodium sulfate attack, the higher the
replacement level the lower the expansion. The grade of silica play an
important role, since 10% replacement of good silica fume are enough to keep
expansion below0.1% while for the same level of protection 15% of poor
quality silica fume replacement is required. The physical and chemical
properties of 28 days fly ash and silica fume mortars are explained in the table
below through the pore volume of both when immersed for one year.
w/c 28 days 1year pore volume
ratio Comp. Total pore water 10% 10%
strength vol Na2SO4 MgSO4
Plain 0.55 45.3 39.8-17.6 33.8 94.8 52.2
mortar (11.1) (83.3) (36.1)
Fly ash 10% 0.54 37.1 22.4-23.6 26.3 25.8
(34.6) (32.9)
30% 0.52 35.8 44.5-15.1 33.2 27.7 22.9
(15.4) (20.9) (38.4)
50% 0.5 23.8 42.8-16.5 38.6 19.9
(13.2) (42.7)
70% 0.48 11.7 62.2-34.6 85.5 43.5
(10.6) (19.5)
Si fume 5% 0.55 44.4 50.7-13.8 30.1 45.6
(11.6) (28.9)
10% 0.54 45.1 36.1-11.6 44.7 46.8 22.4
(22.6) (24.6) (21.4)
20% 0.54 46.6 29-20.7 33.8 55.7
(17.8) (57.6)
43
 30% 0.53 50.2 28.4-21.1 17.8 27.2 68.6
(36.5) (31.2) (87.5)
Table (4-7)
Linear expansion, weight gain and sulfate consumption of concrete exposed to
5% sodium sulfate were strongly reduced when silica fume used in 10%
replacement. Inter grounding of pozzolana with gypsum reduce the effect of
sulfate attack more than when it is just mixed with clinker and gypsum.
MgSO4 attack;
It is considered to be more severe than sodium sulfate attack. Natural and
artificial pozzolana can enhance resistance of mortars to magnesium attack but
some times they can worsen the performance. That performance seems to be
dependent on type of pozzolana used.
OPC containing 25% of fly ash behaves like sulfate resisting in weak MgSO4
but it is of low performance in concentrated solutions.
The table below shows the loss of strength and resisting properties in Portland
and pozzolana mortars through time.
Type Type Compressive strength
of of MPa % of water cured samples
mortar cement 90 d 180 d 1 y 2y 90 d 180 d 1 y 2y
Plain OPC 37.8 12.8 17.4 7 107 61 40 16
SPC 36.7 20.2 8.5 116 61 23
SRPC 40.7 36.6 33.9 32.2 110 93 83 72
15%Si OPC 29.1 22.1 12 63 46 21
fume SPC 36.3 20.4 12.5 99 48 29
SRPC 46.8 17.7 11.7 103 39 23
Table (4-8)
OPC= ordinary Portland cement
SPC= slag Portland cement
SRPC= sulfate resisting Portland cement
Level of effectiveness of pozzolana don't depend much on type of cement
used, it depends more on level of replacement, the following figure prove that.

44
 Figure (4-17)
Influence of aggregates;
Alkali-silica reaction; this reaction forms a more or less viscous gel made up
of alkali- and alkaline earth silicates which tend to absorb water from the
environment and expand.
Conditions essential for alkali-silica reaction:
• High alkali content of cement
• Only a part of aggregates is reactive
• High humidity
Influence of pozzolana; there were cases where pozzolanas were not effective
in preventing expansion of alkali-silica reaction which is ascribed to
insufficient quantity or poor quality of pozzolana. The expansion of mortars
varies with the proportion of reactive aggregates and it reaches maximum at a
certain level "Pessimum effect". The addition of pozzolana reduces this effect
but some times give a similar effect as shown in the following figure.

45
 Figure (4-18)
Generally, partial replacement of high alkali cement with pozzolana produces
great reduction in expansion. However, some fly ashes give a pessimum effect
as shown in the figure.

46
 Figure (4-19)
This is not a general rule since in some fly ashes this peak doesn't appear as
shown in the figure below.

Figure (4- 20)

Addition of pozzolana increase total alkali content but the availability of these
alkalis depends on progress of pozzolanic reaction.
The next figure show that expansion reduction due to alkali-silica reaction
depends on the source of pozzolana which when differ it varies specific
surface area of pozzolana.

47
 Figure (4-21)
In conclusion, all laboratory tests and field experience have shown that
pozzolana reduce expansion provided that replacement is sufficient.
Factors reducing expansion
• Lower permeability
• Lower alkalinity
• High alkali content
• Low portlandite content
• Low C/S ratio for C-S-H

48
Experimental techniques

Ch. (5): Experimental

49
5.1- Determination of free lime in pozzolana procedures
Reagents;
• Solvent: One part by volume pure glycerol to 5 volumes absolute
ethyl alcohol.
• Indicator: 0.18 g of phenol phthaline was dissolved in 2160 ml of
the previous mixed solvent.
• Standard ammonium acetate titrante: 16 g dry crystalline
ammonium acetate was dissolved in 1 liter of distillated water.
Pozzolanas;
1- Standard silica fume
2- Standard Homra
Procedure
1- Sample preparation
To obtain CaO we burn Ca(OH)2 at 900˚c for 1 hour
To prepare testing samples we mix (8:2 lime : pozzolana) and cure them for
24 hours at 50˚c.
2- Standardization
0.5 g of freshly ignited CaO was placed in 200 ml Erlenmeyer flask, about 60
ml of glycerol-ethyl alcohol solvent were added.
A reflux condenser was fitted then the mixture was boiled for 5 – 20 minutes
and then titrated while still nearly boiled with ammonium acetate solution
until the pink color disappears. The boiling continued for 5-20 minutes and the
mixture titrated again, this process was continued till the free CaO content
does not exceed than 0.05 % after 2 hours boiling where no further pink
coloration appears.

3- Samples

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Exactly 0.5 g of sample was put in 200 ml Erlenmeyer flask, 40 ml of
glycerol-ethyl alcohol solvent were added and proceeding as in
standardization of ammonium acetate solution .

5.2- Results and discussion

Percentage of free lime is calculated by the law:
W1 × V2 × 100
%CaO =
W2 × V1

Where: W1 weight of freshly ignited CaO (standard).

V1 ml of ammonium acetate required for ignited CaO.
W2 weight of sample taken
V2 ml of ammonium acetate required for sample.
No. 1 2 3
Fresh 2g Silica
Sample 2g Homra+8g CaO
ignited CaO fume+8g CaO
Results
V1 = 74.5 ml
V2 (Homra) = 65 ml
V2 (Si.fume) = 62.5 ml
In Homra
0.5 × 74.5
%CaO = × 100 = 87.2%
0.5 × 65

In silica fumes
0.5 × 74 .5
%CaO = ×100 = 83 .8%
0.5 × 62 .5

Discussion:
From the results shown the percentage of free lime after 24 h curing for (8:2
lime: pozzolana) sample is as follows

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Pozzolana Homra Silica fumes
%CaO 87.2% 83.8%

The higher percentage in case of using homra indicates that silica fume react
with lime at a higher rate
Then the pozzolanic reaction of silica fume is some what faster than that of
homra.

List of tables
No. Table
1-1 Cement types and uses
1-2 Ingredients of blended cements
2-1 Types of pozzolana
2-2 Chemical composition of incoherent volcanic pozzolana
2-3 Mineralogical composition of coherent volcanic pozzolana
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2-4 Chemical composition of tuffs
2-5 Composition of the three layers in tuffs
2-6 Mineralogical composition of transformed materials
2-7 Chemical composition of diatoms
2-8 Chemical composition of mixed origin pozzolana
2-9 Chemical composition of bituminous fly ash(class F)
2-10 Mineral composition of bituminous fly ash(class F)
2-11 Chemical heterogeneity of fly ash (class F)
2-12 Ash particles classification of class F
2-13 Chemical composition of fly ash (class C)
2-14 Mineralogical composition of fly ash (class C)
2-15 Chemical composition of micro silica
3-1 Pozzolana combination with lime
Hydration products in pastes and excess water for pozzolana
3-2
cement
Nature and amount of hydrated compounds in excess water
3-3
solution of pozzolana-lime mixture
Effect of solvent in solvent replacement water removal of pastes
4-1
on porosity
Porosity results by mercury intrusion for Portland and blended
4-2
cement
Porosity results by mercury intrusion for silica fume and fly ash
4-3
cement
Comparison of shrinkage between Portland and pozzolana
4-4
cements
4-5 The relation between shrinkage and fineness of cements
4-6 Resistance of cements to water leaching
The physical and chemical properties of 28 days fly ash and
4-7
silica fume mortars
Loss of strength and resisting properties in Portland and
4-8
pozzolana mortars through time.
List of figures
No. Figure
The relation between content of CaO and the position of
2-1
maximum of X-ray in background
Relation between specific surface area and pozzolana/lime ratio
3-1
for different water content
Relation between amount of combined lime and pozzolana/lime
3-2
ration
3-3 Relation between amount of combined lime and time of curing
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3-4 Relation between temperature and rate of pozzolanic reaction
3-5 Thermal treatment of pozzolana
4-1 Effect of drying method on porosity and pore size distribution
4-2 Difference in porosity measured by methanol or helium and that
4-3 measured by mercury
Damage caused by mercury intrusion in fly ash containing
4-4
samples
4-5 The relation between compressive strength and time for mortars
4-6 Effect of pozzolana content on strength of mortar
4-7 The effect of pozzolana type on strength on mortar
4-8 Effect of pozzolana fineness on compressive strength
4-9 Influence of Portland cement properties on mortar strength
The amount of leached lime by distillated water from porous
4-10
pozzolana cement and Portland cement.
4-11 Effect of occurrence of both aluminates hydrates and calcium
4-12 hydroxide on formation of expansive compounds in concrete
4-13 Variation of expansion rate according to w/c ratio
4-14 Effect of size of sample on expansion of concrete
4-15 Effect of pozzolana content on strength
Improvement in resistance to sulfate attack caused by increase
4-16
cement dosage
4-17 Effect of cement type on expansion
4-18 Effect of pozzolana addition on expansion "pessimum effect"
4-19 Pessimum effect in some fly ashes
4-20 Fly ashes that don't give pessimum effect
Expansion reduction due to alkali-silica reaction dependant on
4-21
the source of pozzolana

References
1. A.Komar
Chapter (V)- B- Hydraulic binders
Building materials and components, 135-185 (1979- second edition 1987)
2. Lea
Chapter (10)- Pozzolana and pozzolanic cements (Franc Massazza)
Chemistry of cement and concrete, 471-602 ( 1998 )

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