I

Assessment of Beyuda Desert

Natural Pozzolana as cement
supplementary material
By:
Reem El-Samani Ahmed El-Sheikh (093042)
Samer Mamoon Hawari Al Mahi (093045)
Abd El-Gader Taj El-Sir Abd El-Gader (093053)
Mustafa Balla Ahmed Abd-Allah (093095)


A Thesis Submitted to the University of Khartoum in Partial fulfilment of
the requirements for the Degree of B.Sc. of Science in Civil Engineering

Supervisor:
Dr. Yousif Hummaida Ahmed

Faculty of Engineering
Civil Engineering Department
September 2014

II









{

}

: 501 ] ]




III

AKNOWLEDGEMENT

First and foremost, we would like to thank God the almighty, for without
his consent, it would be impossible to achieve what had been done in this
work. . We doubt that will never be able to convey our appreciation fully,
but we would like to express our sincere thanks and gratitude to our
families for their love, encouragement and support in all steps of our life.
And also we would like to express our greatest acknowledgement with
deep gratitude and gratefulness to our supervisor Dr. Yousif Hummaida
Ahmed for his close supervision, valuable guidance, advice and
suggestions, supply of references and careful reviews during the different
stages of the study. He facilitated a good supply of reading matter for the
project study. He pushed us hard to overcome the compilations of this
project with all of his knowledge, experience and critical thinking. He is
great assistance with his effort and continuous encouragement.
We have to select a list of names for the people who gave us great
assistance in the project process. The list must include: Engineer: Yahia
Adam Idriss (Senior concrete lab technician at University of Khartoum-
Civil Department), Ust: Honayda (concrete lab technician at University of
Khartoum-Civil Department) and all staff of concrete lab, Engineer Ali
Yahya Adam (supervisor of concrete lab at Islamic University), Ust:
Hajer (supervisor of sanitary engineering lab at University of Khartoum)
and Ust. Fathy (Soil mechanics lab technician at University of Khartoum)



IV

ABSTRACT
The aim of the study is to investigate the use of Beydoua desert natural
pozzolana BD-NP as cement replacement material.
The approach of the study was based on methods and scope of American
Society for Testing and Materials codes (ASTM-C311) and British
standard codes (BS EN 196-5:2011).
BD-NP specimen in form of pumicite and volcanic ash was procured and
further ground by ball milling. Physical properties namely fineness,
specific gravity (SG), moisture content and loss on ignition (LOI) were
carried out on the ground BD-NP. Also chemical analysis was carried
out on the BD-NP to determine metal oxides percentages.
Pozzolanic activity test was carried out on binder of 80% OPC: 20% BD-
NP according to BS EN 196-5 method.
The water / binder ratio of mortar with (80% OPC: 20% BD-NP) and
sand / binder ratio of 2.75 by weight were determined using hydraulic
mortar flow test to produce equivalent flow of mortar with 100% OPC
0 % BD-NP having water/cement 0.55. This Water / binder was found to
be 0.566to prepare specimen for the compressive strength test.
The tested Physical properties of the BD-NP were found as follows:
fineness of 87.63%, SG of 2.409 MC of 0.77 % LOI of 9.36 %, The
chemical composition of BD-NP showed that the SiO
2
(S) + Al
2
O
3
(A) +
Fe
2
O
3
(F) modulus = 85.8 %.
The 80% OPC: 20% BD-NP mortar produced, 16.73, 23.74, 27.1 & 36.2
MPa in 3, 7, 28 and 91 days respectively compared for 21.91, 26.9, 32.6
and 41.3 MPa for the OPC control mortar.
The overall results of these tests concluded that BD-NP can be classified
as pozzolana class N according to ASTM C 618. The pozzolanicity of
the BD-NP was confirmed by the results of BS EN 196-5 showing
remaining calcium oxide concentration of 2.8mmol/l in the filtrate of
(100 ml water + 16 gm OPC + 4gm BD-NP) compared for the theoretical
9.54 mmol/l.

V


( BD-NB )
.

(ASTM-C311) . (BS EN 196-5:2011)
( pumicite )
. BD-NP , :
. ,
.
00 % 00 %
BD-NP . (BS EN 196-5:2011)
( 00 % 00 % BD-NP )
0..1 ,
( 500 % 0 % BD-NP ) 0.11 .
0.100 .
:
% 0..08 , 0.402 , % 0...
2.80 .
01.0 .%
( 00 % 00 % BD-NP )
50..8 , 08..4 , 0..5 80.0 8 , . , 00 25 .
05.2 , 00.2 , 80.1 45.8 .

( class N )
( ASTM C 618 ) . ,
( 4 + 50
+ 500 ) 0.0 / 2.14 / .



VI

Table of Contents
AKNOWLEDGEMENT ....................................................................... III
ABSTRACT ............................................................................................ IV
..................................................................................................... V
NOTATIONS............................................................................................ X
LIST OF PHOTOGRAPHS .............................................................. XVII
CHAPTER (1) ........................................................................................... 1
INTRODUCTION .................................................................................... 1
1.1 Preface ............................................................................................... 2
1.2 Project aim, project significance& thesis layout ............................... 2
1.2.1 Project objectives and approach .................................................. 3
1.2.2 Project significance ..................................................................... 3
1.2.3 Thesis layout ................................................................................ 4
CHAPTER (2) ........................................................................................... 5
LITERATURE REVIEW ........................................................................ 5
2.1 Cement ............................................................................................... 6
2.1.1 Introduction ................................................................................. 6
2.1.2 History of cement ........................................................................ 6
2.1.3 Cement manufacturing ................................................................ 7
2.1.4 Cement hydration ........................................................................ 9
2.1.5 Cement Industry in Sudan ......................................................... 11
2.2 Pozzolana ......................................................................................... 14
2.2.1 General ....................................................................................... 14
2.2.2Types of pozzolana ..................................................................... 19
VII

2.2.2.1 Natural pozzolana ................................................................ 19
2.2.2.2Artificial pozzolana .............................................................. 21
2.2.3 Pozzolana in Sudan .................................................................... 41
2.2.5 Previous Studies on Natural pozzolana ..................................... 51
CHAPTER (3) ......................................................................................... 61
EXPERIMENTAL SETUP .................................................................... 61
3.1 Materials .......................................................................................... 62
3.1.1 Cement ....................................................................................... 62
3.1.2 Beyuda Desert Natural Pozzolana (BD-NP): ............................ 63
3.1.3 Slaked Lime ............................................................................... 64
3.1.4Graded Standard Sand ................................................................ 65
3.1.5 Water ......................................................................................... 66
3.2 Test methods .................................................................................... 66
3.2.1 Test on Raw Materials ............................................................... 66
3.2.1.1 Fineness ............................................................................... 66
3.2.1.2. Specific gravity................................................................... 69
3.2.1.3 Moisture content .................................................................. 71
3.2.1.4 Chemical Analysis ............................................................... 72
3.2.1.5 Loss on ignition ................................................................... 73
3.2.2 Tests carried out on Binder 80% OPC: 20% BD-NP& its
mortar .................................................................................................. 74
3.2.2.1 Pozzolanicity test for pozzolanic Cement (RIO-FRATTINI
test) .................................................................................................. 74
3.2.2.2Mortar flow of hydraulic Cement Mortar ASTM C1437 .... 81
VIII

3.2.2.3Compressive Strength Test ................................................... 84
CHAPTER (4) ......................................................................................... 90
RESULTS AND DISCUSSIONS ........................................................... 90
4.1Results of tests carried out on raw materials .................................... 91
4.1.1Fineness ...................................................................................... 91
4.1.2 Specific gravity .......................................................................... 91
4.1.3Moisture content ......................................................................... 91
4.1.4 Loss on Ignition (LOI)............................................................... 92
4.1.5 Graded sand ............................................................................... 92
4.1.6 Chemical compositions ............................................................. 93
4.2 Results of test on binder 80% OPC: 20% BD-NP and its mortar ... 94
4.2.1Pozzolanic activity test ............................................................... 94
4.2.2 Hydraulic Cement Mortar Flow&Water Requirement ............. 95
4.2.3Compressive strength & Strength activity Index ....................... 97
4.3Discussion ......................................................................................... 98
4.3.1 Fineness ..................................................................................... 98
4.3.2 Specific gravity .......................................................................... 98
4.3.3 Moisture content ........................................................................ 98
4.3.4Chemical Compositions.............................................................. 99
4.3.5 Loss on Ignition (LOI)............................................................. 100
4.3.6 Pozzolanic activity test ............................................................ 100
4.3.7Mortar flow & water requirement ............................................ 101
4.3.8Compressive strength & Strength activity Index ..................... 101
4.3.9 Previous study on pozzolanic activity test .............................. 105
IX

CHAPTER (5) ....................................................................................... 110
CONCLUSIONS AND RECOMMENDATION................................ 110
5.1Conclusions ..................................................................................... 111
5.2 Recommendations.......................................................................... 112
5.2.1 Recommendations from this study .......................................... 112
5.2.2 Recommendations for future studies ................................... 112
REFERENCES ...................................................................................... 114
APPENDICES
APPENDIX 1: ASTM C311-02 STANDARD TEST METHODS FOR
SAMPLING AND TESTING FLY ASH OR NATURAL
POZZOLANS FOR USE IN PORTLAND-CEMENT CONCRETE
APPENDIX 2: ASTM C 618-99 STANDARD SPECIFICATION
FOR COAL FLY ASH AND RAW OR CALCINED NATURAL
POZZOLAN FOR USE AS MINERAL ADMIXTURE IN
CONCRETE
APPENDIX 3: BS EN 196-5:2011 POZZOLANICITY TEST FOR
POZZOLANIC CEMENT






X

NOTATIONS

C: Centigrade.
F: Fahrenheit.
m: micro meter.
A: Alumina (Al
2
O
3
).
AFm: Monosulphate (C
3

12
).
AFt: Ettringite (C
3

32
).
ASTM: American Society for Testing and Materials.
B.C: Before Christ.
BA: Baggase Ash.
BD-NP: Beyouda Desert Natural Pozzolana .
BET: Brunauer, Emmett and Teller Specific Surface Area Method (BET
Method).
BSI: British Standard Institutions.
C: Calcium Oxide (CaO).
C
2
S: Diacalcium Silicate (2CaO.SiO
2
).
C
3
A: Tricalcium Aluminates (3CaO.Al
2
O
3
).
C
3
S: Tricalcium Silicate (3CaO.SiO
2
).
C
4
AF: Tetracalcium Aluminoferrite (4CaO.Al
2
O
3
.Fe
2
O
3
).
XI

CLSESR: Central Laboratory for Science and Environment and Soil
Researches.
CH: Calcium Hydroxide (Ca(OH)
2
).
CO
3
: Calcium Carbonate.
C-S- H: Calcium Silicate Hydrate.
F: Iron oxide (Fe
2
O
3
).
GGBFS: Ground Granulated Blast Furnace Slag.
Gm: Gram.
K: Potassium Oxide (K
2
O)
KVA: Volcanic Ash of Kass Area in Jebel Marra.
LOI: Loss on Ignition.
M: Magensium oxide (Mg).
MK: Metakawlin.
ml: Millimetre.
MVA: Volcanic Ash of Malam Area in Jebel Marra.
N: Sodium Oxide. NA
2
O
NP: Natural Pozzolana.
OPC: Ordinary Portland cement.
P: Phosphor oxide P
2
O
5
.
PFA: Pulverized Fuel Ash.
RHA: Rise Husk Ash.
XII

S: Silica SiO
2.

: ulphtes O
3.

SAI: Strength Activity Index.
SCBA: Sugar Cane Bagasse Ash.
SF: Silica Fume.
SG: Specific Gravity.
SNP: Sudanese Natural Pozzolana
SSMO: Sudanese standard & methodology organisation.
T: Titanium Oxide TiO
2
.
UK: United Kingdom.
US: United States of America.

XIII

LIST OF TABLES
Table 2.1 Quantities of national and imported cement in Sudan (2003-
2007) (Eljack & Alsaadig 2013). .............................................................. 10
Table 2.2 Distribution of existing & planned factories in Sudan. ............ 18
Table 2.3Chemical composition for different types of pozzolans
according to ASTM C 618 ........................................................................ 1.
Table 2.4: Typical amounts of replacing cement by pozzolana according
to BSEN 197-1. ......................................................................................... 1.
Table 2.5: Particle size variation with distance of Mount St. Helens 1980
eruptions (Siddique 2011). ........................................................................ 00
Table 2.6: Chemical composition of volcanic ash requirements by
ASTM, Indian standard. ............................................................................ 20
Table 2.7: Indian Standard IS 1344 1981 specification for chemical
compositions for clays (on oven dry basis) that is suitable for producing
pozzolana upon calcination. ...................................................................... 24
Table 2.8: Chemical compositions of pozzolana and OPC used (Sanchez
et al 2006). ................................................................................................ 25
Table 2.9: Compressive strength of blended Portland cement with
pozzolana (Sanchez et al 2006).. ............................................................. 25
Table 2.10: Chemical compositions of three types of tile and OPC used
(Araceli & Monica 2009).. ........................................................................ 26
Table 2.11: Compressive strength test results of pozzolanic cement
mortars. ..................................................................................................... 2.
Table 2.12 Oxide composition of UK Portland cement and GGBFS
(Newman 2003). ....................................................................................... 32
Table 2.13: Chemical compositions of (BA) and cement. ....................... 82
Table 2.14: SG for NPBA (Abdalateef et al 2012) ................................... 4.
XIV

Table 2.15 Chemical composition of NPBA used in this study and
another natural pozzolana specimen from Beyuda Desert (Abdalateef et al
2012).. ....................................................................................................... 40
Table 2.16: The Compressive Strength of the Cast Mortars Cubes
(Abdalateef et al 2012). ............................................................................ 40
Table 2.17: The Strength Activity Index (SAI) (Abdalateef et al 2012). . 42
Table 2.18: Chemical composition of Beyouda volcanic tuffs(Mamoun
&Zamzami 2010).. .................................................................................... 42
Table 2.19: Chemical analysis of Beyouda pumice (Mamoun &Zamzami
2010).. ....................................................................................................... 50
Table 2.20: Chemical composition of KVA & MVA (Ibrahim &Ahmed
2013) ......................................................................................................... 50
Table 2.22: Chemical composition of the cement and natural zeolite. .... 55
Table 2.23: Compressive strength of the natural zeolite blended cement
pastes. ........................................................................................................ 50
Table 2.24: Degree of reaction of zeolite blended cement paste. ............. 58
Table 2.25: Chemical compositions of Turkish natural pozzolana and
cement (OPC) used. .................................................................................. 51
Table 2.26: Water to Portland cement plus natural pozzolan ratios of plain
and blended Portland cement pastes. ........................................................ 50
Table 2.27: Compressive strength of blended Portland cement with
natural pozzolana(Adnan Colak 2002).. ................................................... 50
Table 2.28: Chemical compositions of Algerian natural pozzolana of
Bouhamidi deposit and OPC used. ........................................................... 10
Table 2.29: Compressive strength of mortar in different temperatures with
cement replacement ratio (20%) of natural pozzolana. ............................ 10
Table 2.30: Chemical composition for pozzolana (A, B) and OPC used. 12
Table 2.31: Compressive strength of concrete blended cement with
natural pozzolana (A, B). .......................................................................... 60
XV

Table 3.1: physical properties of OPC ...................................................... 60
Table 3.2: Readings of HCl and EDTA volumes used in titration. .......... 80
Table 4.1: Fineness result for BD-NP after Ball milling .......................... 95
Table 4.2: Specific gravity results for BD-NP ......................................... 95
Table 4.3: Moisture content result for BD-NP ......................................... 95
Table 4.4: LOI result for BD-NP .............................................................. 90
Table 4.5: Standard Sand sample (1) ........................................................ 90
Table 4.6: Standard Sand sample (2) ........................................................ 90
Table 4.7: Standard Sand sample (3) ........................................................ 98
Table 4.8: Chemical composition for BD-NP .......................................... 98
Table 4.9: Mix proportions and Results of Mortar Flow Test for OPC
(CONTROL): ............................................................................................ 20
Table 4.10: Mix proportions and Results of Mortar Flow Test for BD-NP:
................................................................................................................... 20
Table 4.11Compressive strength and SAI of cast mortar cubes ............... 2.
Table 4.12 Comparison of BD-NP with other Natural Pozzolana ........... 22
Table 4.13: Eight days Pozzolanic activity tests result .......................... 100
Table 4.14: Eight days Frattini test results for five test materials
quantified using (eq 4.1) 500 .......................................................................







XVI

LIST OF FIGURES
Figure 2.1:Fratini test graph for the three tile-cement blends used by by
Araceli & Monica (2009). ......................................................................... 28
Figure 2.2: Variation of compressive strength with curing time. ............. 40
Figure 2.3: Comparison of degree of reaction of natural zeolite with fly
ash and silica fume. ................................................................................... 58
Figure 4.1 : Diagram for assessing pozzolanicity showing individual
tested samples ........................................................................................... 94
Figure 4.2: Diagram for assessing pozzolanicity showing average of
tested samples. .......................................................................................... 21
Figure 4.3: Development of compressive strength with time. .................. 20
Figure 4.4: Strength and strength activity index (SAI) for 80%
OPC:20%BD-NP in 3 days ..................................................................... 102
Figure 4.5: Strength and strength activity index (SAI) for 80%
OPC:20%BD-NP in 7 days ..................................................................... 102
Figure 4.6: Strength and strength activity index (SAI) for 80%
OPC:20%BD-NP in 28 days ................................................................... 103
Figure4.7: Strength and strength activity index (SAI) for 80%
OPC:20%BD-NP in 91 days ................................................................... 103
Figure 4.8: Comparison between Compressive strength of mortars made
with OPC+ NP from sudan & Abroad .................................................... 104
Figure 4.9: Frattini test results for five test pozzolans after 8 days
curing.................... 500 .................................................................................
Figure 4.10: Strength activity index of five different test materials after 7
and 28 days............................................................................................500
Figure 4.11: Correlation between measured pozzolanic activity of five
test materials using the Frattini test and the strength activity index
test..........................................................................................................502
XVII



LIST OF PHOTOGRAPHS

Photograph 2.1: Metakaolin (MK).
Photograph 2.2: Cool Fly Ash (PFA).
Photograph 2.3: Ground Granulated Blast Furnace Slag (GGBFS).
Photograph 2.4: Silica fume (SF).
Photograph 2.5: Rise husk Ash (RHA).
Photograph 2.6: Bagasse (BA).
Photograph 2.7 Map of Jebel Marrah.
Photograph 2.8: Map of pozzolana location in Beyouda desert.
Photograph 3.1: BD-NP as received specimen (containing some pumicite
boulders).
Photograph 3.2: BD-NP after grinding specimen.
Photograph 3.3: Sieves.
Photograph 3.4: Containers
Photograph 3.5: Sensitive balance.
Photograph 3.6: Oven.
Photograph 3.7: Sieve # 325, size 45m.
Photograph 3.8: Pycnometer.
XVIII

Photograph 3.9: Apparatus of pozzolanic activity test.
Photograph 3.10: Flow mould and flow table.
Photograph 3.11: Balance.
Photograph 3.12: Triplicate set of cubes.
Photograph 3.13: Moulds on vibrator.
Photograph 3.14: Graduated cylinder
Photograph 3.15: Mechanical concrete mixer.
Photograph 3.16: Cube crushing machine.
Photograph 3.17: Curing tank


1









CHAPTER (1)
INTRODUCTION






2

1.1 Preface
Pozzolana is a material containing reactive silica and/ or alumina which
on their own have little or no binding property but, when mixed with lime
in the presence of water, will set and harden like cement.
OPC has become the most widely available cementitious material since
the first half of the 19
th
century. However the up-to-date cement industry
has faced with the challenge of producing more sustainable, less energy
intensive and more durable products without sacrificing the mechanical
properties of the end product. One of the most developments with limited
interference is the blending of supplementary cementitious materials or
pozzolana with OPC. The replacement of a specific amount of cement
with pozzolana decreases the cost and environmental impact of the end
product.
Pozzolana is an important ingredient in the production of alternative
cementing material to Portland cement. The use of pozzolana in blended
cement and concrete applications has been observed to significantly
improve the cement durability, especially the vulnerability to chemical
attack or alkali-aggregate reaction can be mitigated.
1.2 Project aim, project significance& thesis layout
This section summary the research carries out for this project. The
objectives that served as the focus of the work accomplished are first
identified. The significance of the work is then highlighted, followed by
a frame of the project layout.


3

1.2.1 Project objectives and approach
The primary objective of this research Use of Beyuda desert Natural
Pozzolana as cement replacement Material. The approach to achieve it
was carried out as follows:
1. A procurement of sample of Sudanese natural pozzolana from active
quarry Beyo+uda dessert (BD-NP).
2. To test raw material properties in order to perform tests on binder
contain 80% OPC : 20% BD-NP, namely the follow tests :
- Flow and hence identifying water requirement necessary to produce a
flow similar to that of the control OPC specimen
- Compressive strength at 3, 7, 28, and 91 days & hence increasing the
strength activity index (SAI).
3. Presenting results of tests mentioned using pecictions in TM
618-99.
4. Discussion and comparison between BD-NP, local natural pozzolana
and other pozzolana from different countries, in terms of chemical and
physical properties and compressive strength.
1.2.2 Project significance
This project highlights the advantages of pozzolana as cement alternative
material, such as reduction of pollution, environmental protection and
more benefits will be discussed in details. Also to review the use of this
specific type of alternative materials because it is economical substance
more than the pure OPC mix. Moreover to put BD-NP under focus in
order to determine the exact features of our pozzolana to be methodical to
display appropriately to the world.
4

1.2.3 Thesis layout
This thesis is comprised of chapter 1that is introduction.

Chapter 2 is literature review, defining different types of pozzolana
technically, and most important lists of pozzolana in Sudan. Brief history
about uses of pozzolana world-wide, and summarized previous studies
carried out on natural pozzolana.
Chapter 3 describes experimental setup, describes materials and methods
used in this study.
Chapter 4 presents results and discussions of the data acquired from
investigation.
Chapter 5 includes conclusions and recommendations drawn from the
investigation.
Several references and appendices are attached at the end of the Thesis to
simplify the accessibility of the standard codes used.



5










CHAPTER (2)
LITERATURE REVIEW

6

2.1 Cement
2.1.1 Introduction
Cement is a fine powder material manufactured with very precise
processes from argillaceous and silicon minerals. Mixed with water, the
cement transforms into a paste that binds and hardens when submerged in
water. Because the composition and fineness of the powder may vary,
cement has different properties depending upon it is constitutes. There are
many types of cement available, the most common is OPC. OPC is a
basic ingredient of concrete, mortar and most non-specialty grout
(Wikipedia 2014).
Concrete is a composite material consisting of aggregates (gravel and
sand), cement and water. As a construction material, concrete can be cast
in almost any shape desired, and once hardened, can become a structural
(load bearing) element. Portland cement may be grey or white.
Although cement is one of the oldest building materials around, its
production process is a mix of traditional chemistry and hi-tech
equipment to make the cement used in homes, hospitals and schools
around the world.
Production of OPC consumes huge amount of energy varies between 4-5
GJ/ton.
2.1.2 History of cement
Portland cement is essentially calcium silicate cement, which is produced
by firing lime, chalk and an appropriate quantities of clay or shale at a
temperature of 1500C (Newman& Choo 2003).
First calcium silicate cement was produced by Greeks and Romans, who
used finely ground volcanic ash mixed with lime and water to produce a
7

hardened mortar which resist the weathering. Concrete use this type of
cement was used in a great Roman civil project such as the arches of
Colosseum, and the dome in the Pantheon.
In the mid-18
th
century Jones meaton discovered a certain lime with
appropriate level of S, A that reacts with water to yield durable hydrates.
This type was used with pozzolana from Italy and clay from south Wales
to construct the Eddystone Lighthouse in 1759.
In 1796 James Parker developed Roman cement by calcining stones
extracted from London clay then grinding the resulting clinker to a fine
powder. This materil ws used first in Brunels Thmes tunnel, lso in
tephensons Britnni bride over the Meni strits (Calcrete 2008).
Joseph Aspdin (1820) in his British patent described a process by mixing
lime with clay in form of slurry and heating to drive off CO
2
and water.
After grinding, the resulting fine powder was named Portland cement will
produce The term Portlnd ws used becuse of its colour similrity to
the Portland stone from Dorset, UK.
The cements produced in the first half of 19
th
century did not have the
same chemical composition as modern Portland cement. This was due to
the fact that the temperature achieved was not high enough to form the
tri-calcium silicate C
3
S component that has a main share on strength of
cement (Newman & Choo 2003).
2.1.3 Cement manufacturing
The main technical innovation in cement manufacture has taken place
over approximately the last 150 years. The rotary kiln was introduced at
the end of the nineteenth century. This enabled a homogeneous product
to be manufactured that had a consistently high enough temperature to
ensure C
3
S formation.
8

The nature of the product changed moderately in chemical and mineral
composition during the twentieth century. Because of improved energy
efficiency the advantages of production technology were pronounced,
providing reduction in the environmental impact and lower labour
intensity.

It should be noted that in the early twentieth century introduction of the
rotary kiln technology was published by the UK and the USA standards.
Both standards required the strength of a briquette of cement paste to
reach minimum values at 7 and 28 days.

The main components of cement are limestone with a high lime content,
and clay containing the silica.
Kilns processes used in cement manufacturing are two types, wet process
and dry process.

The wet process kilns were used in the first half of the twentieth century
using 40% moisture content of total mass providing homogeneous row
mix easily.

In the second half of the twentieth century dry process kiln was
developed. In this type of kiln, the energy-consuming stage of de-
carbonating limestone consumes energy before the feed enters therotary
kiln. The main advantage of this process is providing high output using
short and small-diameter rotary kiln.

The dry process is the preferred method nowadays that used in cement
manufacturing. In this method, the raw materials are ground to fineness
in range of 10-30% retained on a 90 m sieve depending on the nature of
9

raw materials. This helps achieving a satisfactory combination under
normal operating conditions. The homogenized raw blend is fed into a
slightly inclined rotary kiln with a sufficient temperature that ensures
removal of any amount of water. The temperature in the kiln is gradually
increased with length. In the next stage the mix temperature is upraised
to approximately 600C, decomposition of CO
3
and chalk producing
quicklime CaO. Final stage in the kiln is rising the temperature of mix to
1500C and as a result of the tumbling action and the partial melting it is
converted into the granular material known as clinker. Then the clinker is
cooled to 60C in the cooler forming particles of size 2-25 mm, and the
heat exchanged is used to increase the temperature of air going back into
the kiln. Finally the clinker is grounded with gypsum (CaSO
4
.2H
2
O) to
produce cement with fineness in the range of 2-80 microns (0.002- 0.080
mm) (Calcrete 2008).
Cement manufacturing requires huge energy and there are many types
offuel that can be used, but generally coal furnace is used in the modern
kilns. In cement production every 100 tonnes of clinker consumes
approximately 12 tonnes of coal. (Newman & Choo 2003)
2.1.4 Cement hydration
When water and cement are mixed, a number of chemical reactions
involving the silicates and aluminates phases in the cement are initiated.
These phases combine with the water producing the hydration products
that form hardened cement paste.
Cement hydration is complex and it is appropriate to consider the
reactions of the silicate phases (C
3
S and C
2
S) and the aluminate phases
(C
3
A and C
4
AF) separately. (Calcrete 2008)
10

C
3
A reacts at first with water and it is the most rapid of all. It needs to be
controlled to void flsh setting, this chieved by the ddition of
gypsum (
2
). In this reaction: AFt (C
3

32
) forms to slow down
the hydration by forming a barrier around the cement grains. This is
described in equation (2.1-a). After the consumption of gypsum in AFt.
The more rapid dissolution of dehydrated forms of gypsum ensures an
adequate supply of dissolved calcium and sulfate ions. It will be more
effective in controlling the reaction of finely divided or highly reactive
forms of C
3
A.
In most commercial Portland cements there will be insufficient sulfate
available to sustain the formation of Aft. When the available sulphate has
been consumed the Aft reacts with C
3
A to form a phase with a lower
content known as monosulfate (AFm). This is described in equation (2.1-
b). Over the long term and after cement hardening, the C
3
A reaction with
gypsum is undesirable as they deteriorate the strength of the cement,
usually manifested as sulphate attack (Calcrete 2008).
C
3
6
2

3

32
(2.1-a)
C
3

2

3

12
(2.1-b)
C
4
AF reaction takes place after a certain proportion of the sulphate has
been consumed and the AFt coating broken.
The reaction of C
4
AF is of little importance compared to others because it
add a little to strength and develop little heat of reaction as equation (2.2).
C
4
F
6
AFH
12
(2.2)
Both C
3
S and C
2
S react with water to produce an amorphous calcium
silicate hydrate known as(C-S-) gel which is the min glue tht binds
the sand and aggregate particles together in concrete. The C
3
S reaction is
much faster than C
2
nd under stndrd temperture conditions of
11

20C approximately half of the C
3
S present in typical cement will hydrate
by 3 days and 80% by 28 days, this reaction is summarized in equation
(2.3). In contrast, the hydration of C
2
S does not normally proceed to a
significant extent until 14 days. The C-S-H produced by both C
3
S and
C
2
S has a typical Ca/ Si ratio of approximately 1.7. This is considerably
lower than the 3:1 ratio in C
3
S and the excess Ca
+2
is precipitated as
calcium hydroxide (CH) crystals. C
2
S hydration also results in some CH
formation and the chemical reaction is described inequation (2.4).
The following equations approximately summarize the hydration
reactions:
2C
3
6
3
S
2
H
3
+ 3CH (2.3)
2C
2
4
3
S
2
H
3
+ CH (2.4)
(Newman & Choo 2003)
2.1.5 Cement Industry in Sudan
The cement manufacturing in Sudan started in 1947 by establishing
Atbara Cement Factory with a design capacity 220,000 tons per year.
Recently Sudan has seven operating cement factories, five of them
located in Nahr EL-neel state and only one in EL-jazirah State and
another in White Nile State. The design capacity for the seven factories
22.4 thousand tons per day, but the operating capacity in 2012 is 17.65
thousand tons per day. The main raw materials required to produce
cement in Sudan are lime stone, desert clay, river clay and gypsum,
which are available in the most areas of Sudan.
Table 2.1 shows the quantities of national and imported cement available
for consumption during the period (2003-2007). (Eljack & Alsaadig
2013).
12

Table 2.1: Quantities of national and imported cement in Sudan (2003-
2007) (Eljack & Alsaadig 2013).
Year National
production (tons)
Imported cement
(tons)
Total (tons)
2003 296 1573 1869
2004 307 1130 1437
2005 331 1667 1998
2006 267 1631 1898
2007 354 2000 2354

During the period (2000-2010) about 40 licenses had been issued for
new factories distributed over a number of states to cover the gap in
consumption and provide surplus for export, Table 2.2 shows the
distribution of existing and planned factories in the Sudan according to
the Ministry of Industry (2013).







13

Table 2.2: Distribution of existing & planned factories in Sudan.
State Operational
factories
Deactivated
factories
Under
construction
Un
implement
Total
River
Nile State
5 1 1 12 19
Red Sea
State
- - - 9 9
Khartoum
state
- 1 - 4 5
EL-
jazirah
State
1 - - 1 2
South
Kurdofan
State
- - - 2 2
EL-
gadarif
State
- - - 1 1
Blue Nile
State
- - - 1 1
White
Nile State
1 - - - 1
Total 7 2 1 30 40
14

2.2 Pozzolana
2.2.1 General
A pozzolana is a natural or artificial material containing silica in a
reactive form. By themselves, pozzolana has little or no cementations
proprieties. However, in a finely divided form and in the presence of
moisture they will chemically react with CH to form cementing
compounds. Pozzolana must be finely divided in order to expose a large
surface area to the alkali (Ca-rich) solutions for their reaction to proceed.

The name pozzolana was originally used for glassy pyroclastic material
produced by violent eruptive volcanic action. It is now used as a generic
term to describe all materials that exhibit reactivity with lime and set
harden to develop strength in the presence of water (Davey 1961, cited in
Newman & Choo 2003).

There are many types of pozzolanic materials either natural or artificial
such as volcnic sh, pumice, oplineshles, burnt cly nd fly sh, etc
as discussed in details in Section 2.2.2.
Human beings have used natural pozzolana from 6000-7000 years ago.
Malinowski et al. (1997) reported that the oldest example of a hydraulic
binder, dating from 5000-4000 B.C, was a mixture of lime and natural
pozzolana, a diatomaceous earth from the Persian Gulf. The next oldest
pozzolanic concrete users were the Egyptians in around 2,500 B.C. The
other old report of its use was in the Mediterranean region where the
pozzolana was volcanic ash produced from two volcanic eruptions
between 1600 and 1500 B.C. and the Romans from 300 B.C. The
Romans found that by mixing a pink sand-like material which they
15

obtained from Pozzuoli near Naples, Italy with lime they obtained a far
stronger material. So they nmed the mteril pozzoln The pink
sand turned out to be fine volcanic ash and they had inadvertently
produced the first 'pozzolanic' cement.

Pozzolana was used for a long time in Italy where considerable reserves
of natural pozzolana are found. There are structures in Rome such as the
Pantheon and masonry structures mortar such as the Pont du Gard
Aqueduct near Noames in southern France shown a remarkable durability
up to nowadays. This despite their subjection to aggressive environment
for more than 2100 years.
Also the British have a share in the history of pozzolana, the idea of
utilizing coal fly ash in concrete was investigated by McMillan and
Powers in 1934 and in subsequent research by Davis et al (1935, cited in
Newman & Choo 2003).In the late 1940s UK research was carried out
(Fulton and Marshall, 1956) which led to the construction of the
Lednock, Clatworthy and Lubreoch Dams during the 1950s with fly ash
as a partial cementitious material. These structures are still in excellent
condition.
Clays or shales suitable for use as a pozzolana are very widespread and
are readily available in almost all regions of the world. They have been
used as cement replacement materials on large-scale construction
programs in a number of countries, particularly the US, Brazil, Egypt and
India. For example, in Egypt, a lime-calcined clay mortar was used in the
core of the first Aswan dam built in 1902 and an OPC-calcined clay
mixture was used in the construction of the Sennar dam in Sudan in
1920s.

16


Pozzolanic chemical reactions and properties
The general chemical components of any pozzolanic material is S, A and
F and other minor constituents. When a pozzolanic material is added to
cement the pozzolanic reaction occurs between the silica acid and the
calcium hydroxide CH or lime, this is a by-product of the hydration of
Portland cement. The reaction can be described in equation (eq2.5)

Ca(OH)
2
+ H
4
SiO
4

2+
+ H
2
SiO
4
2 -
+ 2 H
2
O
2
SiO
4
2 H
2
O
(eq2.5)

Or it can summarize in abbreviated in cement shorthand:
(eq6)

As sited before C
3
S is a main component of cement and when hydrated
produce CSH. Its the hydration product in very finely divided state and
because of its extra ordinary high surface area; it provides binding
property (Lea and Hewlett 1997). The chemical properties of pozzolana
will vary depending on the source of the raw materials and the types of
pozzolana.
Table 2.3 Summarises the chemical composition for different types of
pozzolana according to ASTM C 618.




17


Table 2.3: Chemical composition for different types of pozzolana
according to ASTM C 618
Chemical
composition
%
Class
F
PFA
Class
C
PFA GGBS SF
Calcined
clay
Meta-
kaolin
S 52 35 35 90 58 53
A 23 18 12 0.4 29 43
F 11 6 1 0.4 4 0.5
C 5 21 40 1.6 1 0.1
0.8 4.1 9 0.4 0.5 0.1
N 1.0 5.8 0.3 0.5 0.2 0.05
K 2.0 0.7 0.4 2.2 2 0.4
Total alkalis 2.2 6.3 0.6 1.9 1.5 0.3

Typical amounts of adding Pozzolana (by Mass) to Concrete
Table 2.4: Typical amounts of replacing cement by pozzolana according
to BSEN 197-1.
PFA Class C 15-40 %
PFA Class F 15-20 %
GGBS 30-45 %
SF 5-10 %
Calcined clay 15-35 %
MK 10 %




18

Benefits of using pozzolana in concrete
In recent years the cement market has been dominated by one product,
OPC. In many countries, particularly those of the South OPC are an
expensive and sometimes scarce commodity and this has severely limited
the construction of affordable housing in much of the Third World.
The real need in the Third World is not for a high strength and fast setting
materials. Most buildings such as houses, schools, clinics, are relatively
small, are not built in a hurry, and do not require excessive strength.
The United Nations Centre for Human Settlement, UNCHS, estimates
that only 20% of the worldwide uses of cement require the strength of an
OPC and another 40% has intermediate strength requirements, and the
remaining 40% used for applications such as mortars, plasters, foundation
concrete, concrete blocks, and soil stabilization, where grade cement low
could be used.
Pozzolans provide an excellent technical option for many uses of OPC at
a much lower cost. They have the potential to make a significant
contribution toward the provision of low-cost building materials and
consequently affordable shelter. (Suleiman 2008)
Lithification.
Reduced Permeability and Voids and Micro-cracking.
Reduces Expansion and Heat of Hydration
Reduces Creep and Cracks.
Increases long term Compressive Strength.
Increases resistance to chloride and sulfate Attack.
Reduces alkali-aggregate reaction.
19

Protects steel reinforcement from corrosion.
Increases abrasion resistance
Improves Durability
Friendly Environmental.
Economical.
(Naturalpozzolan 2014)
2.2.2 Types of pozzolana
2.2.2.1 Natural pozzolana
Natural pozzolana is a glassy amorphous material and mainly of volcanic
origin, like volcanic ash pumice and volcanic tuff but also found on form
of diatomaceous earth.
2.2.2.2 Volcanic pozzolana
Volcanic pozzolana founded in volcanic regions resulting from explosion
of magma that cooled rapidly. They are rich in glass in an unaltered or
partially altered state.
Ash is created when solid rock shatters and magma separates into minute
particles, volcanic ash almost in fine powdered state may need little or no
grinding, lso doesnt need het tretment to improve pozzolnic
reactivity. Fragments larger than 2 or 3 mm are generally called pumice,
and those from this size down to powder are termed pumicite or ash/dust,
pumice required grinding. The density of individual particles varies
between 700 and 1200 kg/m
3
for pumice (Hossain & Lachemi 2006)
The size of ash particles, that fall on the ground decreases exponentially
with increasing distance from a volcano. Also, the range in grain size of
20

volcanic ash typically diminishes downwind from a volcano. The
distribution of ash particle sizes can vary widely as shown in Table 2.5.
Table 2.5: Particle size variation with distance of Mount St. Helens 1980
eruptions (Siddique 2011).
Distance from the
Volcano (km)
Mean particle diameter
(mm)
0 4.000
54 0.100
150 0.063
235 0.047
414 0.038
621 0.034

Volcanic ash typically consists of tiny particles composed of varying
proportions of volcanic glass, minerals or crystals, and other rock
fragments (lithics).
The main chemical composition of volcanic ash suitable to use as
pozzolans according to the specifications of American and Indian
standards, is shown in Table 2.6.
Table 2.6: Chemical composition of volcanic ash requirements by ASTM,
Indian standard.
Chemical oxides Mass portions (%)
S 45-65
A + F 15-30
C+ M+ Alkalis Up to 15
LOI Up to 12
21

2.2.2.3 Artificial pozzolana
It can be classified to three main categories:
1) An output of heat treatment of natural materials
Metakaolin
Kaolin (Al
2
Si
2
O
5
(OH)
4
) is one of the clay minerals, resulting from the
natural decomposition of feldspars and other clay minerals. Kaolin is
white in colour and has a high melting point 1780C, kaolin shown in
photograph 2.1

Photograph 2.1: Metakaolin (MK).
Kaolin is one of the raw aluminium productions where the percentage of
aluminium it up to 35% and used in the manufacture of ceramics and
porcelain, also uses kaolin in the refractory industry (lining of furnaces
and incinerators and reactors) and ceramics. Also it used as an absorbent,
protective and insulation of electrical current and in paper paint
industries, and white limestone industry. When kaolin is heated to at
450C de-hydroxylation occurs and the hydrated alumina-silicates are
22

converted to materials consists predominantly of chemically combined
Al, Si and O
2
atoms. The rate at which water of crystallization is
removed increases with increasing temperature and at 600C where it
proceeds to completion (Newman 2003).
Metakaolin (Al
2
Si
2
O
7
) is formed in kilns when kaolin is heated at a
temperature between 700C and 800C. The calcined product is cooled
non-rapidly and ground to a fine powder. The metakaolin formed in this
way has a highly glee structure.

2 Al
2
Si
2
O
5
(OH)
4
ET l
2
Si
2
O
7
+ 4 H
2
O (eq. 2.7)

Metakaolin possess high pozzolanic activity and has a high affinity for
reacting with lime
The physical properties of metakaolin depend very much on the
quality of the raw material used, the calcination temperature and the
finishing processes.
Calcined Clay and shale
Burnt clay was the earliest material used as pozzolana, in the form of
crushed clay bricks, pottery or tiles which were mixed with lime and
water to produce cement mortars. Using calcined clay as a pozzolana is a
widespread in many countries. For example in Egypt, a lime-calcined
clay mortar was used in the core of the first Aswan dam built in 1902 and
an OPC-calcined clay mixture was used in the construction of the Sennar
dam in Sudan (Rahma et al 2011, cited in Yusra and co. project).
Raw materials for calcined clay pozzolanas should be free from coarse
sand or gravel greater than about 0.6mm in diameter.
23

In tropical climates, clay deposits are often subjected to a form of
chemical weathering which leaches out the silica and alkalis resulting in
an accumulation of ferric and aluminium hydroxides. The soils produced
are bauxite (aluminium bearing) and lateritic (iron bearing). Although
these soils are low in silica, normally considered essential for a
pozzolanic reaction, both will exhibit some pozzolanic reactivity when
calcined. In general, the reactivity of laterite is low but bauxite can show
reasonable results and its use as a pozzolana should be considered if
silica-bearing clays are not available.
The early stages of processing calcined clay pozzolanas are similar to the
moulding and firing process for clay bricks, tiles or pottery, and
traditionally the rejects from these industries have been used as
pozzolanas. The optimum calcining temperatures for clay pozzolanas are
slightly below those for clay bricks or tiles and therefore better results are
likely to be obtained if the moulding and firing process are designed
specifically for pozzolana production. The Indian Standard (IS1344 1981)
gives the following range of temperatures for different types of clays:
Montmorillonite type 600 to 800C
Kaolinite type 700 to 800C
Illite type 900 to 1000C

In practice, most clay soils consist of a mixture of minerals, and a
calcination temperature of 700-800C is normally considered suitable.
The optimum period of calcination will vary with clay type but is
normally around one hour or less.
24

Rotary kilns have been the most common means of calcining clays and
have been extensively used in the US and Brazil. Natural gas or oil is
normally used as a fuel and outputs vary from 12.5 to 100 tonnes per day.

Table 2.7: Indian Standard IS 1344 1981 specification for chemical
compositions for clays (on oven dry basis) that is suitable for producing
pozzolana upon calcination.
Constituent Content by
weight (%)
S+A+F 7
S 49
C
M

Alkalis
Water soluble materials
LOI

Previous studies on calcined clay in Europe (Spain)
Sanchez et al (2006) investigated the use of crushed tiles as pozzolana.
They found that, the sample used in tests consisting of crushed and
ground ceramic tile (clay tile). The cement-to-replacement proportions
were used as follow: 100:0 and 85:15 by weight with water/binder ratio is
0.5. Table 2.8 show Chemical compositions of pozzolana and OPC used
in tests.


25


Table 2.8: Chemical compositions of pozzolana and OPC used (Sanchez
et al 2006).

The results of the compressive strength of the 4040160 mm concrete
specimens according to UNE-EN 196-1:2005 with using pozzolana and
time of curing as shown in Table 2.9.
Table 2.9: Compressive strength of blended Portland cement with
pozzolana (Sanchez et al 2006).
Compressive strength (MPa)
Age in days 0% of pozzolana 15% of pozzolana
1 9.8 9.5
28 46 43

The pozzolanic activity was tested with cement-to-replacement is 80:20
by weight. The results indicated that, the samples of ground ceramic tile
Chemical
compositions
Pozzolana (%) Cement (%)
S 67.03 19.60
A 19.95 4.41
F 6.29 3.30
C 0.11 63.21
M 1.37 4.20
- 3.00
K 3.54 0.50
N 0.21 0.30
LOI 0.47 1.40
26

displayed acceptable pozzolanic activity, having strength activity index
68% after 7 days, 73% after 28 days, and 82% after 90 days.

Previous studies on calcined clay in Southern America
(Argentina):
Araceli & Monica (2009) investigated three different kinds of discarded
tile products. They were studied in order to test their pozzolanicity: non
glazed (T), natural glazed (E) and black glazed (N) tiles. The discarded
tiles were crushed and ball milled; the resulting powders were sieved
through a 44 m.
There is no big difference between the chemical compositions of three
types of tile (E, N, and T) as shown in table 2.10, in addition to chemical
composition of OPC used.

Table 2.10: Chemical compositions of three types of tile and OPC used
(Araceli & Monica 2009).
Tile E (%) N (%) T (%) Cement (%)
S 63.57 64.04 63.69 21.44
A 19.50 19.18 19.35 3.40
F 7.24 6.96 7.11 4.20
C 1.56 1.64 1.72 63.45
M 1.36 1.37 1.38 0.57
K 1.26 1.30 1.26 1.18
Na 3.80 3.73 3.77 0.04
0.02 0.01 0.02 2.91
LOI 0.56 0.60 0.52 1.82

27

According to the chemical analysis of ground tiles N, T and E, given in
Table 2.10, the sum of the major components, (S + A +F), is around 80%.

The preparation of cement-tile mortar blends for compressive strength
test was carried out by using the w/c ratio at 0.4 and two cement-tile ratio
(80:20,70:30). The compressive strength was determined on
40mm40mm160mm specimens. In all cases, the average value of five
specimens is reported.

Table 2.11: Compressive strength test results of pozzolanic cement
mortars.
Proportion and type of
tile
Compressive strength of
mortars (MPa)

7 days 28 days
0% 31.2 43.4
20% T 30.2 40.36
30% T 27.5 38.0
30% E 24.0 33.0
30% N 23.4 32.5

Evidently, in the early stage, the strength is almost proportional to the
amount of cement present in the blended cement. In the case of sample
20T, with 20% replacement, the mechanical strengths are closer to the
control. A reduction in compressive strength is observed when the
quantity of pozzolana is 30% (as in 30T, 30E and 30N). Compressive
strength values for the blended cements were greater than 75% of that of
the OPC. The lower strength values found for 30N and 30E, in
comparison with 30T, are more difficult to be explained. Probably, some
subtle factors related to the composition of enamels and in the case of N
tile, the double fire process could influence the mechanism of
28

pozzolanicity and strength. According to the data, which show the effect
of the age of hydration and the amount of pozzolana present in the
blended cement, during the 7 to 28 days hydration period, the beneficial
effect in strength resulting from the pozzolanic reaction is substantial.
As can be seen in table chemical compositions, the appreciable alkaline
content in the chemical composition of tiles could contribute to the
activation of the pozzolanic reaction at early ages.
From these test results, it can be concluded that the presence of <30% of
ceramic waste additions to an (OPC) does not significantly change the
cement compressive strength when the pozzolanic effect is incorporated.
The reactivity of the pozzolanic tiles could be assessed by Fratini tests
applied in two specimens for each type of tile (T,E,N) with 30%
replacement of cement. The results are presented as concentration of
CaO (mM/l) Vs total alkalinity (mM/l). The Fratini test was positive, the
results obtained for the samples at 7 and 28 days are lower than the points
on the solubility isotherm, as shown in Fig 2.1.


Figure 2.1: Fratini test graph for the three tile-cement blends used by
Araceli & Monica (2009).


29

2) An output of heat treatment industrial wastes
Coal fly ash
The first reference to the idea of utilizing coal fly ash in concrete was by
McMillan and Powers in 1934. Fly ash become more widespread, it used
in all countries approximately. The utilization rates of fly ash vary
greatly from country to country, from as low as 3.5% for India to as high
as 93.7% for Hong Kong (Meyer 2009).
Pulverised Fly ash (PFA) is a finely divided residue resulting from the
burning of coal at coal fire power plants, as shown in photograph (2.2).
When coal burns in a power station furnace between 1250C and 1600C,
the incombustible materials combine to form spherical glassy droplets of
silica S, A and F and other minor constituents.

Photograph2.2: Coal fly ash (PFA).
PFA is a by-product of coal combustion found as fine powder no need for
grinding, added to cementdirectly, has low heat of hydration which makes
y sh populr cement substitute for mss structures
30

Concrete with PFA has better strength and durability than concrete
product without it. PFA is generally less expensive than OPC, a high
volume y sh concrete ws dvnced by Mlhotr who developed mixes
with 60% and more of the Portland cement replaced by PFA (Meyer
2009). Also have demonstrated that the addition of PFA improves the
dispersion of the Portland cement particles and improving their reactivity.
When PFA added to concrete little pozzolanic reaction occurs during the
first 24 hour at 20C between the reactive silica S and CH as shown in
equation (eq2.5).
Presence of fly ash slow down the reaction of C
3
S within the Portland
cement at early ages, so lower early strengths are achieved. However, at
the middle stages C
3
S production is accelerated due to the provision of
nucleation sites on the surface of the fly ash particles. CH carves the
surface of the glassy particles reacting with the SiO
2
or the Al
2
O
3
-
SiO
2
framework. The finer the PFA, the greater surface exposed for
reaction, the higher temperature, the superior reaction rate. At later ages
the contribution of PFA to strength gain increases greatly, if there is
adequate moisture to continue the reaction process.

Ground Granulated Blast Furnace Slag (GGBFS)
GGBFS production began in Germany around 1880 and was first used in
combination with OPC. Since then it has been used extensively in many
European countries. GGBFS is a by-product of iron industry, it is a
glassy granular material formed when molten blast furnace slag is rapidly
cooled by immersion in water, GGBFS shown in photograph (2.3)
Portland blast furnace cements have different names, for example in UK
and US named as UK low-heat slag cement and Germany Eisenportland
31

and Hochofen cements and France 'ciment de haut fourneau', while in a
Belgium , known as the Trief process. Use of GGBFS as a separate
cementitious material has become widespread in many different
countries, because is not only used as partial Portland cement
replacement, but can be activated with other alkalis as sodium hydroxide
or sodium silicates (water glass). (Newman and Choo 2003)

GGBFS also improves many mechanical and durability properties of
concrete also have a lower hydration heat. Moreover, it can be replace
OPC by 50% - 80% of the total binder weight.

Photograph 2.3: Ground Granulated Blast Furnace Slag (GGBFS).
The chemical composition of GGBFS will vary depending on the source
of the raw materials and the blast furnace conditions as shown in Table
2.13.

32

Table 2.12: Oxide composition of UK Portland cement and GGBFS
(Newman 2003).
Oxide Composition (%)
Portland
cement
GGBFS
C 64 40
S 21 36
A 6 10
F 3 0.5
M 1.5 8

2 0.2
K 0.8 0.7
N 0.5 0.4

Silica fume (SF)
The terms condensed silica fume, micro-silica, silica fume and volatilized
silica are often used to describe the by-products extracted from the
exhaust gases of silicon, ferrosilicon and other metal alloy
smeltingfurnaces, SF is shown in photograph (2.4)

Photograph 2.4: Silica fume (SF).

33

SF is produced during the high-temperature reduction of quartz in an
electric arc furnace where the main product is silicon or ferrosilicon.
High-purity quartz is heated to 2000C with coal, coke or wood chips as
fuel and an electric arc introduced to separate out the metal. As the quartz
is reduced, it releases silicon oxide vapour. This mixes with oxygen in the
upper parts of the furnace where it oxidizes and condenses into
microspheres of amorphous silicon dioxide.
The fumes are drawn out of the furnace through a pre-collector and a
cyclone, which remove the larger coarse particles of unburnt wood or
carbon, and then blown into a series of special filter bags. (Newman and
Choo 2003)
F is n ultrfine mteril with sphericl prticles less thn m in
dimeter, the verge being bout 5 m This mkes it pproximtely
100 times smaller than the average cement particle. The bulk density of
SF depends on the degree of densification in the silo and varies from 130
(undensified) to 600 kg/m
3
. The specific gravity of silica fume is
generally in the range of 2.2 to 2.3. The specific surface area of SF can be
measured with the BET method or nitrogen adsorption method. It
typically ranges from 15,000 to 30,000 m
2
/kg.
The powder is normally grey in colour but this can vary according to the
source. Operation of the furnace, the raw materials and quality of metal
produced, will all have an effect on the colour of the SF.
Because of its extreme fineness and high silica content, SF is a very
effective pozzolanic material. Standard specifications for silica fume used
in cementitious mixtures.
34

SF is added to Portland cement concrete to improve its properties, in
particular its compressive strength, bond strength,and abrasion resistance.
These improvements stem from both the mechanical improvements
resulting from addition of a very fine powder to the cement paste mix as
well as from the pozzolanic reactions between the silica fume and
free calcium hydroxide in the paste.
Addition of SF also reduces the permeability of concrete to chloride ions,
which protects the reinforcing steel of concrete from corrosion, especially
in chloride-rich environments such as coastal regions and those of humid
continental roadways and runways (because of the use of deicing salts)
and saltwater bridges (Rachel 1994)
Past to the mid-1970s, nearly all SF was discharged into the atmosphere.
After environmental concerns necessitated the collection
and landfilling of SF, it became economically viable to use silica fume in
various applications, in particular high-performance concrete. Effects of
SF on different properties of fresh and hardened concrete include:
a) Workability: With the addition of silica fume, the slump loss with time
is directly proportional to increase in the silica fume content due to the
introduction of large surface area in the concrete mix by its addition.
Although the slump decreases, the mix remains highly cohesive.
b) Segregation and bleeding: SF reduces bleeding significantly because
the free water is consumed in wetting its large surface area, hence the free
water left in the mix for bleeding also decreases. SF also blocks the pores
in the fresh concrete so water within the concrete is not allowed to come
to the surface.

35

3) An output of heat treatment of Agro-wastes
Such as Rice Husk, Groundnut Shell, Bamboo Leaf and Sugar Cane
Bagasse can be burnt and their ashes possess Pozzolanic activity.
Ash result from burning agricultural wastes has a high percentage of
active silica that is good for use as pozzolana (Luther 1990).

Rice husk ash (RHA)
Rice husk is waste product of rice milling; it is available in large
quantities in many parts of the world, shown in photograph (2.5).

Photograph (2.5): Rise husk Ash (RHA).

36

Every five tons of husks produce about one ton of ash, 120 million tons
of husk could be available annually on a global basis so there are possibly
24 million tons of RHA available as a pozzolana.

RHA has been utilized as a pozzolana in cement production in many third
World countries including China, the Indian sub-continent, South-east
Asia and, in smaller quantities, in some regions of Africa and South
America).
These RHA normally contains approximately 90% silica that means
highly pozzolanic reactivity, if burnt under controlled conditions at
temperatures below 700C for 1 hour. This transforms the silica content
of the ash into amorphous phase, otherwise the silica becomes crystalline
and loses a degree of reactivity.(Practical Action, The Schumacher Centre
for Technology and Development)
RHA contains silica in amorphous and extremely cellular form, with 50-
1000 m
2
/g surface area. Therefore, the use of RHA cement handling and
enhanced stability, reduce the heat generation, thermal cracking and
plastic shrinkage.
Bagasse ash (BA)
Bgsse is the brous residue from sugr cne juice extrction nd is one
of the most valuable by-products in sugar and alcohol industry. Shown in
photograph (2.6).
37


Photograph (2.6): Bagasse ash (BA).
Brazil and India are largest producers of sugarcane in the world. India
produces about 300 million tons per year and these increases annually.
(Ganesan, Rajagopal&Thangavelb 2007). More than 200,000 tons of
bagasse is produced every year in Thailand.
BA contains amorphous silica and shows good pozzolanic properties, but
its uses re limited nd most of it disposed in lndlls Recently it used s
addition in cement industry, which reduce the amount disposed as waste
and beneficial for the environment.
BA is recently accepted as a pozzolanic material, can replaced by 10%,
20% and up to 30%, the optimum amount of bagasse ash in concrete is
10% it produces high-strength concrete. Raw bagasse ash has a large
particle size and a high porosity. It can be ground up into small particles
when it is dry using ball mills with steel and alumina balls. Usage of
ner bgsse sh results on upgrded mechnicl properties of mortr nd
concrete it increases early strength, reduces water permeability and
38

improves chloride penetration resistance. (Nuntachai, Chai J &Kraiwood
2009).
Sugar factories use different process of burning and collecting which
affects the physical and chemical properties of the ash.
The specic surfce re of B is found to be three times higher thn
OP, the density, specic grvity nd men grin size of B re found to
be less than those of OPC. BA contains high levels of S, A and carbon
content (>15%).
It has a net calometric value of around 8000 kJ/kg, with a moisture
content of around 50 % by weight and ash content in the range 45
% by weight.
Also it is interesting that the 7 days compressive strength value of 20%
BA concrete is equivalent to the 14 days compressive strength value of
control specimen, and the 14 days compressive strength is equivalent to
that 28 days compressive strength value of control specimen, further
observed that 28 days compressive strength is equivalent to 90 days
compressive strength value of control specimen.(Ganesan, Rajagopal &
Thangavelb 2007).
LOI in bagasse ash has a high effect on the compressive strength and
sulfate resistance, it depends on the ignition temperature, which is about
(500-800) C. Usually LOI vary from 1.81% to 0.52% at 800 or 1000C
respectively.
The development of compressive strength in mortars containing ground
bagasse ash having high LOI (larger than 10%) were slightly slower than
mortars containing ground bagasse ash having low LOI (less than 10%).
However, at the later age, mortars containing either low or high LOI of
39

ground bagasse ash had similar compressive strengths. Water
consistency of the blended cements increases depending on the increase
of BA weight, cause of higher surface area as compared with OPC,
although initial and final setting times increase. (Nuntachai, Chai J
&Kraiwood 2009).

Previous studies on BA Pozzolana in Asia (India)
Singh et al (2000) investigated hydration of bagasse ash BA blended OPC
hs been studied B obtined from The Knori ugr Works,
ptingnj, Kushingr ws used s blending component nd its
chemical compositions are given in Table 2.13 with that of Portland
cement used.

Table 2.13: Chemical compositions of (BA) and cement.
Chemical composition BA (%) Cement (%)
S 63.16 19.75
A 9.70 4.84
F 5.40 3.26
C 8.40 62.66
M 2.90 4.19
K - 0.54
N - 0.06
2.87 2.13
LOI 6.90 -

Blended cements were prepared by mixing Portland cement with different
amounts of BA (10, 20 and 30%) by weight, and water-binder ratio (w/c)
40

of 0.5to measure the compressive strength. The variation of compressive
strength with BA and time is shown in Fig. 2.2. The compressive
strength in the case of control increased with hydration time. In the
presence of 10% BA, these values also increased with time and were
always higher than that of control. However, at higher addition of BA
(>10%), the values were lower and much lower at 28 days of hydration.
Thus, 10% addition of BA to Portland cement may be considered as the
optimum limit. The increase in compressive strength in the presence of
10% BA may be both due to physical and chemical processes. BA is fine
powder with high specific surface area and in cement paste it may lead to
segmentation of large capillary pores. It may also introduce a large
number of nucleation sites in the system for the rapid precipitation of
hydration products. Further, the pozzolanic reaction between CH and S
and the hydration of S itself in the alkaline environment will be
responsible for the increased compressive strength.

Figure 2.2: Variation of compressive strength with curing time.



41

2.2.3 Pozzolana in Sudan
The natural deposits of pozzolanas are available in Sudan in huge
amounts and untapped resources particularly, in the Bayuda Desert,
Meidob hills and Jebel Marra in Darfur (Suleiman2009). Scientific
researches about pozzolana in Sudan are few and a significant part of
which is a preliminary researches. In spite of using pozzolanic materials
in Senar dam construction (1919 -1925), there was no wide practical
initiative about using pozzolana. In (1999) investigation carried out by
Economic Alternatives Organization which had many success elements.
Also maybe there was other experience which needs more studies about
the results to realize the whole idea. There are many types of pozzolanic
materials in Sudan, especially natural pozzolana. But it had no enough
Geologicalsurveys.
Much evidence gives us an idea about the places where the deposits of
raw natural pozzolana are available. The volcanic ash is obtainable at
JabalMarra in Darfur, Jabal Abo-hadded in Kordofan, Bayuda desert in
northern state and Al gadarif region. But the diatoms are available at
northern Darfur, Kabkabya region, Al gregreeb,aljazzera region and
Katol mountain in northern Kordofan.
There are other pozzolanic materials which can be used in commercial
exploitation, such as Pumice, Obsidian and Scoria. But the problem is
that no enough geological investigations to obtain those materials.
Artificial pozzolanic materials available in Sudan are, Fragments of red
bricks and baggasse ash which is available at sugar factories as a by-
product of burning Sugar-cane. It is worth notice that baggasse as a
hazard in itself due to self-ignition phenomenon. Also baggasse used in
electrically generation.
42

In this regard the organization built an experimental unit to produce
pozzolanic cement. Volcanic ash and red bricks fragments were used to
produce pozzolana and pozzolanic lime cement.
Great success was achieved by the experiments done.
In term of producing cost the savings were about 27%.
In term of using 10% Portland cement to pozzolanic lime cement in
finishes good results achieved and the cement strength was good
with time and showed great resistance against humidity and rain.
In term of using pozzolanic cement in mortar the savings were
about 30%.
Also one of the important investigations done by the organization is a
study about a residential house of 200m (build area) combined of
foundations, grid beams and columns. The comparison was in cost
between using OPC and pozzolanic cement with a replacement of 50% in
finishes considering labour costs, expenses and profits. The result was the
replacement provided saves up to 22% of building total coast. It should
be pointed that the percentage of saving will increase in upper floors
considering that no foundations and grade-beams. Savings will be even
much more in load bearing buildings because of using more mortar.

Pozzolana in Jebel Marra Darfour :
Jebel Marra has a considerable proportion of the tuffs on northern side of
the mountain, almost consist entirely of fragments of pumice, photograph
(3.7) shows location of Jebel Marra in Sudan.
The target area is located about 150km to the west of Neyala and
accessible by paved road from Nyala to Zalingei.
43

Also Natural pozzolana (volcanic ash) is available at Kas and Almalum
regions. Kaolin was used at Rahad Abyad 40 kilometre to the south from
Nyala and peanuts shell ashes from edible oil factories.
Area of volcanic ash deposits at Jebel Marrais about 3700 km and
determination of raw material needs geological and geophysical studies.
Usually volcanic ash is thrown far distances from craters up to ten
kilometres, further more water transports it far away distances. An
example for that process is Al Kas region which is 60 km from the carter
and Al Malum region which is 50 km to the east of the mountain.
(Ibrahim & Ahmed 2013).

Photograph (2.7): Map of Jebel Marrah.
Pozzolana in Bayuda desert
The quarry sites of pozzolana raw material lie at 63 Km South of Merowe
city in the volcanic field of the Bayuda Desert in the Northern State. The
44

area of the pozzolana raw material occurs in Jebel Mazrub and Jebel
Hebeish, bounded by:
Longitudes 6 8 8 - 8 5 E
Ltitudes 8 9 - 8 9 68 N
(Suleiman 2008)


Photograph (2.8) shows the maps of Beyouda desert in sudan.(EL-
haj2010)
45

The quarry is accessible by trucks during all season of the year, from
Khartoum by Shrian Al Shimal paved road to Merowe and 63Km by
unpaved road.
The area is characterized by high ridges and the drainage system is
formed by a network of wadis draining towards the Nile.
Previous Investigation
Most of the previous work done in the Beyuda Desert was based on
geology of the area rather than prospecting work on large resources and
Industrial minerals.
Almond et al. 1969, as cited in Suleiman 2008, have estimated the total
volume of pyroclastic rocks at 9km
3
but did not mention them as valuable
building materials.
German exploration project in 1976/78 in the entire Beyuda Desert
revealed an outstanding result mentioned a huge amount of pozzolanic
materials such as volcanic ash, tuffs, pumice, tephra and scoria.
Recently, the geological Research Authority of Sudan (GRAS) has given
great concern for large resources of pozzolanic deposits in the Beyuda
Desert. Most of these natural pozzolanic deposits exhibited positive
pozzolanic activities after studies. These materials were found suitable as
pozzolanic when added from 25% up to 50% as cement replacement
without adversely affecting the strength properties of concrete.
According to the testing results, Beyuda pozzolana can be used as a
replacement of cement up to 30% for use in structural concrete
applications competing with structural PC concrete up to 50%
replacement level for use in plasters, mortars, renders for non-structural
purposes such as interlock pavements, walling blocks and roofing tiles.

46

Geology
The field of main volcanic pozzolana lie in the northern part of Beyuda
Desert extends over a length of50km and width of 20km occupies an area
of almost 1000km. Essentially the field of volcanic material differs in its
geologic-geotectonic position. Preservation of primary volcanic
morphology was excellent and the youngest of volcanoes indicate that the
activity was geologically recent.
The central mountains of the Beyuda Desert are 900m height. Basaltic
lava flows, tephra and tuffs almost covers the crystalline basaltic structure
of volcanic.
Pozzolanic materials found in the target area were pumice, welded tuffs,
volcanic ash and tephra. They are largely lying unexploited.
Since the welded tuffs and unconsolidated volcanic ash has a glassy
structure and contain more silica than other volcanic materials. They are
potentially more pozzolanic compared to others.
Jebel Hebeish and Jebel Mazrub represents are the main isolated centres
that contain the most deposits of pozzolanas.
Jebel Hebeish
Jebel Hebeish crater is 800m diameter and bounded by a rim of outward-
dipping tephra of 60m height above the crater floor to the north-west, but
only 20m high in the south.
The total reserve of pozzolanic materials in Jebel Hebeish is about 10
million tonnes (suliman 2008).


47

Jebel Mazrub
Jebel Mazrub is typical composite volcano, has a cone shape of 180m
height above the plain and skirted by sub-circular lava field of 3km
diameter. The conies built of thin bedded ash and thicken beds of cinder
breccia and agglomerate.
The total reserve of pozzolanic materials in Jebel Hebeish is about 33
million tonnes (Suleiman 2008).
Previous Studies on Natural pozzolana in Sudan
Abdalateef et al (2012) investigated Sudanese Natural Pozzolans from
Beyouda desert (Abuzaid works) noted as NPBA.
They tested the fineness of NPBA, they found that the retained
percentage of NPBA from sieve 325 (45m) is 38.6. Table 2.14 shows
the specific gravity for NPBA.
Table 2.14: SG for NPBA (Abdalateef et al 2012)
Specimen Replicate 1 Replicate 2 Replicate 3 Average
NPBA 2.83 2.85 2.85 2.84

Table 2.15 show the chemical composition of NPBA used in this study
and another natural pozzolana specimen from Beyuda Desert.



48

Table 2.15: Chemical composition of NPBA used in this study and
another natural pozzolana specimen from Beyuda Desert(Abdalateef et al
2012).
Oxide NPBA % NPBW-Boulder
%
S 40.31 40.34
A 12.44 10.40
F 12.74 12.14
0.015 0.014
C 5.31 11.45
K 0.70 11.76
N 4.29 11.66
M 9.35 7.10
LOI 8.74 1.60

Compressive strength test was done by 707070 mm mortar cubes of
each mix of the mixes shown in tables 2.16 and SAIs shown in table 2.17.
The cement: pozzolana replacement ratio is 80:20 with water/binder ratio
for NPBA is 0.504.

Table 2.16: The Compressive Strength of the Cast Mortars
Cubes(Abdalateef et al 2012).
Samples Compressive strength (Mpa)
28 days 62 days 91 days
NPBA 30.0 31.1 39.3
49


Table 2.17: The Strength Activity Index (SAI) (Abdalateef et al 2012).
Samples SAI
28 days 62 days 91 days
OPC 1.00 1.00 1.00
NPBA 0.96 0.75 1.01


Mamoun &Zamzami (2010) studied and evaluated natural pozzolans
collected from quarry site in Beyuda Desert.
They tested tow samples from volcanic tuffs deposit and pumice deposit
and determined the chemical composition as shown in table 2.18 and
table 2.19.

Table 2.18: Chemical composition of Beyouda volcanic tuffs (Mamoun
&Zamzami 2010).
Chemical
components
S A F C M

N K LOI
Percentage
of weight
(%)
56.4 9.12 7.61 6.63 6.41 0.424 0.82 1.08 10.8


50



Table 2.19: Chemical analysis of Beyouda pumice(Mamoun &Zamzami
2010).
Chemical
components
S A F C M

N K LOI
Percentage
of weight
(%)
51.89 10.13 9.67 7.79 6.63 0.424 0.19 1.06 11.4

Ibrahim & Ahmed (2013) studied and evaluated natural pozzolans
collected from tow regionsof Jebel Marra. They donated as KVA (Kass
area) and MVA (Malam area) tested volcanic Ash and determined their
chemical composition as shown in table 2.20.
Table 2.20: Chemical composition of KVA & MVA (Ibrahim &Ahmed
2013).
Material Chemical Composition %
S A F C M K N LOI
KVA 63.1 15.3 5.33 0.864 0.291 0.022 5.23 2.35 2.2
MVA 56.5 15.5 4.33 2.22 0.652 --- 3.90 4.30 6.6




51

2.2.5 Previous Studies on Natural pozzolana
Pozzolana in Asia (China)
Lam et al (1999) investigated the natural zeolite. Which is one of types
of natural pozzolans does not need treatment. They found that, the
chemical compositions of natural zeolite and Portland cement used shown
in Table 2.21.

Table 2.22: Chemical composition of the cement and natural zeolite.


The cement-zeolite pastes were prepared at two water-to-cementitious
materials ratios: 0.25 and 0.3. Zeolite was used as a direct replacement of
cement by weight basis at the levels of 15%, and 20%.
The compressive strength of the cubes (70mm70mm70mm) was tested
at the ages of 3, 7, 28, 90, and 180 days, and the results in Table 2.23.


Chemical compositions Zeolite (%) Cement (%)
S 72.03 19.61
A 11.90 4.82
F 0.67 3.32
Ca 1.69 2.54
M 1.19 63.92
0.03 2.63
LOI 7.09 1.86
52

Table 2.23: Compressive strength of the natural zeolite blended cement
pastes.
Mix Compressive strength
(MPa).

w/binder
ratio
Zeolite
(%)
3 days 7 days 28 days 90 days 180
days
0 73.02 81.91 107.4 120.60 124.73
0.25 15 69.61 81.32 96.01 109.53 127.90
25 63.50 82.89 103.23 107.33 123.73
0 62.50 73.26 87.15 105.30 111.87
0.3 15 61.01 68.94 87.75 100.94 117.17
25 50.31 67.35 90.82 106.50 118.83

The results of the compression test are shown in Table 2.17, when
compared with OPC paste, at the ages of 3 days and 7 days, zeolite
replacements slightly reduced the compressive strength. At the age of 28
days and after, the compressive strength of the pastes with zeolite
replacement was almost the same as the OPC pastes. The zeolite in the
pastes with a lower W/C ratio appeared to contribute better to strength
than that in the pastes with a higher W/C ratio. For example, at the age of
7 days, the pastes with 15% and 25% zeolite replacements with a W/C
ratio 0.25 achieved strength values equivalent to that of the PC paste. But
those with the same zeolite replacements with a W/C ratio of 0.3
achieved only 93% of the strength of the corresponding OPC paste
Table 2.24 shows the variation of degree of reaction with time. The
cement/zeolite ratio was used is 80:20.

53

Table 2.24: Degree of reaction of zeolite blended cement paste.
Mix Degree of reaction of zeolite
(%)

W/C ratio
(%)
Zeolite (%) 3 days 7 days 28 days 90 days 180 days
0.25 15 5.20 9.15 29.36 36.15 52.14
0.30 25 4.68 8.44 27.95 35.44 50.16
0.25 15 5.17 9.08 28.94 36.32 53.15
0.30 25 4.93 8.92 28.45 36.14 51.09

Lam et al (1999) compared the degree of reaction of zeolite blended
cement paste with the degree of reaction of fly ash and silica fume
blended cement pastes. It measured by the same procedure used in this
investigation, are reported in another study carried out by them. The
comparison between the degree of reaction of zeolite, fly ash and silica
fume blended cement pastes shown in Fig 2.3, and the replacement ratio
of silica fume blended cement paste is 15% and the ratio of fly ash
blended cement paste is 25%, with a W/C of 0.3.

Figure 2.3: Comparison of degree of reaction of natural zeolite with fly
ash and silica fume.

54

At the age of 3 days, a degree of reaction of approximately 5% was
recorded for the zeolite. Such a value is similar to that of the fly ash in a
fly ash blended cement paste with a 25% fly ash replacement. It is,
however, lower than that of the silica fume in silica fume blended cement
paste with a 15% silica fume replacement. At the age of 28 days, the
degree of reaction of the zeolite was approximately 29%, while the
degrees of reaction of the fly ash and the silica fume were 16% and 35%,
respectively. At the latter ages, the degree of reaction of the zeolite was
still higher than that of the fly ash but lower than that of the silica fume.
At 180 days, approximately 50% of the zeolite had been reacted.
Generally, from Fig. 2.3 it can be seen that the reactivity of zeolite is
higher than that of fly ash but lower than that of silica fume.

Natural pozzolana in Europe (Turkey)
Adnan Colak (2002) published his research result of blended natural
pozzolana with OPC pastes. The blend with a composition of 80% OPC
and 20% natural pozzolana and 1% naphthalene-type super plasticizer.
Table 2.25 shows chemical compositions of natural pozzolana and
Portland cement (OPC) used in tests.




55

Table 2.25: Chemical compositions of Turkish natural pozzolana and
cement (OPC) used.

The (S+A+F) proportion affecting the pozzolanic activity within the
material is 80.6% that goes beyond the limit of 70% determined in
Turkish standard (TS 25).
Table 2.27 shows the effect of natural pozzolana content and cure time on
compressive strengths of blended Portland cement pastes with and
without super plasticizer (MPa) paste with dimensions of
40mm40mm40 mm and water / binder ratio shown in Table 2.26.




Chemical
compositions
Pozzolana (%) Cement (%)
S 65.3 20.56
A 2.82 5.38
F 12.48 3.08
C 0.41 63.39
M 0.075 1.31
5.42 2.45
N 0.34 0.45
K 2.9 0.67
LOI 9.8 2.59
56

Table 2.26: Water to Portland cement plus natural pozzolan ratios of plain
and blended Portland cement pastes.
Composition of blend Water / binder ratio
100:0 0.34
80:20 0.355
100:0:1 0.28
80:20:1 0.3


Table 2.27: Compressive strength of blended Portland cement with
natural pozzolana (Adnan Colak 2002).
compressive strengths (MPa)
Cement/pozzolana
ratio
100:0 80:20
Curing time (days) With
s.plas.*
Without
s.plas.*
With
s.plas.*
Without
s.plas.*
7 69.03 68.81 59.19 53.13
28 78.56 76.56 74.38 68.75
90 95.44 93.13 81.41 76.25
180 96.94 94.38 91.88 77.81

*super plasticizer






57

Results show that, the compressive strengths of wet samples without
super plasticizer at 7 days of curing decreased from 68.81 to 53.13 MPa,
as natural pozzolana content increases from 0% to 20%. For the blends
made using the super plasticizer, the decrease is from 69.03 to 59.19
MPa. When the natural pozzolana blended Portland cement pastes with
compositions of 80:20 and 80:20:1(with super plasticizer) is compared,
the reason for the reduction in the 28 day compressive strength is found
to be related to the increase in water content from 0.3 to 0.355. From
these findings, it can be concluded that two mechanisms are responsible
for the strength reduction in the blended Portland cement with natural
pozzolana, i.e., the increase in water and natural pozzolana contents.


Natural pozzolana in Africa (Algeria)
Ezziane et al (2007) investigated an Algerian natural pozzolana, extracted
from the Bouhamidi deposit in the Beni-Saf region (north-west of
Algeria) the chemical compositions of natural pozzolana and OPC used
shown in Table 2.28.
Tests applied with water-binder ratio 0.47 and amount of super plasticizer
1% (by weight of the binder). The specimens were cured under constant
tempertures of , 4 nd 6 It ws prepred contining cement
replacement by 20% of natural pozzolana.





58

Table 2.28: Chemical compositions of Algerian natural pozzolana of
Bouhamidi deposit and OPC used.

The compressive strength results are summarized in Table 2.29. In which
each value represents the average of four tests with error deviation less
than 8%.
Table 2.29: Compressive strength of mortar cured in different
temperatures with cement replacement ratio (20%) of natural pozzolana.
Age in
days
Compressive strength (MPa)
Temperture () Temperture(4) Temperture(6)
0% 20% 0% 20% 0% 20%
1 7.7 5.6 10.7 8.8 14.4 13.4
3 15.2 14.0 19.9 17.1 19.8 20.2
7 22.4 19.8 23.6 21.3 23.8 25.0
28 30.3 33.3 28.1 32.0 27.0 31.2
90 34.0 40.2 31.1 39.0 28.8 35.0

Chemical compositions Pozzolana (%) Cement (%)
S 46.4 19.9
A 17.5 5.6
F 10.5 2.5
C 10.5 64.0
M 3.8 1.8
0.4 3.1
K

1.5 0.7
N 3.4 0.1
LOI 4.31 1.7
59

Results of compressive strength showed that strength increased
significantly with temperature in early age and decreased in lately age.
Presence of natural pozzolana minimized the effect of high temperature
on strength relatively.
Pozzolana in Asia (Jordan)
Yeginobali and Shannagt (1994) investigated the natural pozzolana of Tal
Rimah region of northeastern Jordan. The specimens were volcanic tuffs,
and it was ground to required levels of fineness. Although the two
specimens were from the same source and had similar compositions, their
fineness and activity values were different as noticed in Table 2.30.
Therefore, in this study they were referred to as Pozzlana A and Pozzlana
B. Type of cement used is OPC and its chemical composition shown in
Table 2.30.
Table 2.30: Chemical composition for pozzolana (A, B) and OPC used.
Chemical
composition
Type of pozzolana (%) Cement (%)
A B


S 40.1 38.5 21.2
A 13.4 12.8 6.1
F 12.1 11.9 3.0
C 9.70 9.60 63.2
M 10.0 9.70 1.4
S
-
- 0.01 2.9
K 1.50 1.50 0.9
N 1.40 1.30 -
LOI 9.50 12.5 0.8
60


The water/cement ratio was used in compressive strength test of cocrete
is 0.485 and results of test shown in Table 2.31.
Table 2.31: Compressive strength of concrete blended cement with
natural pozzolana (A, B).
Pozzolana addition Batch
series
Compressive strength (MPa)
7 days 28 days 90 days
Control mix 1 28.77 40.65 48.34
2 28.99 39.59 47.92
15% Pozzolana A 1 29.23 40.30 48.56
2 28.88 40.56 48.14
25% Pozzolana A 1 25.64 36.52 45.34
2 26.18 36.92 45.32
25% Pozzolana B 1 26.02 39.21 46.76
2 25.99 39.63 46.78
35% Pozzolana A 1 18.67 31.26 38.34
2 19.08 30.79 38.32
35% Pozzolana B 1 19.62 32.68 39.12
2 19.26 32.79 40.08

As for the compressive strengths, mixes with 25% pozzolana B
developed 28 and 90 day strengths very close to the control strengths
obtained with the Portland cement. However, with 35% pozzolana B
control strengths were superior at all tested age. Similar mixes containing
pozzolana A had slightly lower strengths than the ones containing
pozzolana B.
61










CHAPTER (3)
EXPERIMENTAL SETUP

62

3.1 Materials
3.1.1 Cement
Local Sudanese OPC produced by AL-Shamal Company branded as
(Mass cement) was used. Table 3.1shows physical properties of the
OPC,as reported by concrete laboratory of Khartoum University, Faculty
of Engineering, Nile Avenue, Khartoum Sudan.
Table 3.1: Physical properties of OPC
Test No. Test conducted Results Requirements of
SSMO*
164:2002
1 Consistency 30.0% -
2 Soundness - Not more than
10 mm (+1)
3 Setting times
(min)
a- Initial
b- Final

178 min
269 min

Not less than 60
min
Not more than
390 min
4 Compressive
Strength
(

)
a- 2-days
1.
2.
3.
b- 28-days
1.
2.
3.



24 (

)
24.3 (

)
25.4 (

)

58.9 (

)
60.9 (

)
62.8 (

)




Equal or Greater
than 10
(

)



Equal or Greater
than 42.5
(

)


63

3.1.2 Beyuda Desert Natural Pozzolana (BD-NP):

The specimen of BD-NP procured from Beyuda Desert in the Northern
State, some 63Km South of Merowe.
The specimen is mixture of pumicite and powder of BD-NP, Its colour is
grey similar to OPC as shown in photograph 3.1.


Photograph 3.1: BD-NP as received specimen(containing some pumicite
boulders).
After grinding Pozzolana as shown in photograph 3.2the tests were done
according to ASTM C311.
64


Photograph 3.2: BD-NP after grinding specimen.

3.1.3 Slaked Lime
Calcium hydroxide (CH) is a colourless crystal that is created when
calcium oxide (called lime or quicklime) is slaked with water. It can also
be manufactured by mixing an aqueous solution of calcium chloride and
an aqueous solution of sodium hydroxide. A traditional name for calcium
hydroxide is slaked lime, or hydrated lime. ASTM C311 recommends
the use of technical grade hydrated lime. However, commercial grade
lime procured from Algamair, in Omdurman was used in this project.
The C content of this lime was analysed by Chemical laboratory of
Central Laboratory for Science and Environment and Soil Research
(CLSESR), Khartoum, Sudan.

65

3.1.4Graded Standard Sand
Graded sand is standard sand predominantly graded between 600-m
(sieve No. 30) sieve and 150 -m (sieve No.100). As it defined in ASTM
C778. The used sieves is shown in photograph 3.3.

Photograph 3.3: Sieves.

Standard sand was prepared in the laboratory from natural silica sand
used in Khartoum area according to the requirements for graded standard
sand specified in ASTM C778.

66

3.1.5 Water
Tap water was used for mixing of all specimens and saturated lime for
curing of control OPC and 80%OPC: 20%BD-NP specimens.
There was a mistake curing the control specimen OPC in saturated lime
water.
3.2 Test methods
3.2.1 Test on Raw Materials
3.2.1.1 Fineness
Scope
There are two methods for obtaining pozzolanic materials fineness,
namely by air permeability apparatus using ASTM C204, or by wet sieve
analysis using 45-m sieve (No325) according to ASTM C430.
Wet sieve analysis laboratory test on sieve # 325 (standard process) was
used in this study.
Apparatus
Containers (photograph 3.4)
Sensitive balance (photograph 3.5)
Oven (photograph 3.6)
Distilled water
Sieve # 325, size 45m (photograph 3.7)

67


Photograph 3.4: Containers

Photograph 3.5: Sensitive balance.

68


Photograph 3.6: Oven.


Photograph 3.7: Sieve # 325, size 45m

69


Test Procedure
50 grams of the BD-NP sample were weighed and then placed on clean
and dry 45m (sieve No. 325). The ASTM C430 requires that, spray
nozzle in specific pressure should be used to wash the sample. However,
due to unavailability of these equipment, sample was wetted thoroughly
with gentle stream of tap water and generalized pressure by hand, till the
water passed through the sieve become showing no dirt. The retained
weight of sample was oven dried at temperature 1052 C.
Calculation
The results were analysed using equations (eq3.1 ,eq3.2)
Retained% =

100% (eq 3.1)

Passed% = 100% - retained% (eq 3.2)
Where:
Ws weight retined on the sieve after washing and oven-drying.
Wt total weight before washing and after oven-drying to rid moisture
from received sample.
3.2.1.2. Specific gravity
Scope
Specific gravity (SG) is defined as ratio of mass of unit volume of a
material, at a stated temperature, to the mass of the same volume of gas-
free distilled water at the stated temperature.

70

Apparatus
Pycnometer (50 ml) (Photograph 3.8)
ensitive blnce (accuracy 0.001 gm)
Distilled water
Pozzolana sample of about 10 gm.


Photograph 3.8: Pycnometer.

Test Procedure
The pycnometer was washed carefully and oven dried at temperatureof
about 105C for about 5 minutes. Then the pycnometer was weighed and
is weight was recorded as (W1). About 10 gm of Pozzolanas smple ws
added to the pyncometer and weighed, its mass was recorded as (W2).
71

Two samples were prepared and placed into the pycnometer separately.
Then sufficient distilled water was added to the pozzolana to submerge
the specimen. The mixture was shaken by hand for about one minute and
left for ten minutes to settle down. After that the pycnometer was filled
with distilled water to remove the entrapped air and weighed. This weight
was logged in as (W3). Finally the pycnometer was emptied, cleaned and
filled with distilled water and weighed, the weight was recorded as (W4).
Calculation
The SG was calculated using the following equation:

()()
(eq.3.3)
Where:
W1: weight of empty pycnometer
W2: weight of pycnometer + 8 gm of sample
W3: weight of pycnometer + 8 gm of sample + distilled water
W4: weight of pycnometer + distilled water
3.2.1.3 Moisture content
Scope
Moisture content (M.C) is defined as the amount of water in a material
determined under prescribed conditions and expressed as a percentage of
the weight of the moist specimen.



72

Apparatus
Containers.
Oven.
Sensitive balance.
gms of pozzolana sample.

Test Procedure
Three samples of grinded BD-NP wereput on three dishes (W1). The
assembly of sample + dish were oven dried at temperature 105C for 24
hour then weighed again after drying (W2). The moisture content was
calculated for each sample (eq 3.4) after weighed empty dishes (W
dish
).
The mean moisture content was obtained.
Calculation
The moisture content was analysed using equation (eq 3.4)
M.C% =

100% (eq 3.4)

Where:
Ww weight of loss water (W1-W2)
Ws weight of totl smple (W1-W
dish
)

3.2.1.4 Chemical Analysis
Scope
Clause 4.1.2 of ASTM sttes tht The chemicl component
determinations and the limits placed hydraulic cement in concrete, but
73

collectively help describe composition nd uniformity of the mteril
Chemical analysis was carried out by Environmental Laboratory of the
Faculty of Engineering, University of Khartoum . In this study the
chemical composition of the pozzalana was determined using methods
described in the applicable sections of Test Methods ASTMC114.
3.2.1.5 Loss on ignition
Scope
Loss on Ignition (LOI) is a test used in inorganic analytical chemistry. It
consists of strongly heating and igniting a sample of the material at a
specified temperature, allowing volatile substances to escape, until its
mass ceases to change.
Apparatus
Sample of pozzalana.
Sensitive balance.
Muffle furnace.
Crucible.
Test Procedure
Loss on ignition was determined in accordance with the procedures
outlined in Test MethodsASTM C114. However, the material remaining
from the determination of moisture content was ignited to constant mass
in an uncovered porcelain, not platinum, crucible at 750 50C (1382
190F).
Calculations
Loss on ignition %
=
(A/B) 100 (eq 3.5)
Where:
A = loss in mass between 105 and 750C (221 and 1382F)
74

B = mass of moisture-free sample used.

3.2.2 Tests carried out on Binder 80% OPC: 20% BD-NP& its
mortar
3.2.2.1 Pozzolanicity test for pozzolanic Cement (RIO-FRATTINI
test)
Scope
European Standard specifies the method of measuring the pozzolanicity
of pozzolanic cements conforming to EN 197-1. This standard does not
apply to Portland pozzolana cements or to pozzolans.
The pozzolanicity is assessed by measuring the concentration of Ca
+2
,
expressed as CaO, present in the aqueous solution in contact with the
hydrated cement after a fixed period of time. The CaO concentration is
then comparedwith the quantity of Ca
+2
capable of saturating a solution of
the same alkalinity. The material is considered to satisfy the test, i.e.
gives a positive result and the material is pozzolanic. If the concentration
of Ca
+2
in the tested solution is lower than the saturation concentration.

Apparatus
500 ml cylindrical container
Funnels.
Filter pper, (men pore dimeter of bout m)
250 ml vacuum flask.
250 ml and 400 ml beakers.
50 ml and 100 ml pipettes
50 ml burette.
75

Uniform temperature enclosure, controlled thermostatically at
(401) C.
500 ml and 1 000 ml volumetric flasks.
250 ml conical flask.
Sensitive balance
Stirrer glass rod
pH meter, capable of measuring to an accuracy of 0,05.
Photograph 3.
Graduated cylinder of 10ml or 20 ml.
Some of the apparatus shown in photograph 3.9


Photograph 3.9: Apparatus of pozzolanic activity test.



76

Chemical Reagents
Concentrated l ( = 8 to 1.19 g/cm
3
).
HCl concentration, about 0.1mol/l.
Dilute HCl.
Methyl orange indicator
Sodium hydroxide (powder), (NaOH).
NaOH solution, prepared by dissolving (100 1) g of NaOH
powder in water and making up to 1 000 ml.
CaCO
3
dried to constant mass at (200 10) C (purity greater than
99.9 %).
EDTA, (dihydrated disodium salt of ethylenediaminetetra-acetic
acid).
EDTA solution, about 0,03mol/l.
Sodium carbonate powder, (Na
2
CO
3
), dried to constant mass at
(250 10) C.
Calcon indicator.

Test Procedure
Standardization of the EDTA solution:
0,0005 g of CaCo
3
(m1) was weighted and placed into a 400 ml beaker
and filled with approximately 100 ml of distilled water. The beaker was
covered with a watch glass then carefully 10 ml of HCL was introduced,
the solution was stirred with a glass rod until the dissolution is complete,
the solution was heated in a boiler in order to expel the dissolved CO
2
.

The solution was cooled to room temperature, then transferred to a
volumetric flask, the beaker and watch glass was washed carefully with
77

distilled water, and the aliquots were added to the solution and made up
to 1000 ml with distilled water.
50 ml of CaCO
3
solution was pipetted into a beaker suitable for the
measuring apparatus. Then diluted with distilled water to a volume
suitable for the operation of the apparatus. A pH meter was used to adjust
the pH of this solution to 12.5 with the NaOH solution.

The end-point was determined by the following method

Visual determination of the end-point
About 0.1 g of the calcon indicator was added to the calcium solution.
The solution was stirred and titrated with the 0.03 mol/l EDTA solution
until the color changed from purple to blue. The volume of EDTA
solution used in titration was logged as V
1
. V
1
was used to calculate the
standardization factor (f
1)
using (eq 3.6).

Standardization of the 0.1mol/l solution of hydrochloric acid 0.0005 g of
sodium carbonate was weighed (m
2
) and added to the 250 ml conical
flask and dissolved in 75 ml of distilled water. Five drops of the methyl
orange indicator was added to the solution and titrated with the 0.1mol/l
diluted hydrochloric acid until the color changes from yellow to orange.
The volume of 0.1 mol HCL solution used in titration was logged as V
2.

The volume V
2
used to calculate the factor (f
2)
, using (eq 3.7).
Storage and filtration of the sample
100 ml of freshly boiled water was pipetted into cylindrical container,
sealed and placed in the uniform temperature enclosure (401) until
equilibrium is reached (about 1 h). The container was removed from the
78

uniform temperature enclosure. Fourgm of pozzolans and 16 gm of OPC
are mixed together and placed into the container. The container was
sealed immediately. The container was shaked vigorously by hand for
about 20 s to avoid formation of lumps.
The container was replaced in the uniform temperature enclosure (40C).
After a period of 8 days in the uniform temperature enclosure, the
container was removed and the solution was filtered immediately under
vacuum through the funnel into the vacuum flask using dry double filter
paper in less than 30 s (to avoid absorption of atmospheric carbon dioxide
and any appreciable lowering in temperature of the solution). The
vacuum flask was sealed immediately and the filtrate cooled in room
temperature.
Determination of the OH
-
concentration
The vacuum flask was Shake to homogenize the filtrate. Then 50 ml was
pipetted of the solution into the 250 ml beaker. Five drops of MO
indicator were added and the total alkalinity was determined with the
0.1mol/l dilute HCL. The titration end-point corresponded to the color
change from yellow to orange, the diluted HCL volume used in titration
was logged as V
3
. The titrated solution (A) was kept for the determination
of Ca
+2
concentration.
The OH
-
concentration was calculated, in mmole per litre, using (eq 3.8).
Determination of the CaO concentration
The titrated solution (A) was used. The pH was adjusted to 12.5, with
NaOH solution by using the pH meter. The solution was titrated with 0.03
mol/l EDTA solution determining the end-point by using the previous
method, the EDTA solution volume used in titration was logged as V
4
.
79

The calcium oxide concentration [CaO] was calculated in mill moles per
litre, from the formula (eq 3.9).
Readings
m
1=
1.0005 gm
m
2 =
0.2002gm
V
1 =
5.0 ml
V
2 =
39.2 ml

Table 3.2: Readings of HCl and EDTA volumes used in titration.
Sample No. V
3
(ml)

V
4
(ml)

1 25.9 2.0
2 27.1 1.2
3 27.4 1.0
Average 26.8 1.4

Calculations
f
1 =
16.652 (m
1
/V
1
)................................ (eq 3.6)
Where:
m
1
is the mass of calcium carbonate, in grams;
V
1
: is the volume of EDTA solution used for the titration, in milliliters
f
1=
16.652 (1.0005/5) = 3.332 gm/ml
f
2 =
188.70 (m
2
/V
2
)................................ (eq 3.7)
80

f
2 =
188.70 (.2002/39.2) = 0.964 gm/ml
Where:
m
2
: is the mass of sodium carbonate, in grams;
V
2
: is the volume of hydrochloric acid used for the titration, in milliliters
[OH] - = 2 V
3
f
2
................................ (eq 3.8)
Where:
V
3
: is the volume of 0,1mol/l hydrochloric acid solution used for the
titration, in millilitres;
f
2
: is the factor of 0,1 mol/l hydrochloric acid solution.
[OH]
-
= 2 26.8 0.964
= 51.67mmol/l
[CaO] = 0.6 V
4
f
1
................................ (eq 3.9)
Where

V
4
:is the volume of EDTA solution used for the titration, in milliliters;
f
1
:is the factor of the EDTA solution.
[CaO] = 0.6 1.4 3.332= 2.8mmol/l
The results are drawn at chapter four.

81

3.2.2.2Mortar flow of hydraulic Cement Mortar ASTM C1437
Scope
The Standard Test Method for Flow of Hydraulic-Cement Mortar covers
the determinations of flow of hydraulic-cement mortars, and of mortars
containing cementitious materials other than hydraulic cement according
to the ASTM C 1437. It shows much mortr specimen ows when it is
unconned nd consolidted Mortr ow is process control test
procedure is like to a slump test for concrete and used to measure relative
consistence but with different mould dimensions hnges in ow
indicate variability in the materials and/or the batching process that may
not be observed from slump testing lone Mortr ow is more sensitive
than the concrete slump test for stiff concrete mixtures. It is sensitive to
several parameters including water content; ne ggregte grdtion,
cementitious chemistry, mixing time, air content, and concrete
temperture ll interct to ffect mortr ow
The flow value of the mortars containing Pozzolana must be 5% of the
control mix flow which will be calculated using (eq 3.10).
Flow as percentage (%) =

(eq 3.10)
Where:
S.D: spread diameter.
O.D: original diameter.
The test was carried out at the Civil Engineering Laboratory of
Omdurman Islamic University.


82

Apparatus
Flow mould, a brass conical mould with 10cm internal diameter at
base and 5cm internal diameter at top, height of 9cm.photograph
(3.10)
Flow table, consists of a 30 cm diameter polish steel plate with 3
engraved annular circles 7, 12 and 20cm diameter. The table top is
arranged for a free fall of 12.5mm by a cam action.
Tamper.
Trowel.
Calliper.
Balance. Photograph3.11


Photograph 3.10: Flow mould and flow table.


83


Photograph 3.11: Balance.


Test Procedure
242 ml water was added to 500gm OPC and 1375 gm standard sand to
measure the control flow. Mix of BD-NP specimens and OPC with
weight (20:80) respectively and water /binder ratio 0.484 and the same
amount of standard sand to measure the flow. The spreading of mortar
was applied by 15 hits in 15 seconds. The flow was calculated using (eq
3.10) and compared to OPC if its value was found equal to the OPC value
5was adopted otherwise another trial was done to achieve a flow with
the limit stated before.


84

3.2.2.3Compressive Strength Test
Scope
To determaine strength activity index (SAI) as described in clause 4.1.1
of ASTM C311-02 Is used to determine whether BD-NP specimens
produce an acceptable level of strength development when used with
hydraulic cement in concrete.
Four replicates of 70 70 70 mm mortar cubes of each mix of the mixes
shown in Tables (4.9 and 4.10)
The water binder ratios W/B as determined from ASTMC1437 mortar
flow and BD-NP water requirement in section 3.2.2.1
Clause 26.2 of the ASTM C311-02 requires that SAIs to be evaluated on
either 7 or 28 days on 20% BD-NP +80%OPC (for all samples) mortars
cured in sturted lime wter (c)
Apparatus
Three sets of triplicate 70mmx70mmx70mm cubes joint together.
photograph 3.12
Sensitive platform balance.
Blade.
Scoop.
Ruler.
Mechanical vibrator, as shown in photograph 3.13
Graduated cylinder photograph 3.14
Mechanical concrete mixer. photograph 3.15
Cube crushing machine. photograph 3.16
Curing tank. photograph 3.17
85


Photograph 3.12: Triplicate sets of cubes


Photograph 3.13: Moulds on vibrator.
86





Photograph 3.14: Graduated cylinder

87


Photograph 3.15 : Mechanical concrete mixer.

Photograph 3.16: Cube crushing machine.
88



Photograph 3.17: Curing tank


Test Procedure
The sets of triplicate 70x70x70mm cubes was cleaned and oiled.
Ingredients were weighed as shown in Tables (4.10to 4.13). The dry
ingredients were poured in the mixer and mixed for one minute. Water
was added and mixed for four minutes.
Moulds were filled with 35 mm thick layer of a mortar and vibrated by
the mechanical vibrator for one minute. Another layer of 35mm thick
was filled and vibrated for another one minute.
89

The cast cubes were labelled to be test at (3, 7, 28 and 91) days. Cubes
were cured in saturated lime wter (c) till the specific test dy
The strength activity indices (SAIs) with OPC were calculated using (eq
3.11):

( )
Where:
A = Average compressive strength of test mortars made of 80%OPC:
20%BD-NP cubes. (MPa)
B = Average compressive strength of OPC control mix cubes. (MPa)













90









CHAPTER (4)
RESULTS AND DISCUSSIONS


91

4.1Results of tests carried out on raw materials

4.1.1 Fineness
Table 4.1: Fineness result for BD-NP after Ball milling.
No Weight
(gm)
Weight (gm) retained
on sieve No 325
(45m)
%Retained
on sieve No
325 (45m)
%Passed on
sieve No 325
(45m)
1 50.01 6.14 12.30 87.70
2 50.01 6.28 12.60 87.40
3 50.04 6.12 12.20 87.80


4.1.2 Specific gravity
Table 4.2: Specific gravity results for BD-NP.
No W1 W2 W3 W4 SG Average
1 24.840 35.060 81.120 75.120 2.422
2.409 2 38.550 46.770 93.240 88.480 2.395

4.1.3 Moisture content
Table 4.3: Moisture content result for BD-NP.
No W1 W2 W3 W4 W5 M.C
%
Average
%
1 65.190 64.890 21.970 42.920 0.300 0.699
0.770 2 76.560 76.110 19.970 56.540 0.450 0.796
3 72.040 71.620 20.540 51.080 0.420 0.822

92


4.1.4 Loss on Ignition (LOI)
Table 4.4: LOI result for BD-NP
OXIDE % By weight Average
Lab CLSESR
9.36
LOI 9.95 8.77

4.1.5 Graded sand
Table 4.5: Standard sand sample (1)
Sieve size (mm) Retained weight
(gm)
Retained % Passing %
1.180 0.0 0.0 100.0
0.850 0.0 0.0 100.0
0.600 12.0 4.0 96.0
0.425 93.7 31.3 68.7
0.300 219.5 73.2 26.8
0.150 293.6 97.9 2.1
Pan 300.1 100 0.0

Table 4.6: Standard sand sample (2)
Sieve size (mm) Retained weight
(gm)
Retained % Passing %
1.180 0.0 0.0 100.0
0.850 0.0 0.0 100.0
0.600 8.7 2.9 97.1
0.425 89.1 29.9 70.1
0.300 215.4 72.0 28.0
0.150 290.8 97.8 2.2
Pan 298.5 100.0 0.0

93

Table 4.7; Standard sand sample (3)
Sieve size (mm) Retained weight
(gm)
Retained % Passing %
1.180 0.0 0.0 100.0
0.850 0.0 0.0 100.0
0.600 6.3 3.0 97.0
0.425 82.3 28.0 72.0
0.300 213.5 72.0 28.0
0.150 294.2 98.7 1.3
Pan 298.2 100.0 0.0

4.1.6 Chemical compositions
Chemical compositions of BD-NP were analyzed at the chemical
laboratory of university of Khartoum, faculty of civil engineering, other
sample was analyzed at CLSESR. The average of the results are shown in
Table 4.8.
Table 4.8: Chemical composition for BD-NP
OXIDE % by weight
S 65.400
A 12.700
F 7.480
C 1.970
M 0.420
K 0.140
N 0.110
0.065

94

4.2 Results of test on binder 80% OPC: 20% BD-NP
and its mortar
4.2.1 Pozzolanic activity test
To assess the pozzolanicity of the sample the concentrations of OH
-
and
Ca
+2
(expressed as calcium oxide) in the solution was plotted as standard
curve on Figure 4.2 It represented by the solid line shows the saturation
concentration of Ca
+2
(expressed as calcium oxide) as a function of OH
-
concentration at 40 C. The curve in Figure 4.1 may be expressed
mathematically in the range 45 mmol/l to 90mmol/l [OH
-
] by
[CaO] = 350 / ([OH
-
] 15) (eq.1)
Where the Ca
+2
(expressed as calcium oxide) and OH
-
concentrations are
given in mill moles per liter.
The cement satisfies the test for pozzolanicity when the point plotted is
below the curve of Ca
+2
saturation concentrations i.e. in Zone 1 as shown
on Figure 4.2.


Figure 4.1 : Diagram for assessing pozzolanicity showing individual
tested samples.
95



Figure 4.2: Diagram for assessing pozzolanicity showing average of
tested samples.
Key
1 Pass
2 Fail
X axis OH
-
concentration, mmol/l
Y axisCa
+2
concentration (expressed as CaO), mmol/l

4.2.2 Hydraulic Cement Mortar Flow&Water Requirement
Table 4.9: Mix proportions and Results of Mortar Flow Test for OPC
(CONTROL):

Mix Constituents (gm)


Water/Binder
Ratio

Diameter (cm)

Flow
(%)

Average
Flow
(%) Standard
Sand
OPC BD-
NP
Water* Original Spread
1375 500 0 275 0.55 10 12.3 23
27.25
1375 500 0 275 0.55 10 12.7 27
1375 500 0 275 0.55 10 13.2 32
1375 500 0 275 0.55 10 12.7 27

96

Table 4.10: Mix proportions and Results of Mortar Flow Test for BD-NP:

Mix Constituents (gm)


Water/Binder
Ratio

Diameter (cm)

Flow
(%)

Average
Flow (%)
Standard
Sand
OPC BD-
NP
Water* Original Spread
1375 400 100 288 0.576 10 13.2 32
29.3 1375 400 100 283 0.566 10 12.8 28
1375 400 100 280.5 0.561 10 12.8 28

*2% is maximum absorption ratio according to Satti (2013). But 2.4% of
Sand weight was added to the volume of water of all specimens to get
minimum flow consistence of BD-NP mortars according to Azizan &
Riahi (2014).










97

4.2.3 Compressive strength & Strength activity Index
The results of compressive strength and strength Activity Index of cast
707070 mm mortar cubes is shown in Tables 4.11 with OPC: BD-NP
replacement ratio 80:20. All mortar cubes were cured in saturated lime
water.
Table 4.11: Compressive strength and SAI of cast mortar cubes
Age
Days
Type Weight
(gm)
Load
(KN)
Compressive
Strength (Mpa)
Average
Compressive
Strength
(Mpa)
SAI
765 105 21.43
21.91

1.0 OPC 768 112 22.86
764 105 21.43
3 717 81 16.53
16.73

0.76 80%OPC-
20%BD-
NP
749 85 17.35
738 80 16.32
773 125.4 25.6
26.9

1.0 OPC 762.1 136.2 27.8
750 134.3 27.4
7 759 121 24.7
23.74

0.88 80%OPC-
20%BD-
NP
762 117 23.88
752 111 22.65
785 142 28.98
32.96

1.0 OPC 795 183 37.3
798 160 32.6
28 768.5 132.2 27
27.1

0.82 80%OPC-
20%BD-
NP
777.2 139.2 28.4
769.6 127.3 26
797.6 180 36.7
41.3

1.0 OPC 782.6 217 44.3
812.1 210 42.9
91 767.1 179 36.5
36.2

0.88 80%OPC-
20%BD-
NP
786.8 177 36.1
778.7 176 35.9

98



Figure 4.3: Development of compressive strength with age.

4.3 Discussion

4.3.1 Fineness
Table 4.1 shows that BD-NP specimens passed the criteria specified by
ASTM C618-99 for fineness. BD-NP returned on sieve 325 (45m) was
12.4% witch is lesser than 34%. The great surface area the more
pozzolanic reactivity.
4.3.2 Specific gravity
Table 4.2 shows that average SG for BD-NP is 2.409.
4.3.3 Moisture content
As shown in Table 4.3 BD-NP passed the criteria specified by ASTM
C618 for all classes F, C and N. Where they all state that the maximum
value of moisture content is 3%, and BD-NP sample produced 0.77%.

0
5
10
15
20
25
30
35
40
45
1 10 100
OPC-control
80%OPC:20%BD-NP
Age (Days) Log Scale
S
t
r
e
n
g
t
h

(
N
/
m
m
2
)


99

4.3.4Chemical Compositions
As shown in Table 4.8BD-NPpassed the criteria specified by ASTM C
618 for the S+A+F modulus for class N, F& C, its value is 85.58 which is
greater than 70. It also has low C content and notably low S content.

Table 4.12: Comparison of BD-NP chemical components with other
Natural Pozzolana
OXIDE Sudanese Natural Pozzolana
BD-
NP
NPBA Beyuda
Pumice
Beyuda
V.Tuffs
KVA MVA
S 65.4 40.31 51.89 56.4 63.1 56.5
A 12.7 12.44 10.13 9.12 15.3 15.5
F 7.48 12.74 9.67 7.61 5.33 4.33
C 1.97 5.31 7.79 6.63 0.864 2.22
M 0.42 9.35 6.63 6.41 0.291 0.652
K 0.14 0.70 1.06 1.08 5.23 3.9
N 0.11 4.29 0.19 0.82 2.35 4.3
0.065 0.015 0.424 0.424 0.022 ---
LOI 9.36 8.74 11.4 10.8 2.2 6.6

Table 4.12 compares the chemical composition of BD-NP used in this
research with those of other volcanic ashes from Beyouda desert (NBPA,
Beyouda pumice, Beyouda volcanic tuffs) and from Jebel Marra area
(KVA & MVA). It shows that the BD-NP had the higher silica among
them. The S+A+F modulus of BD-NP was found to be 85.58% which is
the greater and that indicates high pozzolanic activity.
The other chemical compositions show convergent results.
100

4.3.5 Loss on Ignition (LOI)
As far as LOI specification is concerned, Table 4.4 showed that the
specimens satisfied class N specification LOI <10.

4.3.6 Pozzolanic activity test
Figure 4.1 shows that the tested 80% OPC: 20% BD-NP specimen passed
according to EN 196-5 and gave positive results and showed pozzolanic
activity.
As mentioned before EN 196-5 only provides CH solubility data at40C
when [OH-] is between 35 and 90 mmol l/1. However, this is a sufficient
range to be applied to the results in Fig 4.1. Between35 and 90mmol/l
[OH-], the theoretical maximum [CaO] concentration can be calculated
using the formula below:
Max.[CaO]= 350/([OH] 15)

Table 4.13: Eight days Pozzolanic activity tests result.
Material [OH] mmol/l [CaO]mmol/l Theoretical
max.[CaO]
mmol
[CaO]
reduction %
OPC 80%+
BD-NP 20%
51.67 2.1 9.54 77.98

In this way the sample calcium concentration [CaO] may becompared to
the theoretical maximum [CaO] and the result quantified as the difference
between the two values. Finally, this is expressed as a percentage of the
theoretical maximum removed, as shown in table 4.13
101

These result shows that pozzolanic activity of BD-NP is very high with
77.98 % lime removal. Only in eight day, that indicates to high [CaO]
reduction % in 28 days and so greater pozzolanic activity.


4.3.7 Mortar flow & water requirement

Tables 4.9-4.10 shows results of flow hydraulic cement and water/binder
ratios were tried.
The chosen water/binder ratio for (SAI) is 0.5 that gives flow 28% with
difference equal 0.75% of control mix Average flow which acceptable
percentage ( 5%) according to ASTM C1437.
The mixture specimens need water more than control specimens, to give
the same workability. That means increase voids and reduce compressive
strength but additions can used to avoid it.
4.3.8 Compressive strength & Strength activity Index

The results in Tables 4.11 were plotted in Figures 4.4 to 4.7.
Figure 4.4 shows that BD-NP sample have strength activity indices
(SAIs) with OPC of 76%.
Figure 4.5 shows that BD-NP sample have strength activity indices
(SAIs) with OPC of 88% that satisfied ASTM C 618-99 standard for 7
days.
Figure 4.6 shows that BD-NP sample have strength activity indices
(SAIs) with OPC of 82% satisfied ASTM C 618-99 standard for 28 days.
102

Figure 4.7 shows that BD-NP sample have strength activity indices
(SAIs) with OPC of 88% satisfied BS EN 450-1 standard for 91 days.

Figure 4.4: Strength and strength activity index (SAI) for 80%OPC:
20%BD-NP mortars in 3 days


Figure 4.5: Strength and strength activity index (SAI) for 80%OPC:
20%BD-NP mortars in 7 days.
Ratio=1
Ratio=0.76
0
5
10
15
20
25
OPC BD-NP
S
t
r
e
n
g
t
h

(
M
P
a
)

Ratio=1
Ratio=0.88
22
22.5
23
23.5
24
24.5
25
25.5
26
26.5
27
27.5
OPC BD-NP
S
t
r
e
n
g
t
h

(
M
P
a
)

103



Figure 4.6: Strength and strength activity index (SAI) for 80%OPC:
20%BD-NP mortars in 28 days.


Figure 4.7: Strength and strength activity index (SAI) for 80%OPC:
20%BD-NP mortars in 91 days.

Ratio=1
Ratio=0.82
0
5
10
15
20
25
30
35
OPC BD-NP
S
t
r
e
n
g
t
h

(
M
P
a
)

Ratio=1
Ratio=0.88
33
34
35
36
37
38
39
40
41
42
OPC BD-NP
S
t
r
e
n
g
t
h

(
M
P
a
)

104



Figure 4.8: Comparison between Compressive strength of mortars made
with OPC+ NP from Sudan & abroad.

Compressive strength of natural zeolite the highest in all test results of
different pozzolana types abroad, due to low water/binder ratio (0.3) and
high content of S (72.03%) in chemical compositions comparison with
other types , it is an indication of high pozzolanic reactivity. The
replacement ratio of OPC has effect in compressive strength also,
specimens with 25% replacement are greater in compressive strength than
those with 15% in lately days, although it is lower in early days because the
pozzolana become active after days of moulding.
Turkish natural pozzolana (TNP) came second in compressive strength
with water/binder ratio 0.355, it is greater than BD-NP, NPBA water/binder
ratio. TNP has content of S (65.3%) considered equal to BD-NP. NPBA&
BD-NP results in 90 days compressive strength test are close for each
other, with water/binder ratio equal 0.566 for BD-NP, 0.54 for NPBA.
0
10
20
30
40
50
60
70
80
90
100
110
120
3 Days 7 Days 28 Days 91 Days
OPC
BD-NP
NPG
NPBA
Turckish NP
Zeolite 15%
Zeolite 25%
105

BD-NP expected to get great compressive strength than achieved. One
of the main environmental conditions affected negatively on gaining
compressive strength the low room humidity (less than 90%).

4.3.9 previous study on pozzolanic activity test

Donatello, Tyrer & Cheeseman (2010) compared the pozzolanic activity
of metakaolin (MK), silica fume (SF), coal fly ash (FA) , incinerated
sewage sludge ash (ISSA) and sand by using the pozzolanic activity test
(Frattini test) and the compressive strength test, there was significant
correlation between the two tests. Donatello et al categorize Frattini test
as direct method to assess pozzolanic activity by monitoring the presence
of CH and its subsequent reduction in abundance with time as the
pozzolanic reaction proceeds, using chemical titration to determine the
dissolved Ca
2+
and OH
-
concentrations in a solution. Also classifies
compressive strength test as indirect test method measure a physical
property of a test sample that indicates the extent of pozzolanic activity.

Frattini test was done according to the procedure specified in BS EN 196-
5 in the mixture of 80 % OPC and 20% of the tested pozzolana. The
pozzolanic activity of the tested samples was measured after 8 days and
plotted on the graph shown in figure (4.9). The figure illustrate lime
solubility curve, (eq 4.1) calculated the theoretical maximum [CaO]
concentration in order to plot the curve. The results is shown in Table
(4.14)
Max. [CaO]= 350 / ( [OH] 15) (eq 4.1)

106


Figure (4.9): Frattini test results for five test pozzolans after 8 days
curing.
The results are reported in duplicate. Fig(4.9) indicates that samples
containing 80% OPC and 20% test pozzolan, FA, SF and MK show
pozzolanic activity, whereas sand and ISSA are inactive.
Table (4.14): Eight days Frattini test results for five test materials
quantified using (eq 4.1)
Material [OH-]
mmol/l
[CaO]
mmol/l
Theoretical
max.[CaO]
mmol
[CaO]
reduction %
Control 57.4 8.2 8.3 0.6
sand 53.8 9.9 9.0 -9.6
ISSA 61.3 8.1 7.6 1.6
FA 53.2 4.5 9.2 50.7
SF 53.4 11.5 17.2 33.1
MK 37.0 0.9 15.9 94.4

These results show that ISSA and sand are not pozzolanic. The negative
value of % CaO removal for sand samples was surprising as the amount
of calcium in solution appears greater than expected.
107

In theory, any solid precipitated CH crystals present should be retained on
the filter. Results above the solubility curve imply that either some
suspended CH or CSH gel has passed through the filter and/or there is
experimental error in the titration procedure. Negative results should be
normalized to 0% equivalent CaO removal. This approach shows that the
pozzolanic activity of MK is very high with 94% lime removal, FA is
considerable with 51% lime removal and SF is also active but to a
reduced extent, with 33% lime removal.

The procedure used to perform Compressive strength test was based on
BS 3892.
50 50 50 mm mortar cubes was tested after 28 days and the SAI was
calculated for all the samples.
The results are reported as averages of three replicates. The control
mortar strength was 39.9 MPa at 7 days and 49.6 MPa at 28 days. Fig
(4.10) shows that all test pozzolans cause a decrease in strength after 7
days relative to the control. After 28 days, with the exception of MK
samples, there is still a clear difference between control and test sample
strength. If the test pozzolans were completely inert, there should be a
decrease of 20% in the strength development due to the dilution effect.
However, strength is related to other factors than simply the cement
content. In particular, permeability, porosity and hydration reaction
kinetics all influence strength development. For the purposes of this
study, the sand samples are treated as an inert control and assumed as a
base line for zero pozzolanic activity. With this assumption, it may be
concluded that ISSA shows no pozzolanic activity, FA and SF show only
slight pozzolanic activity and MK shows considerable pozzolanic
activity.
108

Figure (4.10): Strength activity index of five different test materials after
7 and 28 days.

Comparison of the strength activity index (SAI) test and the Frattini test:
As both of these tests specify a percentage of pozzolan mixed with PC, it
was decided that it is best to compare identical cement replacement rates,
in this case 20%. The Frattini test results provide an insight into the likely
CH concentration in the pore solution of SAI blocks. From the Frattini
test it was evident that 20% ISSA was not sufficient to decrease the CH
solution concentration. Therefore it is not surprising that SAI blocks
containing 20% ISSA showed no additional strength development
compared to the inert control samples using sand as the test pozzolana.
For both methods, MK showed the highest activity, and it can be
concluded that the removal of CH from solution in the Frattini test at a
high level after 8 days indicates that after 28 days in the SAI test,
sufficient reaction between MK and pore solution CH occurs to form
strength providing CSH gel type phases. There is a significant
109

correlation between results from these two tests and that clarified in
figure (4.11)

Figure (4.11): Correlation between measured pozzolanic activity of five
test materials using the Frattini test and the strength activity index test.











110






CHAPTER (5)
CONCLUSIONS AND
RECOMMENDATION

111

5.1 Conclusions

1. Pumicite and volcanic ash sample of (BD-NP) was supplied from an
active quarry in Beyouda Desert.
2. BD-NP has been confirmed as a pozzolanic material capable to be used as
a cement replacement material.
3. Physical properties were assessed for BD-NP sample after grinding using
Ball mill according to ASTM C311-02 guidelines. Its fineness result was
found to be 87.6% passed on sieve No 325 (45m). The SG value was
found to be 2.409. LOI passed the criteria specified by ASTM C618-99
for class N and F.
4. Chemical analyses were carried out on the BD-NP specimens according
to ASTM C311-02 guidelines. BD-NP passed the criteria specified by
ASTM C618-99 for the S+A+F modulus for class N.
5. Pozzolanic activity test was carried out on binder made of 80% OPC:
20% BD-NP by weight according to BS EN 196-5 method. The
pozzolanicity of the sample was confirmed, showing remaining calcium
oxide concentration of 2.1 mmol/l in the filtrate of (100 ml water + 16 gm
OPC + 4gm BD-NP) compared for the theoretical 9.54 mmol/l which
indicates high pozzolanic activity.
6. The water/binder ratio of mortar with (80% OPC: 20% BD-NP) and sand
/ binder ratio of 2.75 by weight were determined using hydraulic mortar
flow test to produce equivalent flow of mortar with 100% OPC 0 BD-
NP having water/cement 0.55. This Water/binder was found to be 0.566to
prepare specimen for the compressive strength test.
7. The 7 and 28 days Strength Activity Index was found to be 0.88 and 0.82
respectively and the 91 days achieved 0.88 SAI satisfied the criteria
specified in ASTM C 618.
112


5.2 Recommendations
5.2.1 Recommendations from this study

1. BS EN 196-5 testing is very useful test and should be used to
confirm the pozzolanicity of the material.
2. To confirm the activity of the material as pozzolana we should use
the compressive strength test.
3. Avoidance of curing of mortars with 100% OPC in saturated lime
water.
4. It is recommended to use BD-NP as supplementary Cement
material is Sudan.
5.2.2 Recommendations for future studies
1. Full characterization of Sudanese Natural Pozzolana including
all tests mentioned in ASTM C 311-02 and specified in ASTM
C 618-99 including not limited to autoclave expansion, drying
shrinkage of mortar bars, air entraining admixture demand,
soundness, and control of alkali silica reaction (ASR), sulphate
resistance in moderate and high exposures.
2. Investigation of concrete containing Sudanese Natural
Pozzolana as cement replacement properties.
3. Study of financial benefits of using Sudanese Natural Pozzolana
as construction material.
4. Its preferred to use X-ray techniques besides the classical
chemical analysis, X-ray diffraction techniques gives conclusive
evidence regarding the pozzolanicity of the material.
113

5. Use BS EN 196-5 testing method to assess the pozzolanicity of
tested samples with constant OPC: Pozzolana ratio in different
ages to find the age at which the pozzolana has been fully
consumed.
6. Study on different OPC: pozzolana ratios using BS EN 196-5
testing method to asset the optimum addition ratio of pozzolana
to OPC in order to achieve the maximum strength in mortar
mixers.













114

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, ,
.
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-

118









APPENDICES


119

APPENDIX 1: ASTM C311-02 STANDARD TEST
METHODS FOR SAMPLING AND TESTING FLY
ASH OR NATURAL POZZOLANS FOR USE IN
PORTLAND-CEMENT CONCRETE



APPENDIX 2: ASTM C 618-99 STANDARD
SPECIFICATION FOR COAL FLY ASH AND
RAW OR CALCINED NATURAL POZZOLAN
FOR USE AS MINERAL ADMIXTURE IN
CONCRETE




APPENDIX 3: BS EN 196-5:2011 POZZOLANICITY
TEST FOR POZZOLANIC CEMENT