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PhD Thesis

VARIATION IN PROPERTIES OF DIFFERENT PAKISTANI


CEMENTS AND ITS EFFECT ON PROPERTIES OF
CONCRETE

Submitted by

Liaqat Ali Qureshi


(Regd. No: 02-UET-PhD-CE-04)

Supervised by

Prof. Dr. Saeed Ahmed


B.Sc. Civil Engg. (PAK)
M.Sc, Structural Engg. (U.K)
Ph.D. Structures (U.K.)

Department of Civil Engineering


Faculty of Civil & Environmental Engineering
University of Engineering & Technology
Taxila, Pakistan

April 2010
VARIATION IN PROPERTIES OF DIFFERENT PAKISTANI
CEMENTS AND ITS EFFECT ON PROPERTIES OF
CONCRETE

Liaqat Ali Qureshi


(Regd. No: 02-UET-PhD-CE-04)

A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of
Philosophy in Civil Engineering (Structural Engineering)

Approved by

External Examiners

(Lt. Col. Dr. Muhammad Naseem Baig) (Dr. Ataullah Shah)


Principal Engineer, DD & C, Project Director
E-in-C Branch, GHQ, Rawalpindi Allama Iqbal Open University, Islamabad

Internal Examiner (Thesis Supervisor)

(Prof. Dr. Saeed Ahmed)

Department of Civil engineering


Faculty of Civil & Environmental Engineering
University of Engineering & Technology
Taxila, Pakistan
This humble effort is

DEDICATED TO

MY PARENTS
(who always prayed for my success)

&

MY FAMILY
(who always encouraged me)

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ACKNOWLEDGEMENTS

All praises to almighty Allah who bestowed upon me his blessings, which enabled me to
accomplish this assignment.

 I wish to express my deepest gratitude to my supervisor, Prof. Dr. Saeed Ahmed for
his guidance, valuable suggestions, continuous encouragement and cooperation
during this task.

 I pay thanks to the members of my ‘Research Monitoring Committee’, Prof. Dr.


Abdul Razzaq (CED UET Taxila), Prof. Dr. Muhammad Ilyas (UET Lahore) and
Dr. Tariq Mahmood Zaib (PAEC Islamabad), who guided me during my PhD
studies and editing of the thesis. Their support and positive attitude always provided
a hope to complete my work.

 It is indeed an honor for me for expressing my heartiest gratitude to Prof. Dr.


Hashim Nisar (Chairman CED), Prof. Dr. M. A. Kamal (Dean) & Prof. Dr. Abdul
Razzaq (Former Chairman CED & Dean) for providing concentrated support,
conductive environment and continuous encouragement in the department.

 I will offer sincere thanks to Dr. Hafizulla Shah, Manager Quality Control D.G.
Cement Plant Dera Ghazi Khan, for his valuable and consistence guidance,
inspiration, supervision and help in various technical aspects during the course of
research work.

 I am very thankful to Mr. Mushtaq Ahmed (Manager Production Fecto Cement


Islamabad and former manager Q. C. Bestway Cement Hattar) and Mr.
Muhammad Anwar (Manager Q.C. Fecto Cement Islamabad) for providing full

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cooperation and facility in conduction of different tests in their respective
laboratories.

 I am very obliged and thankful to the higher authorities and concerned staff of the
following cement factories to extend their best cooperation in the collection of
clinkar and provide allied laboratory facilities:

1- Bestway Cement Factory Hattar, Haripur.


2- Fecto Cement Factory Sangjani Islamabad.
3- Pioneer Cement Factory Joherabad Khushab.
4- Askari Cement Factory Nizampur, Noushehra
5- DG Cement Factory Dera Ghazi Khan

 And last but not least; I feel a great sense of gratitude for my close friends Engr.
Jahangeer Munir, Engr. Imran Maqbool, Engr. Usman Rasool, Engr. Tahir Sultan
and Engr. Riaz Akhtar who persistently prayed for my success and provided moral
support during the course of my PhD work. I heartily acknowledge their love &
affection and in turn pray for their success in every field of life.

(AUTHOR)

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ABSTRACT

This research work pertains to study the impact of variations in characteristics of various brands
of cement available in Pakistan on the properties of concrete namely, the workability and
compressive strength. The main aim was to study the trends of cement using indigenous raw
materials and its effect on resulting concrete. Fineness/Blaine values were considered as the key
property of cement and its effect on properties of concrete and other cement properties was
investigated. Fineness of cement has substantial effect on the properties of fresh and hardened
concrete. It is an established fact that the finenesses of Portland cements have increased during
the past 50 years and are continuing to increase. Various researchers conducted detailed
investigations on the effect of fineness of cement on properties of concrete. Fineness/blaine
values were varied by grinding cement clinker with gypsum at laboratory ball mill level and its
effect on properties of mortar and concrete was observed. In order to generalize the result,
investigation was conducted and averaged over five cement factories. Fresh cement clinker
collected from selected batch of each factory was ground with 4% gypsum in a laboratory ball
mill. During grinding, fineness was periodically measured using Blaine’s air permeability
apparatus. In this way, six cement samples with different fineness values were prepared from
each factory. In order to confirm uniformity of their oxide ratios, chemical composition of
sample was analyzed by XRF-Cement Spectrometer. Grinding time for each sample was
recorded by the built-in timer of ball mills. A comprehensive testing was carried out on cement
samples prepared in this way.

Comparisons were made between (a) fineness of cement versus consistency, setting time and
compressive strength of cement, (b) slump and compressive strength of concrete, (c) Heat of
hydration and TG loss measured by DTA/TGA tests and (d) grinding time utilized in preparation
of samples in the laboratory ball mill to make relative study of cost of grinding against desirable
properties of mortar & concrete at higher fineness levels. The consistency of cement as well as
compressive strength of mortar cubes and concrete increase while setting time decreases with
increasing fineness of cement. The results obtained are well in accordance with the previous

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published data made on foreign cements. A fineness of 3200 cm2/g has been recommended as
optimum value. Up to this value, increase in strength is more and grinding cost is less. However,
after this value, grinding cost increases while rate of gain of strength ceases. However, an
interesting pattern was noted regarding fineness versus workability for samples from almost all
the sources. Workability of concrete increases with fineness up to 2500 cm2/g then it remains
constant for fineness up to about 3200 cm2/g. Afterwards it again starts increasing. In the case of
projects where high workability is needed, fineness may be raised above 3400 cm2/g but keeping
in mind that it is involved with high grinding cost, thus, making cement uneconomical. So, other
techniques e.g., use of admixtures to improve workability, may be more economical.

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TABLE OF CONTENTS

CHAPTER DESCRIPTION PAGE


NO NO
1 INTRODUCTION 1
1.1 Background to research 2
1.2 Pakistan’s cement industry 3
1.3 Aims and objectives of the research 5
1.4 Scope of the research work 6
1.5 Methodology/Programme 7
1.6 Outline of the thesis 8
LITERATURE REVIEW 9
2 2.1 Introduction 10
2.1.1 Cement manufacturing process 11
2.2 Types of Portland cement 14
2.3 Physical properties of Portland cement 17
2.3.1 Fineness of cement 18
2.3.2 Specific gravity 18
2.3.3 Soundness 18
2.3.4 Standard consistency 19
2.3.5 Setting time 19
2.3.6 Compressive strength 20
2.4 Chemical composition of Portland cement 20
2.5 Variation in cement properties 22
2.6 Effect of cement fineness on concrete properties 23
2.7 Hydration of cement 25
2.7.1 Significance 25
2.7.2 Mechanism of hydration 25
2.7.3 Hydration of aluminate phases 26

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2.7.4 Hydration of silicate phases 30
2.7.5 DTA and TGA Techniques 33
2.7.6 Water Removal Techniques to Stop Hydration 36
2.8 Heat of hydration 38
2.9 Effect of cement variations on workability of concrete 39
2.10 Effect of cement variations on compressive strength 40
2.11 Deterioration of cement with storage 42
2.12 Portland cement concrete – general 43
2.12.1 Water 44
2.12.2 Aggregate 46
2.13 Properties of fresh concrete 51
2.13.1 Workability 51
2.13.2 Compaction 53
2.13.3 Segregation 54
2.13.4 Bleeding 54
2.13.5 Effects of admixtures 55
2.14 Strength of hardened concrete 55
2.15 Durability of hardened concrete 58
2.16 Previous research 61
2.17 Concluding remarks 65
3 EXPERIMENTAL PROGRAMME 66
3.1 Introduction 67
3.2 Preparation of test samples 67
3.3 Flowchart of the program of investigation 68
3.4 Testing for physical properties of cement 69
3.4.1 Fineness 69
3.4.2 Standard consistency 70
3.4.3 Setting time 71
3.4.4 Soundness 72
3.4.5 Compressive strength 73

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3.5 Testing for chemical and compound composition of cement 73
3.6 Testing for hydration of cement 73
3.6.1 Heat of hydration 74
3.6.2 Thermal analysis 74
3.7 Testing on concrete 75
3.7.1 Materials used 76
3.7.2 Mix proportions 77
3.7.3 Workability of concrete 77
3.7.4 Compressive strength 79
4 RESULTS AND DISCUSSION 80
4.1 Introduction 81
4.2 Variation in physical properties of cement 82
4.2.1 Relationship between fineness and standard 82
consistence
4.2.2 Relationship between fineness and setting time 90
4.2.3 Relationship between fineness and compressive 100
strength
4.3 Variation in chemical and compound composition of cement 107

4.4 Effect of variation in fineness of cement on properties of 109


concrete
4.4.1 Workability 110
4.4.2 Compressive strength 114
4.5 Grinding time for samples in laboratory ball mill 121
4.6 Heat of hydration 123
4.7 Hydration studies (DTA/TGA Tests) 124
4.8 Comparison of plant collected versus laboratory ground 132
samples
5 CONCLUSIONS AND RECOMMENDATION 133
5.1 Conclusions 134
5.2 Recommendation 135
5.3 Recommendations for future research 136
REFERENCES 137

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LIST OF TABLES

TABLE DESCRIPTION PAGE


NO No
1.1 Historical data from 2000-2009: Pakistan’s Cement Industry. 4
2.1 Main types of cement produced around the world 15
2.3 Nature of composite cement constituents 16
2.4 Characteristics of Microsilica and Metakaolin 16
2.4 Typical composition (%) of normal, sulphate-resisting & white Portland 17
cement
2.5 The principal hydration stages of Portland cement 27
2.6 Influence of the aluminate/sulphate ratio in the solution phase on setting 29
characteristics of Portland cement pastes
2.7 Accelerating effect of gypsum on setting time, heat of hydration and 31
strength of alite
3.1 Sieve analysis of course aggregates 76
3.2 Sieve analysis of fine aggregates 77
4.1 Results of physical tests of cement samples 81
4.2 Oxide and compound composition of cement from different factories 107
4.3 Chemical composition of test samples prepared for hydration studies 108
4.4 Results of concrete testing 109
4.5 Results of 3-days heat of hydration tests on plant collected samples 123
4.6 Results of DTA/TGA tests 125
4.7 Summary of physical and chemical testing at 3-days age for plant 131
collected samples

x
LIST OF FIGURES

FIGURE DESCRIPTION PAGE


NO No
2.1 Manufacture of Portland cement. 12
2.2 Aerial view of a modern cement plant 13
2.3 Schematic diagram of DTA apparatus 35
2.4 Extrapolation procedure to determine transformation onset temperature 36
3.1 Flowchart of the program of investigation 68
3.2 Grading curve for fine aggregate 78
4.1 Relationship between fineness and standard consistency for cement 83
samples of Factory A
4.2 Relationship between fineness and standard consistency for cement 84
samples of Factory B
4.3 Relationship between fineness and standard consistency for cement 85
samples of Factory C
4.4 Relationship between fineness and standard consistency for cement 86
samples of Factory D
4.5 Relationship between fineness and standard consistency for cement 87
samples of Factory E
4.6 Relationship between fineness and standard consistency of cement 88
(comparison of results from 5 factories)
4.7 Relationship between fineness and standard consistency of cement samples 89
from 5 factories
4.8 Relationship between fineness and setting time for cement samples of 90
factory A
4.9 Relationship between fineness and setting time for cement samples of 91
factory B
4.10 Relationship between fineness and setting time for cement samples of 92
factory C
4.11 Relationship between fineness and setting time for cement samples of 93
factory D
4.12 Relationship between fineness and setting time for cement samples of 94
factory E
4.13 Relationship between fineness and initial setting time of cement 95
(comparison of results from 5 factories)
4.14 Relationship between fineness and final setting time of cement 96
(comparison of results from 5 factories)
4.15 Relationship between fineness and initial setting time of cement samples 98

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from 5 factories
4.16 Relationship between fineness and final setting time of cement samples 99
from 5 factories
4.17 Relationship between fineness and 3-days compressive strength of mortar 101
cubes (comparison of results from 5 factories)
4.18 Relationship between fineness and 3 days compressive strength of mortar 102
cubes (cement samples from 5 factories)
4.19 Relationship between fineness and 7-days compressive strength of mortar 103
cubes (comparison of results from 5 factories)
4.20 Relationship between fineness and 7 days compressive strength of mortar 104
cubes (cement samples from 5 factories)
4.21 Relationship between fineness and 28-days compressive strength of mortar 105
cubes (comparison of results from 5 factories)
4.22 Relationship between fineness and 28 days compressive strength of mortar 106
cubes (cement samples from 5 factories)
4.23 Relationship between fineness and concrete slump (comparison of results 112
from 5 factories)
4.24 Relationship between fineness and concrete slump (cement samples from 5 113
factories)
4.25 Relationship between fineness and 3-days compressive strength of concrete 115
cubes (comparison of results from 5 factories)
4.26 Relationship between fineness and 3-days compressive strength of concrete 116
cubes (cement samples from 5 factories)
4.27 Relationship between fineness and 7-days compressive strength of concrete 117
cubes (comparison of results from 5 factories)
4.28 Relationship between fineness and 7-days compressive strength of concrete 118
cubes (cement samples from 5 factories)
4.29 Relationship between fineness and 28-days compressive strength of 119
concrete cubes (comparison of results from 5 factories)
4.30 Relationship between fineness and 28-days compressive strength of 120
concrete cubes (cement samples from 5 factories)
4.31 Fineness versus grinding time for samples in laboratory ball mill 122
(comparison of results from 4 factories)
4.32 Blaine fineness values versus heat of hydration of plant collected samples 124
4.33 DTA/TGA Results – Sample blaine 3000 cm2/g 125
4.34 DTA/TGA Results – Sample blaine 3100 cm2/g 126
4.35 DTA/TGA Results – Sample blaine 3200 cm2/g 127
4.36 DTA/TGA Results – Sample blaine 3300 cm2/g 128
2
4.37 DTA/TGA Results – Sample blaine 3450 cm /g 129
4.38 Blaine fineness values versus TG loss at 3-days age 130

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NOTATIONS & ABBREVIATIONS

SCCP = State Cement Corporation of Pakistan


FY = Financial Year
CRC = Cement Research Center
CR & DI = Cement Research and Development Institute
RH = Relative Humidity
SSD = Standard Surface Dry
STA = Simultaneous Thermal Analysis
XRF = X-Ray Fluorescence
TGA = Thermo Gravimetric Analysis
DTA = Differential Thermal analysis
IST = Initial Setting Time
FST = Final Setting Time
psi = Pounds per square inch
w/c ratio = Water/Cement ratio
% = Percentage
conc. = Concrete
BS = British Standard
ASTM = American Standard for Testing Materials
EC = European Code
ACI = American Concrete Institute
in. = inch
Kg. = Kilogram
Mpa = Mega Pascals
Kcal = Kilo Calorie

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OPC = Ordinary Portland Cement
cft = cubic feet
wt. = Weight
lbs = Pounds
µVs = Micro Volts
PSDP = Public Sector Development Program

xiv
CHAPTER 1

INTRODUCTION

1
1.1 Background to research

Concrete is the most commonly used building material throughout the world. It is a mixture of
different ingredients such as cement, coarse aggregate, fine aggregate and water. The individual
properties of each ingredient have substantial influence on the properties of concrete. Out of
these ingredients, cement acts as a bonding material for other ingredients. Manufacturing of
cement consists of two main phases. First phase consists of intergrinding raw materials viz. lime,
silica, alumina and iron oxide, mixing them directly in certain proportions and blazing in a large
revolving kiln at a temperature up to about 1450 0C. The material melts and fuses into small balls
having diameter 3 to 25 mm. These balls are called clinker. In second phase, clinker is cooled
and grinding is done in large tube mills, which are kept cool by spraying water on them from
outside. While grinding the clinker, three to four percent gypsum (calcium sulphate) is added so
as to control the setting time of cement. Finely ground cement is temporarily kept in silos from
where it is drawn for packing.

Fineness of cement has great influence on the properties of plastic and set concrete. Various
researchers conducted detailed investigations on the effect of blaine fineness of cement on
properties of mortar and concrete. However, the trend of locally manufactured cements by using
indigenous materials is still an area to be investigated. It is generally believed by cement
manufacturers in Pakistan that fineness of cement increases its strength and workability. Hence
in a competititive environment, they tend to increase the fineness of cement without empirical
evidence, which leads to increase the manufacturing cost of cement and subsequent sale price.
At the same time, it has also been proved that gain in compressive strength ceases at high
fineness values. Therefore, due to increased grinding effort, manufacturing cost of cement
increases without any significant gain in compressive strength. The main aim of this research is
to optimize the relationships between grinding cost and compressive strength as well as
workability with special reference to major brands/types of cement available in Pakistan.

Keeping in view the Pakistani environment and practical importance, this work was concentrated
on influence of blaine fineness of cement on the compressive strength of mortar and concrete.
Opportunity was also taken to see this effect on workability of concrete and consistency as well

2
as setting time of cement. The optimum value of fineness recommended in this research will be
very helpful for cement factories to have a balance between desirable properties of cement and
its grinding cost. This will be helpful in economizing the construction cost and overall
construction industry in Pakistan. The research results will also help the construction
practitioners and researchers to select the appropriate level of fineness of cement for the required
workability and compressive strength at different projects and climatic conditions in Pakistan.
The comparative analysis of the fineness values of the cement proposed by various traditional
building codes and its effect in cement/concrete properties will provide useful data for future
research.

1.2 Pakistan’s cement industry

The cement industry in Pakistan has grown steadily over time. At the time of freedom in 1947,
there were only 4 cement factories with a total output of nearly 0.5 million tons. By 1972, the
number of cement factories increased to 14 and the total output also increased to 2.5 million ton
but this pace could not be continued in parallel with the country’s financial growth. Both
Government and private sectors worked on proposals to set up new factories. Following the new
policy of the Government of Pakistan, cement industry was also nationalized along other
industries in 1972 and the “State Cement Corporation of Pakistan (SCCP)” was constituted and
given the responsibility of production of cement in the country. Taking into account the high
cement demand as compared to supply, cement import was also allowed in financial year (FY)
76-77 and continued until FY 94-95. With a change in strategy of Government control over
industrial units, the nationalized cement factories were put up for privatization along with other
factories. The private sector was allowed to take over cement manufacturing. As a result, the role
of SCCP as market leader went astray gradually and at present it owns only four factories, of
which two have been closed down due to effectiveness and productivity issues. In view of the
high demand during the period of free economic policy, a number of new plants were set up and
many others introduced great extensions to increase their existing output. After FY 2002-03,
most of the cement manufacturers extended their operations and increased output. This sector has
invested about US$ 1.5 billion in scope development over the last six years. The past data of
Pakistan’s cement production from 2000-2009 is given in Table 1.1.

3
Table 1.1: Historical data from 2000-2009: Pakistan’s cement industry (Munir 2009)

July to Productio Increase Local Increase/ Exports Increase/ Total Increase/ Capacity Surplus
June n Capacity (%) Dispatches Decrease (Million Decrease Dispatches Decrease Utilization Capacity
(Million (Million (%) ton) (%) (Million (%) (%) (Million
ton) ton) ton) ton)
2000 -
15.534 -5.16 9.993 -0.04 - 0.00 9.933 -0.04 63.95 5.600
2001
2001 -
15.723 1.22 9.833 -1.01 0.107 100.00 9.940 0.06 63.22 5.783
2002

2002 -
16.321 3.81 10.980 11.66 0.430 303.60 11.410 14.80 69.91 4.911
2003
2003 -
16.936 3.77 12.545 14.25 1.160 169.52 13.705 20.11 80.92 3.231
2004
2004 -
17.909 5.75 14.788 17.88 1.565 34.95 16.353 19.33 91.32 1.555
2005
2005 -
20.955 17.01 16.907 14.33 1.505 -3.83 18.412 12.59 87.87 2.543
2006
2006 -
30.251 44.36 21.034 24.41 3.188 111.83 24.223 31.56 80.07 6.028
2007
2007 -
37.151 22.83 22.596 7.30 7.717 142.02 30.286 25.03 81.51 6.871
2008
2008 -
41.760 12.39 19.394 -14.07 11.381 47.48 30.775 1.61 73.69 10.986
2009

The cement industry in Pakistan is separated into two broad categories based on the northern and
southern regions. There are 29 cement plants registered in the country having an installed
production output of 44.07 million ton. Of these, 19 units are located in the north with an
installed production output of 35.18 million ton (80%) while 10 units are located in the south
with an installed production output of 8.89 million ton (20%). There are four foreign groups,
three army based groups and 16 private groups listed in the stock exchanges. By the end of 2010,
after extension and establishment of new units, the total annual output is expected to be around
51 million ton (Munir 2009)

Due to unavailability of sufficient funds for “Public Sector Development Program (PSDP)”
during 1990 to 2002 period, owing to political instability the average growth rate of cement
industry declined. The period from 2003 to 2009 has been a golden age for the Pakistan

4
construction and cement industry. During this period, the industry has shown tremendous
growth. The boost in the cement sector was initially due to increased construction activities in
Pakistan, reconstruction and rehabilitation of earthquaked areas, rehabilitation activities in the
neighboring Afghanistan and, later tremendous increase in exports of cement from Pakistan.

In Pakistan the “Cement Research Centre (CRC)” was established at Lahore in 1984 under the
supervision of Ministry of Production Pakistan. It was later on given the name as “Cement
Research and Development Institute (CR&DI)”. Latest equipments helpful in cement research
were imported by the institute in this regard. Qualified engineers and scientists were employed to
give latest inputs in this field to improve quality and economy in cement industry of Pakistan.
However, this institute gradually ceased its research activities in the last decade of 20th century
when cement industry was gradually switched from state control to private sector. Currently, this
institute has practically no contribution in the research activities of cement industry. Most of the
staff has left the institute and costly equipment purchased at that time has become out of order
and thus obsolete.

Due to lack of research and development activities in the cement manufacturing industry of
Pakistan in one hand and shortage of qualified material scientists on the other hand, very little
research has been carried out on the use of indigenous materials as cement substitutes. This
research will help in filling this knowledge gap at local level.

1.3 Aims and objectives of the research

1. To investigate the variation in physical properties of cement from different factories in


Pakistan;
2. To study the variation in chemical and compound composition of cement from different
factories in Pakistan; and
3. To evaluate the influence of variation in chemical and compound composition of cement
on workability and compressive strength of concrete.
4. To compare the fineness of cement from selected factories with the range specified by
various building codes around the world and its relative merits and demerits.

5
5. To recommend the appropriate level of cement fineness for the desired workability and
compressive strengths of concrete for various projects and climatic conditions.
6. The reduction in production cost of cement due to optimized study regarding clinker
grinding.

This study is limited to the investigation of the effects of variation on workability and
compressive strength of concrete cast by cements from selected factories. However, it is
important to study other physical properties namely, dimensional stability and transport
properties of concrete. It also necessary to evaluate the durability properties of concrete
containing cement from different sources. Nevertheless, findings from this research should
provide a strategy to consider cement from different factories in concrete production, but it is not
intended that the findings are applied to each factory without considering the variability of the
cement.

1.4 Scope of the research work

The scope of work involves preparation of cement samples with different fineness values by
laboratory grinding of clinkers collected from different cement factories and ultimately
conduction of the following tests:

(a) Cement Tests


i. Chemical composition determination by XRF-cement spectroscopy.
ii. TGA/DTA tests
iii. Heat of hydration
iv. Setting time
v. Consistency
vi. Compressive strength of mortar cubes

(b) Concrete Tests


i. Sieve analysis of coarse aggregate
ii. Sieve analysis of fine aggregate

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iii. Slump test
iv. Compressive strength of concrete cubes

1.5 Methodology/Program

Research work was conducted in two phases. In first phase, clinker was collected from selected
batches of the following five factory:

1- Bestway Cement Factory Hattar, Haripur.


2- Fecto Cement Factory Sangjani Islamabad.
3- Pioneer Cement Factory Joherabad Khushab.
4- Askari Cement Factory Nizampur, Noushehra
5- DG Cement Factory Dera Ghazi Khan

In order to avoid any impact on their business interests and fulfill the requisite research ethics,
these factories have been randomly named as A, B, C, D, and E. Samples of different
blaine/fineness values were prepared from clinkers collected from these factories and physical
and chemical tests already mentioned in section 1.4 were performed. Methods of preparation of
samples for different tests are explained in detail in Chapter 3 and results, thus, obtained are
presented, analyzed and discussed in detail in Chapter 4.

In second phase of research work, the trend of increase in compressive strength of mortar &
concrete cubes with increasing blaine/fineness was further explored by collecting samples of five
different practical blaine values, directly from sampling point of the grinding mill of an industrial
plant. After performing routine physical tests, hydration studies were carried out with the help of
DTA/TGA tests on the pastes prepared from plant collected samples. Heat of hydration for
samples was also measured. Again method of preparation of samples for DTA/TGA tests is
explained in detail in Chapter 3 and results, thus, obtained are presented, analyzed and discussed
in detail in Chapter 4. The samples collected from industrial plant augmented our studies done on
laboratory prepared samples in phase one.

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1.6 Outline of the thesis

The second chapter of the thesis is on literature review. In this chapter, the manufacturing
process of cement, chemical and compound composition of cement and hydration of cement
reported in the literature are reviewed, in order to achieve a good understanding of the
background information on cement. The properties of concrete (workability and compressive
strength) are also reviewed in this chapter.

The third chapter introduces various stages of the experimental program and describes the test
methods/techniques used during the course of this research. Detailed description of the methods
adopted in preparing the test samples including casting, curing and conditioning of samples are
also described in this chapter.

In the fourth chapter, the results have been discussed. This is done under three headings:
(i) Variation in physical properties of cement, (ii) Variation in chemical and compound
composition of cement and (iii) Effect of variation in cement on properties of concrete.

The fifth chapter draws together the main conclusions from this research work and gives
recommendations for future research.

8
Chapter 2

LITERATURE REVIEW
 

9
2.1 Introduction

Concrete is the most widely used building material now-a-days. Its properties greatly depend on
the proportions and properties of its constituents. As cement is the major component of concrete
and usually has relatively low unit cost, the selection of its proper type and use has vital
importance in obtaining the balance of its desired properties in most economical way for any
particular concrete mix. Type I/II Portland cements, which can provide sufficient levels of
strength and durability, are the most common cements used by concrete users. However, some
situations require the use of special cements to provide advanced levels of properties. For
example, the need for high-early strength cements in pavement repairs and the use of blended
cements in hostile environments with aggregates subjected to alkali-aggregate reactions are
examples of such situations. The selection involves the exact knowledge of the connection
between cement and performance required and, in particular, between kind of cement and either
strength or durability or both the properties of concrete.

ASTM C 150 defines Portland cement as "hydraulic cement (cement that not only hardens by
reacting with water but also forms a water-resistant product) produced by pulverizing clinkers
consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms
of calcium sulphate as an inter ground addition." Clinkers are small balls (diameters, 5-25 mm)
of a fused material that is formed when a raw mixture of prearranged composition is heated to
very high temperatures. The low cost and common availability of the limestone, shale and other
naturally occurring raw materials make Portland cement one of the most economical materials
extensively used over the previous century throughout the world. Concrete becomes one of the
most adaptable construction materials available in the world. The production and composition of
Portland cements, its hydration processes, and its chemical and physical properties have been
frequently studied and researched, with numerous reports and papers written on all aspects of
these properties.

10
2.1.1 Cement manufacturing process

Since calcium silicates are the primary constituents of Portland cement, the raw material for the
production of cement must provide calcium and silica in suitable forms and proportions.
Naturally occurring calcium carbonate materials such as limestone, chalk, marl, and sea-shells
are the common industrial sources of calcium, but clay or dolomite (CaCO3.MgCO3) are usually
present as impurities. Clays and shales, rather than quartz, are the preferred sources of additional
silica in the raw-mix for making calcium silicates because quartizitic silica does not react easily
with lime.

Clay minerals contain alumina (Al2O3), iron oxide (Fe2O3), and alkalies. The presence of
aluminum, iron and magnesium ions, and alkalies in the raw mix has a mineralizing effect on the
formation of calcium silicates; that is, they facilitate the formation of the calcium silicate at
considerably lower temperatures than would otherwise be possible. Therefore, when sufficient
amounts of iron and alumina minerals are not present in the primary raw materials, these are
purposely incorporated into the raw mix through addition of secondary materials such as bauxite
and iron ore. As a result, besides the calcium silicate compounds, the Portland cement clinker
also contains aluminates and aluminoferrites of calcium (Mehta & Monteiro 1993). To facilitate
the formation of the desired compounds in Portland cement clinker it is necessary to homogenize
the raw-mix before heat treatment. That is why the materials are subjected to a series of crushing,
grinding, and blending operations. From chemical analyses of the stockpiled materials, their
individual proportions are determined by the compound composition desired in the clinker; the
proportioned raw materials usually inter ground in ball or roller mills to particles below 75 m.

In the wet process of cement manufacture, the grinding and homogenization of the raw mix is
carried out in the form of slurry containing 30 to 40 percent water. Modern cement plants favors
the dry process, which is more energy efficient than the wet process because the water in the
slurry must be evaporated before clinkering. For the clinkering operation, the dry-process kilns
equipped with multi-stage suspension pre-heaters, which permit efficient heat exchange between
hot gages and the raw-mix, require a fossil-fuel energy input on the order of 800 kcal/kg of
clinker compared to about 1400 kcal/kg for the wet-process kilns. Figure 2.1 shows a simplified

11
Figure 2.1 Manufacture of Portland cement.

12
flow diag
gram of the wet & dry processes
p fo
or Portland ccement manuufacture. Ann aerial view
w of a
modern cement
c plantt is shown in
n Figure 2.2.

Figure 2.2 Aerial vieew of a moddern cement pplant

mical reactio
The chem on taking plaace in the cem
ment kiln maay be expresssed as follow
ws:

Limesstone CaO
O + CO2 ------------------ ((2.1)
Clay SiO2 + Al2O3 + Fe2O3 ------- ((2.2)

3CaaO. SiO2
Clay + Limestone 2CaaO. SiO2 ------------------- ((2.3)
3CaaO. Al2O3
3CaaO. Al2O3.Fee2O3

n the Portlaand cement manufacturiing process consists off pulverizingg the


The finaal process in
clinker to
o an averagee particle beetween 10 an
nd 15 µm. T
The operation is carried out in ball m
mills,

13
also called finish mills. Approximately 5 percent gypsum or calcium sulfate is usually inter
ground with clinker in order to control the early setting and hardening behavior of the cement.

2.2 Types of Portland cement

Different types of Portland cement are manufactured to meet up various physical and chemical
needs for definite purposes, such as durability and high-early strength. In order to facilitate the
discussion, a list of various generic types of Portland cement produced around the world is
summarised in Table 2.1. It is to be noted that the descriptions given in this Table are very
general and National Standards may have specific limits for the contents of constituents and
there may be several different ‘sub-types’ of cement with different levels of pulverised fuel ash
and ground granulated blast-furnace slag and mixes of slag, pulverised fuel ash and limestone
powder.

The composite cements are those in which a proportion of the Portland clinker is replaced by
industrial by-products, such as “Ground Granulated Blast-Furnace Slag (GGBS)” and pulverised
fuel ash (pfa, also known as fly ash), certain types of volcanic materials (natural pozzolans) or
limestone. Table 2.2 gives the characteristics of the constituents of composite cements. In
addition, microsilica (MS) and metakaolin (MK) are also used as supplementary cementitious
material in concrete to improve various physical and durability properties of concrete. The
characteristics of MS and MK are summarized in Table 2.3.

14
Table 2.1 Main types of cement produced around the world (Shetty 1982)

BS EN
Type Designation Constituents Applications
notation
Normal Pure CEM I Clinker and calcium All types of
Portland cement sulphate construction except
those exposed to
sulphate exposure.
Sulphate- Pure BS EN Low C3A clinker and Concrete exposed to
resisting 197-4 calcium sulphate sulphate attack.
Portland cement
Pure CEM I Special low iron Architectural finishes.
White Portland
content clinker and
cement
calcium sulphate
Portland Composite CEM II Clinker, pulverised All types of
pulverised fuel fuel ash and calcium construction, where
ash cement sulphate concrete is required to
have improved sulphate
resistance and
protection against
alkali-silica reaction,
mass concrete.
Portland slag Composite CEM III Clinker, granulated All types of
cement blast-furnace slag and construction, where
calcium sulphate concrete is required to
have improved sulphate
resistance and
protection against
alkali-silica reaction,
mass concrete.
Portland Composite CEM II Clinker, limestone and All types of
limestone calcium sulphate construction.
cement
Pozzolanic Composite CEM II Clinker, natural All types of
cement pozzolan and calcium construction,
sulphate particularly where
concrete is to improve
the durability.
Masonry Composite BS EN Clinker, limestone and Brickwork, blockwork
cement 413-10 air-entraining agent and rendering.

15
Table 2.2 Nature of composite cement constituents (Newman & Choe 2003)

Constituents Natural pozzolan Pfa Ggbs Limestone


Reaction type Pozzolanic Latently Hydration
hydraulic modifier
SiO2 (%) 60-75 38-64 30-37 3
Al2O3 (%) 10-20 20-36 9-17 0.5
Fe2O3 (%) 1-10 4-18 0.2-2 0.5
CaO (%) 1-5 1-10 34-45 51
MgO (%) 0.2-2 0.5-2 4-13 2
SO3 (%) <1 0.3-2.5 0.05-0.2 0.3
Na2O (%) 0.5-4 0.2-1.5 0.2-1 0.2
K2O (%) 1-6 04-4 0.3-1 0.1
Loss of ignition (%) 2-12 2-7 0.02-1 42
Specific gravity 2.30-2.80 2.30 2.90 2.70
Specific surface area 300-600 300-600 300-500 400-900
(m²/kg)

Table 2.3 Characteristics of Microsilica and Metakaolin (Newman & Choe 2003)

Oxides (%) Microsilica Metakaolin


SiO2 92.0 52.1
Al2O3 0.70 41.0
Fe2O3 1.23 4.3
CaO 0.30 0.09
MgO 0.21 1.4
SO3 0.33 -
Na2O 1.23 0.01
K2O 0.82 0.62
Loss of ignition 3.18 0.48
Specific gravity 2.20 2.40
Specific surface area (m²/kg) 15000-20000 12000-15000

16
The mineralogical composition of cement used in special purposes varies, as can be seen from
Table 2.4. In this table, the typical chemical composition of normal, sulphate resisting and white
Portland cements is summarised.

Table 2.4 Typical composition (%) of normal, sulphate-resisting & white Portland
cement ((Newman & Choe 2003)

Normal Sulphate-resisting White

SiO2 20.4 20.3 24.6


Insoluble residue 0.6 0.4 0.07
Al2O3 5.1 3.6 1.9
Fe2O3 2.9 5.1 0.3
CaO 64.8 64.3 69.1
MgO 1.3 2.1 0.55
SO3 2.7 2.2 2.1
Na2O 0.11 0.10 0.14
K2O 0.77 0.50 0.02
Loss of ignition 1.3 1.3 0.85
Free lime % 1.5 2.0 2.3
LSF % 96.6 97.3 95
SR % 2.55 2.33 11.2
AR % 1.76 0.71 6.3
Calculated mineral composition
C3S 57 62 67
C2S 16 12 20
C3A 9 0.9 4.5
C4AF 9 16 0.9

2.3 Physical properties of Portland cement

ASTM C 150 has notified certain requirements regarding physical properties for each type of
cement. These properties comprise: (i) fineness (ii) specific gravity (iii) soundness, (iv) standard
consistence, (v) setting time, (vi) compressive strength, (vii) heat of hydration and (viii) loss of
ignition. All of these properties have an effect on the functioning of cement in concrete. Out of
these properties only those which are important are discussed in the following section.

17
2.3.1 Fineness of cement

Fineness of cement is the total surface area of cement grains available for hydration. It
determines the level of grinding of cement clinker in grinding mill of plant and affects the rate of
hydration. Greater the fineness more is the surface available for hydration, resulting greater early
strength and more rapid release of heat (the fineness of Type III is greater than that of Type I
cement) (U.S. Department of Transportation 1990). The Wagner Turbidimeter and the Blaine air
permeability test for determining cement fineness are both required by the American Society for
Testing Materials (ASTM) and the American Association for State Highway Transportation
Officials (AASHTO). Average value of fineness of modern cement ranges from 3,000 to 5,000
cm2/g (Higginson 1970).

2.3.2 Specific gravity

Specific gravity is not a sign of the quality of the cement, but is required for calculations during
concrete mix design. The specific gravity of Portland cement is approximately 3.15 (Neville
1995).

2.3.3 Soundness

Soundness refers to the capability of the cement paste to maintain its volume after setting, and is
associated with the existence of extreme amounts of free lime or magnesia in the cement or
supplementary cementitious material. A cement paste should not undergo a large change in
volume once it has been set. However, some expansion may occur due to gradual hydration or
due to some other reactions of some compounds there in the hardened cement, namely free lime,
magnesia and calcium sulfate. Free lime absorbs moisture and expands many times to its original
volume and develops considerable heat and thus causes disintegration of concrete in which this
cement is used. Expansion in OPC is limited to 10 mm or 0.5%.

18
It is essential that cement concrete does not undergo large changes in volume after setting. This
change in volume is known as unsoundness and may cause cracks, distortion and disintegration
of concrete. Bektas et al. (2008) investigated the effect of Portland cement fineness on the results
of ASTM C1260 tests. He concluded that mortar-bar expansion was promoted with increased
cement fineness regardless of clinker alkali, aggregate reactivity or soak solution normality.

2.3.4 Standard consistency

Consistency indicates the degree of density or stiffness of cement. Therefore, it is necessary to


determine the amount of water content for a given cement to get a mixture of required
consistency. Consistency of cement is measured by vicat apparatus. The paste is said to be of
standard consistency, when the penetration of plunger, attached to Vicat apparatus, is 33-35 mm.
The moisture content of the standard paste is written as a percentage by weight of the powdered
cement. The normal range is between 26-33%. This test precedes the test of cement for
soundness, setting time, tensile strength or for compressive strength (Neville 1995).

2.3.5 Setting Time

To enable the concrete to be laid in position properly the initial setting of cement should not start
too quickly. Once the concrete has been laid it should harden rapidly so that the structure could
be put to use early. Initial setting of cement is that step in the process of setting, after which if
any cracks appear do not reunite. Final setting is that when it has occurred, sufficient strength
and hardness is attained.

As soon as water joins the cement, it forms gel that causes the paste to stiffen. However, this
stiffening does not affect workability until initial set takes place. Thus, setting describes “The
strength of the cement paste”. Setting may also be understood as “setting refers to a
transformation from a fluid to a hard state”. During setting, the paste attains some strength. But it
is different from hardening, which refers to the increase of strength of a set cement paste.The
setting process is associated with temperature changes in the cement paste. Initial set is related to
a quick increase in temperature and final set to the highest temperature. Setting time decreases

19
with rise in temperature. Setting time of cement can be increased by adding some admixture, as
sodium carbonate. The setting time of cement is measured using vicat apparatus with different
penetrating attachments.

2.3.6 Compressive Strength

The compressive strength of concrete is one of the most important mechanical properties. In
most structural applications, concrete is employed primarily to resist the compressive forces. In
those cases where other stresses (for e.g. tensile) are of primary importance, the compressive
strength is still frequently used as a measure of the resistance because this strength is the most
convenient to measure. For the same reason, the compressive strength is generally used as a
measure of the overall quality of the concrete, when strength itself may be relatively
unimportant.

2.4 Chemical composition of Portland cement

Different types of cements are differentiated from each other on the basis of their chemical
composition. ASTM C 150 imposes the standard chemical needs for each type. AST defines the
following phase compositions in Portland cement: tricalcium silicate (C3S), dicalcium silicate
(C2S), tricalcium aluminate (C3A), and tetracalcium aluminoferrite (C4AF). However, these
phases would occur at an equilibrium state of all constituents in the mix and do not present
effects of burn temperatures, quenching, oxygen availability, and other practical kiln conditions.
The actual compounds are mostly multifaceted chemical crystalline and amorphous
compositions, named by cement chemists as "elite" (C3S), "belite" (C2S), and different forms of
aluminates (Mehta & Monteiro 1993). The performance of each type of cement depends on the
concentration of these components. Role of these compounds, their hydration behaviour, and
their effect on the behaviour of cements are given in full detail in literature. Some of the most
comprehensive references regarding the chemistry of cement consists of those written by Bogue
(1955), Taylor (1964), and Lea (1970). Various analytical methods such as X-ray diffraction and
analytical electron microscopy are used by scientists in order to explain in detail the reaction of
cement with water (hydration process) and to enhance its properties.

20
In simplest way, results of these researches have shown that early age hydration of cement is
mainly controlled by the content and action of C3A, counterbalanced by the ratio and type of
sulphate ground together with the cement. C3A hydrates very speedily and will affect early
bonding characteristics. Anomalous hydration of (C3A) and less control of this hydration by
sulphate can result in such problems as flash set, false set, slump loss, and cement-admixture
incompatibility (Previte 1977; Whiting 1981; Meyer and Perenchio 1979).

Growth of the internal structure of hydrated cement (referred to by many researchers as the
microstructure) starts after the concrete has set and continues for months (and even years) after
placing. The mechanical performance and durability of the concrete is affected by the
microstructure of the cement hydrates. In terms of cement composition, the C3S and C2S contents
will have the main effect on long term growth of structure, although aluminates may contribute
to development of compounds such as ettringite (sulfoaluminate hydrate), which can bring about
expansive disruption of concrete. Cements with high content of C3S (especially those that are ore
finely ground) will hydrate more and lead to increased early age strength. However, the
hydration products formed will, actually, make it more difficult for hydration to continue at
mature ages, resulting in an ultimate strength lower than required in some cases. Cements high in
C2S content will hydrate much more slowly, resulting in a compact final structure and a higher
long-term strength. Due to competition, the relative proportion of C3S to C2S, and the overall
fineness of cements, has been increasing over the past few decades. Indeed, Pomeroy (1989)
notes that early age strengths of concrete achieved today could not have been tested in the past
except at very low water-to-cement ratios (w/c's), which would have declared concretes
unworkable in the absence of HRWR. This aptitude to achieve required strengths at a higher
workability (and hence a higher w/c) may cause many durability problems, as it is now proved
that higher w/c consistently leads to higher permeability in the concrete (Ruettgers, Vidal, and
Wing 1935; Whiting, 1988).

One of the main aspects of cement chemistry interesting for cement users is the effect of
chemical admixtures on portland cement. Since the early 1960s most authorities have allowed or
required the use of water-reducing and other admixtures in highway pavements and structures

21
(Mielenz 1984). A broad category of chemical admixtures have been inducted in the concrete
industry over the last three decades, and civil engineers are more and more concerned about the
positive and negative influences of these admixtures on cement and concrete operations.
Substantial research concerned with admixtures has been carried out in the United States. Air-
entraining agents are extensively used in the highway industry in North America, where concrete
will have to face repeated freeze-thaw cycles. Air-entraining agents have no considerable
influence on the rate of hydration of cement or on the chemical composition of hydration
compounds (Ramachandran and Feldman 1984). However, a raise in the cement fineness or a
reduction in cement alkali content normally enhances the dose of an admixture required for a
given air content (ACI Comm. 225R 1985). Water reducers or retarders affect cement
compounds and their hydration. Lignosulfonate-based admixtures influence the hydration of
C3A, which affects the setting and early hydration of cement. C3S and C4AF hydration is also
affected by water reducers (Ramachandran and Feldman 1984). Research conclusions presented
by Polivka and Klein (1960) showed that alkali and C3A contents affect the necessary admixtures
to attain the desired mix. It looks that set retarders, for example, are more useful with cement of
low alkali and low C3A content, and that water reducers appear to enhance the compressive
strength of concrete having cements of low alkali content greater than that of the concrete having
cements of high alkali content.

2.5 Variation in cement properties

Cement has several varying properties. These are for example:

1. Composition of clinker minerals


2. Microstructure of clinker minerals
3. Amount and form of calcium sulphate
4. Amount and form of alkalies
5. Material temperature
6. Particle size gradation (fineness)
7. Particle shape

22
Until now, the most observed single property of cement has been the fineness that is expressed in
specific surface according to the Blaine method. Several tests and long time monitoring,
however, have shown that Blaine fineness is not a sufficient parameter for explaining the
variations in the properties of fresh concrete mix or early age properties of hardened concrete.
This seems to be the case especially with superplasticized mixes where superplasticizer and
cement compatibility reportedly can cause problems or at least differing workability with various
combinations.

2.6 Effect of cement fineness on concrete properties

Sufficient research has been carried out investigating the relationships between Portland cement
particle size distribution (PSD), the hydration kinetics and set cement paste strength properties
(Frigioine and Marra, 1976; Osbaeck and V. Johansen, 1989; Pommersheim, 1987; Knudsen,
1984; Wakasugi et al., 1998 and Taylor, 1997). For a specified water-to-cement (w/c) ratio, a
drop in median particle size generally outcomes in an enhanced hydration rate and, therefore,
improved early qualities such as higher early strengths. For to this, Portland cement finenesses
have normally improved over the years. However, Mehta (1997) has recommended that on
durability basis, finer cements may not always be preferred over coarser ones. Moreover, it has
freshly been pointed out that in high-performance concretes with comparatively low w/c ratios,
coarser cements may show equal long-term performance to finer cements (Bentz and Haecker,
1999), resulting in considerable economy of energy due to a decrease in grinding time. This
recommendation was based on simulation studies of the degree of hydration vs. time
performance of a collection of cements ground to different finenesses.

In common situations, cements with a greater fineness level will tend to hydrate rapidly and
result high early age strength, due to this fact, use of finer cements in the mix. design of high
early strength concrete is common, although the strength development at greater ages may be
lesser as compared to coarser cements. Moreover, finer cement causes a stronger reaction with
alkali reactive aggregate, and makes the cement, though not necessarily concrete, display a
higher shrinkage and a greater proneness to cracking (Neville, 1995)

23
According to Jaspers (1951), a given specific surface in cement could be produced with a variety
of particle-size distributions. Basically, strength and other properties of cements are functions of
the amount hydrated and initially this will be related to the specific surface rather than to particle
grading. As hydration proceeds, however, the finest particles become completely hydrated and
the surface area of the remaining anhydrous material will become progressively less related to
the original value, and more dependent on the original particle size distribution. Their work
indicates that there, at 1-day, strength is related more or less linearly to the specific surface, but
at longer ages it is influenced also by the kind of particle-size distribution. The maximum
strength at relatively short ages with a given specific surface would be produced by particles of
roughly uniform size, but this is not necessarily true at longer ages nor, in fact, could such a
gradation be produced with existing types of grinding machinery.

Celik (2009) studied the effect of particle size distribution and surface area upon strength
development of cement. He correlated variation in fineness of cement on the basis of its particle
sizes and strength of cement and concluded that fineness has a great effect on 2 days strength. At
increased ages, strength is affected more by the concentration of coarser particles as compared to
finer ones. Zhang and Napier (1995) also worked on effect of particle size distribution, chemical
composition and surface area upon strength development of cement. He correlated particle size
distribution, chemical composition and surface area and by modelling, optimized clinker
grinding by simulation modelling.

Bentz, et al. (1999) conducted research over effects of cement particle size distribution on
operational properties of Portland cement-based materials. He recommended that coarse grains
require more time to set, although they practically set at a lower degree of hydration. Their gain
in strength will go slowly than that of finer cements, also, coarser cements will show a lower
initial heat release rate. The authors also gave argument for using coarser cements as far as
development of high performance concretes is concerned. Beuselink et al., (1998) discussed
different techniques of determining particle size distribution of cements and compared their
salient features.

24
2.7 Hydration of cement

2.7.1 Significance

Anhydrous Portland cement cannot bind sand and rock; it acquires the adhesive property only
when mixed with water. This is because the chemical reaction of cement with water, commonly
referred to as the hydration of cement, yields products that process setting and hardening
characteristics. The chemistry of concrete is essentially the chemistry of the reaction between
Portland cement and water. In any chemical reaction the main features of interest are the changes
in matter, the changes in energy, and the speed of the reaction. These three aspects of a reaction
have great practical importance for the user of Portland cement. Knowledge of the substances
formed when Portland cement reacts is important because the cement itself is not a cementing
material; its hydration products have the cementing action. Knowledge of the amount of heat
released is important because the heat is sometimes a help and sometimes a hindrance.
Knowledge of reaction speed is important because it determines the time of setting and
hardening. The initial reaction must be slow enough to enable the concrete to be poured into
place. On the other hand, after the concrete has been placed rapid hardening is often desirable.

2.7.2 Mechanism of hydration

The hydration of Portland cement (PC) involves the reaction between clinker minerals, calcium
sulphate and water. Although extensive research has been conducted on the hydration of PC, the
hydration mechanism is still not fully understood. The hydration process has been
comprehensively reviewed by Taylor (1997). It is believed that the general principle of hydration
is the dissolution of anhydrous phases to the precipitation of much less soluble products,
typically colloidal and micro-crystalline hydrates which form the hardened paste (Bensted and
Barnes, 2002). The process can be divided into four consecutive periods, as summarised in
Table 2.5.

25
2.7.3 Hydration of aluminate phases

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

From the standpoint of hydration of Portland cement, it is also convenient to discuss the
hydration reactions of C3A and ferroaluminate together because when the latter reacts with water
in the presence of sulfate, the products formed are structurally similar to those formed from the
hydration of C3A. For instance, depending on the sulfate concentration, the hydration of C4AF
produces either C6A(F)S3H32 or C4A(F)SH18, which, in spite of differences in chemical
composition, have crystal structures that are similar to ettringite and low sulfate, respectively.
However, the part played by the ferroaluminate compound in the early setting and hardening
reactions of the Portland cement paste depends mainly on its chemical composition and
temperature of formation. Generally, the reactivity of the ferrite phase is somewhat slower than
C3A, but it increases with increasing alumina content and with decreasing temperature of
formation during the clinkering process. In any case, it may be noted that the hydration reaction
of the aluminates described below are applicable to both the C3A phase and the ferrite phase in
Portland cement through, for the sake of simplicity, only C3A is discussed.

Several theories have been postulated to explain the mechanism of retardation of C3A by
gypsum. According to one theory, since gypsum and alkalies go into solution quickly, the
solubility of C3A is depressed in the presence of hydroxyl, alkali, and sulfate ions. Based on the
contents of aluminate and sulfate ions in the solution, the crystalline product which is
precipitated may be either calcium aluminate trisulfate hydrate or the calcium aluminate
monosulfate hydrate. In solutions saturated with calcium and hydroxyl ions, the former
crystallizes in the form of short prismatic needles and is also known as high-sulfate or by its
mineralogical name, ettringite.

26
Table 2.5 The principal hydration stages of Portland cement
(Bensted and Barnes, 2002)
Relevance to physical
Processing stage Chemical process Physical process
properties of concrete
First minutes Rapid dissolution of Large initial bust of Rapid formation of
(wetting and free lime, sulphate heat, mainly from aluminate hydrates, plus
mixing, and aluminate dissolution of gypsum and syngenite
0-15 minutes) phase; immediate aluminate phases, influences rheology and
formation of Aft; plus some from may also affect the
superficial alite and CaO. subsequent
formation of C3S. microstructure.
Induction period Nucleation of C-S- Low heat evolution Continued formation of
(agitation, H; rapid decrease in rate; Aft and AFm phases;
transport, placing SiO2 and Al2O3 to slow formation of can influence
and finishing, very low levels; early C-S-H and workability, but it is
15-120 minutes) CH becomes more AFt leads to formation of C-S-H that
supersaturated and continuous increase usually leads to the
portlandite of viscosity. onset of normal setting.
nucleates.
Acceleration Hydration of C3S Rapid formation of Change from plastic to
period accelerates and hydrates leads to rigid consistence (initial
(setting and early reaches maximum; solidification and and final set); early
hardening, CH supersaturation decrease in strength development.
2 to 14 h) decreases. porosity;
Post-acceleration Decelerating rate of Decrease in rate of Continuous strength
period formation of C-S-H heat of evolution; increase due to
(demoulding, and portlandite continuous decreasing porosity; but
continued from both C3S and decrease in as an ever-diminishing
hardening, C2S; porosity; rate; hydration
> 20 h) Renewed hydration particle to particle continues for years if
of aluminates to and paste to water is available;
give AFm phases. aggregate bond paste will shrink due to
formation. drying.

The monosulfate is also known as low-sulfate and crystallizes in the form of thin hexagonal
plates. The pertinent chemical reactions may be written as follows:

Ettringite
[AlO4]- + 3[SO4]2- + 6[Ca]2+ + aq. C6AS3H32 -------------------- (2.4)

27
Monosulfate
[AlO4]- + [SO4]2- + 4[Ca]2+ + aq. C4ASH18 ----------------------- (2.5)

Ettringite is normally the first hydrate to be crystallized because of the high sulfate/aluminate
content in the solution stage during the first hour of hydration. In normally retarded Portland
cements, which contains 5 to 6 percent gypsum, the precipitation of the ettringite imparts
stiffening (loss of consistency), setting (solidification of the paste), and early strength
development. Then, after the exhaustion of sulfate when the proportion of aluminate ions in the
solution goes high again due to changed hydration of C3A and C4AF, ettringite becomes unstable
and is slowly converted into the monosulfate phase, which is the final product of hydration of
Portland cements containing more than 5 percent C3A:

C6AS3H32 + 2C3A + 22H 3C4ASH18 -------------------- (2.6)

Since the aluminate-to-sulfate balance in the solution phase of a hydrated Portland cement paste
primarily determines whether the setting behavior is normal or not, various setting phenomena
affected by an imbalance in the A/S ratio, which have practical significance in the concrete
construction practice, are illustrated in Table 2.6, and are discussed below (Mehta & Monteiro
1993):

Case I: When the rates of availability of the aluminate ions and the sulfate ions to the solution
phase are low, the cement paste will remain workable for about 45 min; thereafter it will start
stiffening as the water-filled space begins to get filled with ettringite crystals. Most so-called
normal-setting Portland cement belong to the category. The paste becomes less workable
between 1 and 2 h after the addition of water, and may begin to solidify within 2 to 3 h.

Case II: When the rates of availability of the aluminate ions and the sulfate ions to the solution
phase are high, large amount of ettringite form rapidly and cause a considerable loss of
consistency in 10 to 45 min, with solidification of the paste between 1 and 2 h. Freshly produced
high-C3A cements containing more than normal amounts of alkali sulfates or calcium sulfate
hemihydrate are generally characterized by this type of behaviour.

28
Case IIII: When am
mount of reaactive C3A is
i high but the soluble sulfate preesent is less than
required for normal retardation, hexagonal-p
plate crystalls of monosuulfate and caalcium alum
minate
hydrates form quicklly and in larrge amounts causing thee cement passte to set in less than 455 min
after the addition of water.
w The phenomenon
p is known ass quick set.

Case IV
V: When littlle or no gyp
psum has beeen added too a ground Portland cem
ment clinkerr, the
hydration
n of C3A is rapid and th
he hexagonaal-plate calccium aluminaate hydratess start forming in
large am
mounts soon
n after the addition
a of water, caussing almostt an instantaaneous set. This
phenomeenon, know
wn as flash
h set, is associated
a with large heat evolution and poor
w
ultimatettrength.

Tab
ble 2.6 Influence of the aluminate/ssulphate rattio in the soolution phasse on settingg
charracteristics of
o Portland cement passtes (Locherr et al. 19800)

29
Case V: When the C3A in cement is of low reactivity, as is the case in partially hydrated or
carbonated cements which have been improperly stored, and at the same time a large amount of
calcium sulfate hemihydrate is present in the cement, the solution phase will contain a low
concentration of aluminate ions but will quickly become supersaturated with respect to calcium
and sulfate ions. This situation will lead to the rapid formation of large crystals of gypsum with a
corresponding loss of consistency. The phenomenon, called false set, is not associated with large
heat evolution and can be remedied by vigorous mixing of the cement paste with or without
additional water.

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

Lea (1971) has shown that, unlike the suppression of solubility of the aluminate compounds, the
solubility of the calcium silicate compounds is actually increased in the presence of sulfate ions
in the solution phase. Typical data on the effect of gypsum addition on the strength development
rate of pure alite cements are shown in Table 2.7. In conclusion, although the primary purpose of
gypsum in Portland cement is to retard the hydration o aluminates, a side effect is the
acceleration of alite hydration without which the industrial cements would harden at a slower
rate.

2.7.4 Hydration of silicate phases

The hydration of C3S and C2S in Portland cement produces a family of calcium silicate
hydrates which are structurally similar but vary widely in calcium/silica ratio and the content of
chemically combined water.

30
Table 2.7 Accelerating effect of gypsum on setting time, heat of hydration and strength of
alite (Mehta et al. 1979)

Physical Properties Type I/II Portland Alite Cement*


Cement No gypsum 3% gypsum
Setting time (h)
Initial 3.0 8.5 4.5
Final 6.0 11.5 7.5
Heat of hydration (cal/kg)
3 days 61 59 63
7 days 75 61 66
28 days 83 85 81
Compressive strength [MPa]
3 days 13.4 8.62 11.0
7 days 21.4 14.2 16.8
28 days 34.9 26.2 27.6
90 days 36.9 36.9 37.0

Since the structure determines the properties, the compositional differences among the calcium
silicate hydrates have a little effect on their physical characteristics.

The microstructure and properties of calcium silicate hydrates formed in Portland cement pastes
were described earlier. In general, the material is poorly crystalline and forms a porous solid
which exhibits characteristics of a rigid gel. In the literature, this gel has sometimes been referred
to as tobermorite gel, after a naturally occurring mineral of seemingly similar structure. The use
of this name is no longer favoured because the similarity in crystal structures is rather poor. Also,
since the chemical composition of the calcium silicate hydrates in hydrating Portland cement
pastes varies with the water-cement ratio, temperature, and age of hydration, it has become rather
customary to refer to these hydrates simply as C-S-H, a notation that does not imply a fixed
chemical composition. On complete hydration the approximate composition of the material may
be assumed as C3S2H3; this composition is therefore used for stoichiometric calculations.

The stoichiometric reactions for fully hydrated C3S and C2S pastes can therefore be expressed as

31
2C3S + 6H C3S2H3 + 3CH ---------------------- (2.7)
2C2S + 4H C3S2H3 + CH ---------------------- (2.8)

In addition to the fact that similar reaction products are formed on hydration of both the
tricalcium silicate and the dicalcium silicate present in Portland cement, the following points
should be noted.

First, stoichiometric calculations show that the C3S hydration would produce 61% C3S2H3 and
39% calcium hydroxide, whereas the C2S hydration would produce 82% C3S2H3 18% calcium
hydroxide. As the high specific surface area and, consequently, the adhesive property of the
hydrated cement paste are essentially due to the formation of the calcium silicate hydrate, it is to
be expected that the ultimate strength of a high- C3S Portland cement would be lower than a high
C3S cement. This, indeed, is confirmed by the data from several research investigations (Lea
1971).

Second, if the durability of a hardened cement paste to acidic and sulfate waters is reduced due to
the presence of calcium hydroxide, it may be expected that a cement containing a high
proportion of C3S will be more durable to acidic and sulfate environment compared to a cement
containing a high proportion of C3S. This conclusion is also generally confirmed by laboratory
and field experience. From the standpoint of durability to chemical attacks, some cement
standards attempt to limit the maximum permissible C3S in cement, others recommend the use of
pozzolans in order to remove the excess calcium hydroxide from the hydrated cement paste.
Third, it can be calculated from the above stoichiometric equations that C3S and C2S require 24
and 21 percent water, respectively, for complete hydration.

The stoichiometric equations of C3S and C2S hydration do not tell anything about the reaction
rates. From the standpoint of instability of the crystal structure described earlier and the heat of
hydration data given below, it is apparent that C3S would hydrate at a faster rate than C2S. in the
presence of gypsum, C2S in fine particles of cement begins to hydrate within an hour of the
addition of water to cement, and thus contributes to the final time of set and the early strength of
hydrated cement paste. The relatively quicker rate of C3S hydration in finely ground Portland

32
cements has become an important factor in the production of high-early-strength Portland
cements.

2.7.5 DTA and TGA Techniques

Differential Thermal Analysis (DTA) and Thermo Gravimetric Analysis (TGA) techniques are
of great significance in cement research. DTA and TGA is not only used in identifying various
materials but also has been successfully used to follow reactions by heating the reactions
gradually to elevated temperatures. Almeida and Sicheri (2006) also performed
thermogravimetric analysis of polymer modified mortars with silica fume.
Principle:
Differential Thermal Analysis (DTA) is the analytical technique in which temperature
differential between the sample and a non-reactive reference material is monitored while the two
substances are subjected to the identical heating program. The thermal curve is a plot of the
temperature difference as a function of the temperature of one of the two substances. Normally
the temperature difference is recorded as a function of the temperature of the reference
substance. The sample and reference substance are kept in separate containers with in the same
furnace. To ensure identical heating the containers are kept close (with in 1 cm) to each other.
The reference substance is usually thermally inert throughout the temperature interval used for
the study. Alumina (Al2O3) is used as reference material. DTA can be used to study any process
in which heat is absorbed or evolved. Among the endothermic process that can be studied by
using DTA are melting, boiling and sublimation. Absorptive processes are often exothermic and
can be studied using DTA. Thermal curves obtained with DTA show peaks corresponding to
processes in which the temperature of the sample is increased or decreased relative to the
temperature of the reference substance. Upward deflections usually correspond to exothermic
reaction and downward deflections to endothermic reactions. The temperatures at which the
peaks are observed in the thermal curve can be used for qualitative analysis by comparison with
curve recorded under similar conditions with known materials. Peak areas or peak heights are
used for quantitative analysis. DTA is simpler and quicker to perform than X-ray diffraction but
suffers from several experimental limitations, of which the overlapping of adjacent peaks is
perhaps the greatest. A technique often useful for quantitative analysis is to add to the reference

33
sample different amounts of one component already identified in the test sample until the peaks
for that component disappear, indicating approximately equal amounts of that component in both
samples. This so-called double differential technique sometimes allows quantitative
identification to less than 1% or a sensitive similar to that of X-ray diffraction (Ivindra et al.
2005).

With the completion of the thermal change, the specimen usually retains the temperature of the
inert material. In some cases, the zero line shows a drift after a thermal transformation and is
attributed to the differences in characteristics between the specimen and the inert material. Metal
sample holders reduce baseline drift but the peaks in that case tend to be small because of rapid
heat transfer through the sample holder. In comparison to metal holders, ceramic holders give
larger peaks because of their lower thermal conductivity, thus permitting the same sensitive with
a smaller sample or less sensitive recording device.

Atmospheric control in the furnace is sometimes used to suppress an undesired reaction, to


enhance desired reaction or to resolve overlapping peaks by varying the pressure of a gaseous
reaction product. Rapid heating rates are claimed to have certain advantages, they certainly
enable larger peaks to be obtained with small samples, but may also have certain disadvantages.
Particle size can influence the curve and it is recommended that all specimen should pass a 100
mesh sieve. Uniform and reproducible packing of the specimen in the sample cup is essential.
Careful tempering by hand has been claimed to give reproducibility to within ± 1%. For
quantitative work, each specimen should be diluted to less than 30% with inert material.
Enhanced response can be obtained from a small specimen by placing the active material in a
thin layer around the thermocouple junction, with inert material above and below. So far as the
selection of inert material is concerned, the inert material should be of same particle size as the
material being investigated.

In thermo gravimetry, the mass of the sample is measured either as a function of temperature or
time. The plot of the mass or the percentage of the initial mass as a function of temperature or
time, is a thermal curve, generally, the mass changes are caused by loss of a volatile component,

34
such as water
w from th
he sample. The
T change in
i mass can be used for quantitativee analysis annd the
temperatu
ure at which
h the change takes place is useful forr qualitative analysis.

Apparattus (DTA an
nd TGA)
Basic DTA
D equipm
ment consistts of a furrnace, a teemperature regulator, a sample bblock,
thermoco
ouple and a temperaturee recording system. In the third caavity of the block a sepparate
thermoco
ouple is emb
bedded to measure
m the temperaturre of the specimen. Thee block with the
specimen
n is placed in
i the furnaace. Temperaature regulat
ation is accoomplished byy a motor ddriven
autotranssformer whicch controls voltage
v to the furnace wiires, which aare usually m
made of nichhrome
(to 1000oC) or platinum alloys (tto 1750oC).

Figure 2.3 Schematic diagram off DTA apparratus


The appaaratus that simultaneous
s sly heat the sample andd monitors itts mass is a thermo ballance.
Mass measurement
m ts are mad
de with a highly ssensitive m
microbalancee which iss an
electromechanical deevice.

35
xtrapolation procedure to determine transformattion onset tem
Fiigure 2.4 Ex mperature

The beam
m of the baalance is con
nstructed fro
om quartz. It is attacheed to a metaallic arm hooused
between the poles of
o an electro
omagnet. Motion
M of the balance iss detected bby observingg the
deflection
n of a high beam
b on a photosensitiv
p ve null detecctor which iss attached too the beam oof the
balance. A deflectio
on of the beam is autom
matically com
mpensated bby a changee in current flow
through the
t electrom
magnet which
h restores th
he beam to itts original pposition. Thee electrical ssignal
related to
o the mass on
n the balance and is disp
played on thee read-out deevice.

2.7.6 Water
W rem
moval techn
niques to stop
s hydraation

Hydration studies arre carried ou


ut after stopp
ping hydratiion reactionss at specifieed curing ages by
removing
g pore waterr that is avaiilable for hy
ydration reacctions in the cement passte. Four metthods
are used by research
hers all over the world: These are the solventt replacemennt of water by a
hydrophiilic organic liquid, moree commonly
y referred too as solventt replacemeent method
d, and
oven, vacuum or freeeze drying of water. However,
H eacch of these m
methods of w
water removaal has
been proved to alter the delicate microstructture of the haardened cem
ment paste annd may causse the
structural and physiccal disintegraation of som
me of the cem
ment hydratees, especiallyy ettringite (AFt),
monosulp
phate (AFm
m) and C–S–H
H, because more
m water is linked wiith these phaases. In harddened

36
cement pastes containing large amounts of AFt, as in calcium sulphoaluminate cements, the
dehydration of ettringite has been proved to result in shrinkage cracking.

1. SOLVENT REPLACEMENT

In this method, bound/pore water present in cement pastes is replaced with the help of organic
liquids such as propanone (acetone), methanol, and isopropanol. By this method, composition
and microstructure of the hydrating paste is changed. Organic liquids are not completely
removed but absorb onto the surface of hydrating C3S and present there without affecting the
microstructure or phases. There may be a reaction with CH leading to aldol condensation, and as
aresult, thermogravimetric analysis (TGA) results are affected. Thermogravimetric (DTG) peaks
for calcium carbonate at about 630 °C are influenced by applying acetone to stop cement
hydration. These outcomes could be due to an aldol reaction catalysed due to presence of CH.

It was recommended by some other researchers that presence of organic matter such as acetone,
does not have any influence when carrying out X-ray diffraction (XRD) works. Solvent
replacement with isopropanol formed samples in which fine pores were slightly broken and that
this method best conserved the finest pores as compared to oven drying and freeze drying.
Methanol and isopropanol caused least stress to the microstructure of the hardened cement
pastes. By taking into account changes in length and weight of grains in cement pastes dipped in
isopropanol and methanol, Methanol reacts with hydrated cement by penetrating the C–S–H, but
observed that there was no reaction between isopropanol and hydrated cement. Methanol reacts
with hardened cement paste and that the length of CH crystals increased when dipped in
methanol, isopropanol, and acetone.

2. FREEZE DRYING

Freeze drying technique is a sufficient drying method for use with MIP, it most likely produces
major loss in the C–S–H related to thermo mechanical stress. Pores of hardened cement pastes
were broken by freeze drying method. Freeze drying leaves a large amount of water in the
microstructure of the hardened cement paste, while for thermogravimetric analysis and scanning
electron microscopy, freeze drying was reasonable.

37
3. OVEN DRYING

In oven dying method, drying of paste in oven at 105 °C partially dehydrates the C–S–H and
pores present in the hardened cement samples are smashed. After oven drying, cracks are visible
in the microstructure of the hardened cement sample with the crack density increasing as the
drying conditions turn more difficult. In oven drying at 105 °C, ettringite and C–S–H perhaps
leave a noticeable amount of non-evaporable water, so that oven drying at 105 °C and even
60 °C is inappropriate for preserving the fragile microstructure of hardened cement paste.

4. VACUUM DRYING

High vacuum drying degraded ettringite and monosulphate, and severely damaged the pore
structure, escalating the pore volume of hardened cement paste. Vacuum drying samples of
hardened cement paste formed stresses and microcracks similar to those observed for samples
dried in an oven at 60 °C and 105 °C, while vacuum drying removed considerably less water
than oven drying at 105 °C. Knapen, et al. (2006) performed a comparison between Vacuum
Drying and Solvent Exchange Techniques.

2.8 Heat of hydration

The compounds of PC are non-equilibrium products of high-temperature reactions and are,


therefore, in a high-energy state. When PC is hydrated, the compounds react with water to
acquire stable low-energy states, and the process is accompanied by the release of energy in the
form of heat. In other words, the hydration reactions of PC compounds are exothermic.
According to Mehta and Monteiro (1993) for a typical PC, approximately 50% of the potential
heat is liberated within the first 3 days and 90% within the first 3 months of hydration. The
significance of heat of hydration in concrete is that the heat of hydration studies can be used for
characterising the setting and hardening behaviour of PC, and for predicting the temperature rise
in concrete. These measurements are also useful in predicting the strength development of
concrete.

38
2.9 Effect of cement variations on workability of concrete

The properties of fresh concrete are very vital because they help to decide the techniques needed
for its handling and compaction. Also these properties influence the properties of hardened
concrete to a great extent. The different aspects of the class of fresh concrete need different
requirements. So, a number of definitions are in common practice, each concentrating over a
different aspect of concrete behaviour: consistency, flowability, mobility, pumpability,
compactability, finishability and harshness. These definitions are, however, one-sided and
qualitative referring different things to different people. The term workability is commonly used
to represent all of the properties mentioned above. To be a little more exact, workability is often
defined in terms of the quantity of mechanical work or energy required to make full compaction
of concrete without segregation. Recent studies have shown that the cement variations have a
greater influence on the workability and on the early reactions of concrete than is generally
thought of. These variations are greater with superplasticized mixes but problems can exist also
with normal concrete mixes. The unexpected variations may lead to serious disturbances in
production in the form of poor compaction, too low early strength and strand slippages. This is
causing increased waste in production and considerable economical losses particularly at hollow
core slab factories. Cement variation is difficult to measure or control at a precast plant. The
quality information presently available from the cement supplier is not detailed enough to predict
the behaviour of cement in a concrete mix.

As per A. M. Neville (1971, 1995), more the water content of paste of standard consistency, finer
the cement is, but on the other hand an increase in the Blaine value of cement slightly increases
the workability of a concrete mix. W.H. Price (1951) and US BUREAU OF RECLAMATION
(1956) also verified this. Wuherer et al., (1950) concluded that increase in fineness may slightly
increase the amount of water required to give a neat cement paste of standard consistence but, in
contrast, reduce slightly the amount needed to obtain a given workability in a concrete mix.
According to E. C. Higginson (1970), the workability of concrete is increased by increasing the
cement fineness. For air–entrained concretes, the effect of fineness of cement on workability is
not too much pronounced. He also claimed that increasing the fineness of cement from 2700 to
about 4000 cm2/g, reduces the water requirement of concrete. However, increasing the fineness

39
of cement beyond a certain optimum limit increases the water requirement of concrete. Kwan
and Wong (2008) worked on determining belongings of packing density, excess water and solid
surface area on plasticity of cement pastes. As per results, increase in packing density will
increase excess water content and workability is governed by excess water to solid volume and
excess water to solid surface area ratios.

2.10 Effect of cement variations on compressive strength

The strength of a hardened concrete largely depends upon the (i) water-cement ratio, (ii) the
quality and characteristics of cement, (iii) the degree of compaction obtained in the concrete, (iv)
curing and (v) the age of the concrete. The strength increases, as the concrete becomes older.
Generally speaking, strength is largely independent of the type of grading of the aggregate and
the mix proportions. These factors influence the water content required to produce a given
degree of workability and therefore affect the strength indirectly. Although the improvement in
compressive strength for a defined increase in cement content depends mainly on the type of
aggregate used and the cement content itself, on average, for lightweight aggregate, a 10%
higher cement content will give just about 5% higher strength (Clarke, 1993).

F. M. Lea (1971) concluded that more finely the cement is ground, greater is the strength, and
particularly the early age strength, it yields. The author conducted research on fineness versus
tensile strength of cement pastes. Tensile tests on neat cement pastes show that beyond a certain
limit, which lies between 1 and 10 % residue on a 170-mesh, the strength decreases with finer
grinding, and a similar effect has occasionally been observed for the tensile and compressive
strength of mortars of dry consistency, i.e. with a water: cement ratio below 0.35. Kuhl (1931)
suggested that there exists a definite optimum limit of fineness, such tests do not, however,
provide any adequate measure of the influence of blaine values on the strength of mortars and
plastic concretes and for these there is, in general, an increase in strength as a given cement is
more finely ground, at least as far as present practical limits of fineness are concerned.

W. H. Price (1951), H. C. Entroy 91964) and M. Venuat (1965) developed curves for 7 days, 28
days, 90 days and 1 year compressive strength verses fineness of cement separately. The effect

40
of fineness of cement on compressive strength varies with the cement and concrete mix. An
improvement in fineness from 1800 to 2500 cm2/g (equivalent to 3200 to 4500 by air
permeability method) enhances the compressive strength at 1 day by 50-100%, at 3 days by 30-
60%, and at 7 days by 15-40%. However, improvement in specific surface beyond about 5000
cm2/g (by air-permeability apparatus) only results in a relatively small increase in strength at less
than 1 day. As per Locher et al., (1966), the grain size tiny proportion below 3 m has been set
up to have the predominate influence on the compressive strength at 1-day while the 3-25 m
fraction has major effect on the 28 day strength. E. C. Higginson (1970) claimed that 28-days
compressive strength of concrete increases with an enhancement in fineness. The difference in
compressive strength due to difference in fineness of cement is significantly less at 1 year’s age.
The author has also claimed that for concrete containing no entrained air, there is a slight
decrease in the static modulus of elasticity at 28 day’s age, as the fineness of cement is
improved. The modulus of elasticity of concrete persistent by sonic method decreases as the
fineness of cement increases.

Svinning et al., (2008) worked on calculation of compressive strength up to 28 days from


microstructure of Portland cement. Alexander (1972) correlated statistics from new research
work and from results published during the past 40 years and conducted regression analysis to
determine the connection between strength, composition and fineness of cement. Haraste and
Bejzjak (1974) conducted a study on the likelihood to resolve the effect of grain size of cement
on the compressive strength of cement mortars by concentrating over all the particles in a set,
under the belief that apart of the individual effect of every particle in the course of hydration
there is an instantaneous and midway effect of all the particles on the same physical property.
Oner et al., (2003) studied the effect of component’s fineness on compressive strength of blast
furnace slag cement. He concluded that in the manufacturing of blast furnace slag cement
(BFSC), it is not only the particle size of the clinker-slag mix, but also of the separate parts,
which govern the choice of the mix composition for a target strength.

41
2.11 Deterioration of cement with storage

Cement has a great avidity for water and will readily absorb moisture from the atmosphere or
from damp material in contact with it. Cement exposed to the atmosphere gets hydrated and loses
strength. When cement is stored in sacks (made of jute), absorption takes place from the air and
strength of the cement is considerably reduced. The absorption by cement, of 1 or 2 percent of
water, has no appreciable effect, but further amounts of absorption retard the hardening of
cement and reduce its strength. If the absorption exceeds 5 per cent, the cement is ruined for all
ordinary purpose.

Cement stored in bulk or in air-tight containers does not deteriorate. It can be stored in covered
barrels or bins. Cement thus stored up to about 2 meters or more in depth can lie for longer than
a year with no more damage than the formation of a crust on the surface about 5 cm thick, which
should be removed before cement is taken for use. Special care is necessary during the rainy
season. Bags should not be opened until cement is to be emptied into the mixer.

The following figures show the average reduction of strength in a 1:2:4 mix. as a result of
storage:-
Storage duration Reduction in strength
(Months) (Percentage)
03 20
06 30
12 40
24 50

Ordinary Portland cement which has been stored for over six months, and rapid hardening
cement which has been stored over two months from the time of leaving the factory, should
always be tested before use. If deterioration is suspected, the test for “setting time”, described
before, should be applied.

42
Test for freshness of cement

Indication of a damaged cement are given by the presence of large lumps of set cement, and
when this happens, the lumps should be screened out unless they are soft enough to be powdered
when pressed in the fingers. It needs to be considered if this cement is to be rejected.

When cement is rubbed between fingers and thumb it should feel like a smooth powder, such as
floor. Grittiness may indicate deterioration. Such cement should be tested for setting time. If
caked material is screened out and the balance used with 10 percent extra cement, the concrete
will be good for common small works, though it will be slow setting.

Storage of cement

Portland cement may be stored indefinitely without loosening its cementing qualities, if it is
protected from moisture. For this reason, it should be stored in dry under tight location as far as
possible. Bulk cement should be stored in weather proof bins. If bagged cement is to be stored
out of doors, the sacks should not be placed directly on the ground and should be covered for
protection against rain.

2.12 Portland cement concrete - general

Portland cement concrete is a hard material cast by allowing a carefully balanced mixture of
Portland cement, fine aggregate, coarse aggregate, and water to set in formworks of the shape
and size of the desired members. The mass of the concrete consists of fine and coarse aggregate.
Cement and water react chemically to unite the aggregate particles into a solid volume. Extra
water, over and above that required for this hydration reaction, is essential to impart the mixture
the workability that makes it to fill the formwork and cover the entrenched reinforcing steel
earlier than setting. Concrete in a broad choice of properties can be cast by suitable modification
of the proportions of the constituent materials. Special cements, special aggregates, admixtures,
and special curing methods permit an even wider variety of properties to be obtained.

43
These properties depend to a considerable level on the ratio of the mix. It also depends on the
carefulness with which the various individual constituents are mixed with each other, and on the
moisture and thermal conditions, in which the mix is subjected throughout its life up to fully
hardening. The mechanism of managing such conditions is known as "Curing". To avoid the
unplanned production of poor concrete, a high level of skillful control and management is
necessary throughout the concreting process.

As already mentioned, main constituents of concrete are cement, fine aggregate, coarse
aggregate and water. In addition, there are a host of other materials, called additives that may be
added to obtain special properties. These include air entraining agents, accelerators, decelerators,
carbon black, fly ash, pozzolans, silica fume, water-reducing agents, superplasticizers, among
others. The use of these admixtures is a specialized subject for experienced professionals and,
therefore, was generally not deemed suitable for inclusion in body of this literature survey. In
section 2.1 to 2.3, we have discussed cement in detail. Now we will study the other main
constituents of Portland cement concrete.

2.12.1 Water

Water initiates the chemical reaction that produces the binding qualities of cement. Without it,
cement is unusable powder and concrete is impossible to make

Effect of impure mixing water


In order to hydrate, cement must have proper amount of water in the paste. It is important to
know the source of this mixing water. Impurities concentrated in sufficient quantity in water
could seriously reduce the strength of concrete, and cause wide variation in setting time. Certain
other chemical compounds may cause unattractive discoloration in concrete surface,
efflorescence (movement of salts to the surface), and excessive corrosion of reinforcing steel.

Testing water for mixing


If the water to be used for mixing is, in any way questionable, it should be submitted for
laboratory analysis before using. There are two ways for this, one practical method is to prepare

44
mortar cubes using the questionable water and compare the 7 and 28 days compressive strength
of these cubes with others, made using water known to be satisfactory. If the strength of the
questionable cubes is at least 90% of the other cubes, the water is judged to be acceptable.

Usually analysis of a city’s water supply is always available from the Municipal Water
Department. It will list dissolved salts (silica, iron, sodium and sulphate) in the water as so many
milligrams per liter (ppm). Water containing less than 2000 milligrams per liter of total dissolved
solids can generally be used satisfactorily for making concrete. Although higher concentration
are not always harmful. They may affect certain cements adversely and should be avoided where
possible. A good thumb rule to follow is, if water is pure enough for drinking, it is suitable for
mixing concrete.

Impurities in mixing water

The following impurities in water may obstruct the setting of cement, may badly influence the
strength of the concrete or produce discoloration of its surface, and may also cause rusting of the
reinforcement:

(1) Carbonates and bicarbonates

While present in water have significant effects on the setting time of different cements, sodium
carbonate may cause very rapid setting, bicarbonate may either accelerate or retard set.
Miscellaneous inorganic salts may be present in mixing water. If it is suspected that significant
amounts of salts are dissolved in the water, it is good policy to test the concrete for retarded
setting times or reduced strength. In general, concentration of salts up to 2000 mg/ltr can be
tolerated in mixing water.

(2) Sewage & industrial substances in mixing water

Sugar, citrates, various types of acids, oils, sewage, and peat fibers can delay the setting of
concrete or lower its strength. These materials are found in water carrying sanitary sewage in

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industrial waste. Waters containing sewage or industrial waste usually has less than 400 gm. of
total solids per ltr. When such water is used in mixing concrete, the reduction in strength is
generally not greater than 10%. However, waste water from paper pulp mills, tanneries, paint
factories, coke plants mills, and chemical and galvanizing industries may contain harmful
impurities.

(3) Oils

Oils of various kinds are occasionally present in mix water. Generally such water makes poor
concrete.

(4) Silt

Silt in mixing water is permissible to a tolerance level of 2000 mg/ltr. Higher concentrations may
not affect strength, but could influence other properties of concrete.

2.12.2 Aggregate

The quality of concrete chiefly depends upon the quality of aggregate because these are the
aggregates that cover at least 3/4th of the total volume of concrete. The main property of concrete
is strength and this property is limited by the strength of aggregates as weak aggregates can
never produce strong concrete. Also the aggregate greatly influence the durability and structural
performance of concrete.

Cement is the most costly constituent of concrete and aggregates were previously assumed as an
inert substance spread throughout the cement paste mainly for economic reasons. As an opposite
view, aggregates may be taken as a building material connected into a cohesive total by means of
the cement paste in a way similar to masonry construction. Actually, aggregate is not purely inert
and its physical as well as chemical properties somehow has an influence on the properties of
concrete.

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As already mentioned, aggregate is cheaper than cement and it is, therefore, economical to put
maximum of it with minimum of cement on economy grounds. But economy is not the only
motive for using aggregate; it possesses considerable technical advantages on concrete, which
include a higher volume stability and better durability than the cement paste alone.

Depending upon their size, the aggregates are classified as under:

(a) Coarse Aggregate


(b) Fine Aggregate

(a) Coarse aggregate

The material whose particles are of such size as are retained on a 3/16// in B.S. test sieve, is
termed as coarse aggregate. The size of the coarse aggregate used depends upon the nature of
work. The maximum size may be 20 cm (9//) for mass concrete work, such as dams etc, and
62.5mm (2.5//) for plain concrete work. For R.C.C. Construction, the maximum (1//) although
20mm (0.75//) of aggregate is commonly adopted.

Crushed hard stone and gravel are the common materials used as coarse aggregate for structural
concrete. Coarse aggregate are usually obtained by crushing granites, gneiss, crystalline lime
stones and good variety of sand stone, etc. Broken brick is a cheap aggregate for plain concrete
but it renders the mix weak in strength. It is not used in R.C.C. work on account of the possibility
of the reinforcement getting rusted due to the high porosity of the aggregate. Clinker slag, coal
ashes, coke breeze also used as aggregate for lightweight & insulating concrete.

(b) Fine aggregate

The material, which passes 3/16" B.S. sieve size, is termed as fine aggregate. Natural sand is the
fine aggregate chiefly used in concrete mix. Sand may be obtained from sea, river, lake, etc, but
when used in a concrete mix, it should be properly washed and tested to ascertain that it is free
from clay, silt, and such organic matters.

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Commonly used fine aggregate in R.C.C. work is sand. It is either round or angular in grains and
is often found mixed in various gradation of fineness. The sand used for mortars should consist
of sharp (angular) grains of various sizes. It is generally considered that rounded particles
(grain), do not interlock sufficiently to produces strong mortars.

Bulking of sand
When dry sand comes in contact with moisture or water, thin film is formed around the particles,
which causes the particles to get apart from each other. This results in an increase in volume of
sand. The volume of damp sand may exceed by more than 30% of the volume of same sand
when dry. This phenomenon is known as bulking of sand. It increases with addition of water up
to about 50% by weight. Further addition of water causes films around the particles to break and
thus the volume of sand gets reduced. It is important to note that dry and fully saturated sand
occupies the same volume.

Factors governing selection of aggregate

a) Strength
A strong aggregate makes strong concrete. Granite aggregate will produce a strong
concrete, whereas pumice or burnt clay aggregate, which are sometimes used where
saving of weight is desired, produce concrete of lower strength.
b) Size
Besides the minimum limit of 3/16" for coarse aggregate there arises the question of
maximum size. Clearly the aggregate must be small enough to enable it to work able in
between and around all reinforcements and into all corners of the work.
c) Particle shape
Suitable particle shape vary between rounded, irregular and angular. For a given
workability, of any concrete mix, angular aggregates require the highest water-cement
ratio and rounded aggregates the lowest. Since the strength of concrete depends so greatly
on water-cement ratio, the selection of particle shape is all important.

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d) Surface texture
Other things being equal, a rough surface gives a stronger concrete than a smooth one. It
is clear that when concrete is subjected crushing, there is tendency for smooth surfaced
particles to slide past one another and to act as wedges disrupting the concrete. Whereas
aggregates with rough surface do not lend themselves so readily to these actions.
e) Grading
For a concrete to be dense and impervious, it is necessary for there to be sufficient water
to fill the voids in the coarse aggregates and sufficient cement to fill the voids in the fine
aggregates. If all the particles were of the same size, the percentage of voids would be
high up to the about 50%. Whereas when the particles are graded the percentages of voids
is considerable reduced. Such grading results in a reduction in the amount of mortar
required to fill the voids.
f) Impermeability
It is essential that aggregate used in concrete for reservoirs, water towers, and other
water-retaining structures, should be impermeable. This is equally important in all
reinforced works because moisture will result in rusting of reinforcements or to the
wedging action of frost, or water contained within the aggregates.
g) Cleanliness
Aggregate must be free from clay, silt, fine dust or other adherent coatings likely to
interfere with the proper mixing of the materials, or likely to weaken the adhesion
between the individual particles in the hardened state.

h) Chemical inertness
Some materials contain traces of sulpher, unburned coal. As a result of chemical actions
of these materials, it causes swelling or disruption of concrete, or may attach the
reinforcement.
i) Cost
In practice an engineer has to balance the value of the aggregate based on the foregoing
considerations against their cost. This, generally, accounts, on their availability and

49
location to the site of the work. Thus a granite which has to be hauled a 100 miles may
not be economic, if local stone will give 80% strong concrete at a greatly reduced cost.

Properties of aggregates

a) Bond of aggregate:
The bond between aggregate and cement paste is a factor of vital importance as far as the
strength of concrete is concerned. This bond is created due to the interlocking between
aggregate and the cement paste and depends mainly on the roughness of the surface of
aggregate. The strength of this bond increases with the increasing age of concrete.
b) Specific gravity
Specific gravity is defined as the ratio of weight of the solid to the weight of an equal
volume of pure distilled water. Since aggregate normally have voids in them, absolute
specific gravity may be designated to the volume of the solid material excluding all such
voids.
c) Porosity and absorption
The porosity, permeability, and absorption of aggregate influence the following
properties of aggregate on the bond between it and the cement paste: resistance of
concrete to freezing and thawing, its chemical stability and resistance to abrasion.
d) Strength of aggregate
Strength of aggregate affects greatly the strength of concrete. The effect of aggregate on
the strength of concrete is not only due to the strength of aggregate but also a substantial
level, to its absorption and bond characteristics. Generally strength of aggregate depends
greatly on its compositions, texture and structure.
e) Other mechanical properties of aggregates
These are properties, which are to be measured when the aggregate is to be used in
pavement construction or is to be subjected to high wear & tear:
i. Toughness
Toughness is defined as the resistance of aggregate to failure by impact.
ii. Hardness
It is defined as the resistance to wear.

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2.13 Properties of fresh concrete

2.13.1 Workability

Workability of concrete mixture may be defined as “the ease with which it may be mixed,
handled, transported and placed into the final position with a minimum loss of homogeneity".
Different site conditions required different degree of workability. If for example, concrete is to
be placed by hand in formwork in which there is a great deal of congested reinforcement, the mix
would require a high degree of workability i.e. it would have to be very wet; if, however, a
mechanical vibrator is to be used, a drier mix could be placed satisfactorily

The workability of concrete depends on many factors, the amount of cement, the fineness of
cement and its chemical composition, the amount of water, the grading and shape of fine
aggregate, the grading, shape and surface texture of the coarse aggregates, the ratio of fine to
coarse aggregates and the presence of entrained air or other admixtures.

A workable concrete mix must be fluid enough so that it can be compacted with minimum labor.
A workable concrete does not result in bleeding and segregation. Excellent workability, for
example, normally requires high cement and fine aggregate contents with a low coarse aggregate
content and relatively high water content.

Factors affecting workability

(1) Water
The workability of a concrete increases as the water content of the mix is increased. But increase
in water content would cause a decrease in strength. Excess of water weakens concrete, produces
shrinkage cracks (shrinkage increases with increase in water content), and decreases density.
Water occupies space in concrete and as it evaporates, it leaves voids and cracks. The volume of
water voids may be as much as 10% of the total volume of concrete. Generally speaking, lower

51
the water content, the stronger the concrete but the quantity of water must be sufficient to
produce a workable mix required for the particular method of compaction to be adopted.

Concrete made with low water-cement ratio is unworkable. If stuff or dry concrete is used
honey-combing will result decreasing density and strength. An unworkable concrete results in
incomplete compaction giving rise to air voids. Pressure of 5% air voids will cause a 30%
strength loss. Therefore, there is an optimum value of the water-cement ratio for every mix. The
quality of water has to be restricted within certain minimum limits. Concrete should be around
the reinforcement rods. Sometimes strength has to be sacrificed by adding more water to obtain a
higher degree of workability where concrete has to be placed in narrow and thin section. The
best mix is one which gives the maximum workability with minimum amount of water.

(2) Aggregates
Other things being equal, the workability of concrete is greater with aggregates of larger
maximum sizes. For dry mixes workability is generally greater with rather a coarser aggregates
grading, but for wet mixes better results are often obtained with finer grading.

A smooth and rounded aggregate will produce more workable concrete than sharp angular
aggregate (crushed rock or crushed gravel). A flaky aggregate produces the harshest or most
unworkable concrete. Aggregates producing more workable concrete need less water and hence
give higher strength.

(3) Cement
Cement ground to the upper limits of fineness makes more workable concrete because it is more
cohesive and has less tendency to segregate and bleed. Coarser cement on the other hand,
reduces the stickiness of the mix.

A mix with a very little cement (a lean mix) is harsh and difficult to finish. Flash set occurs,
when hot cement contacts the mixing water; it is actually accelerated hydration. Flash set can
occur in winter when hot water is added to the cement in the mixer. The higher the cement
content, the greater the workability and less the effect of grading.

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(4) Effects of time and temperature
Concrete stiffens because some of the water from the mix is absorbed in the aggregate, some is
lost in evaporation and some is combined in the hydration process. Hot days require the water
content of a mix to be increased to maintain constant workability. As the temperature of the
concrete is increased the percentage of water required to effect a one-inch change in slump also
increases.

Concrete should remain plastic for at least quarter-to-half hour after water is added without
unusual precautions. Continuous agitation will maintain workability for three hours or more but
may cause a significant slump loss. Water added to restore the original slump, will often cause
strength reductions.

2.13.2 Compaction

Concrete must be workable enough to allow compaction to maximum density. Compaction is


important because density is one of factors directly related to strength. It eliminates voids,
bubbles or fissures of entrapped air. Compaction of concrete should proceed immediately after
placing. The concrete mass should be compacted till the cream of the cement starts appearing on
the surface. Over compaction may leave air voids in concrete. Compaction may be done by hand
or mechanical device.

Hand compaction may be done by rodding, tamping, or hammering. Tamping is usually adopted
in compacting concrete for slabs or other such surfaces. Rodding is done for thin vertical
members. While, hammering is done for massive plain concrete works.
Mechanical compaction is done by the use of vibrators. Vibrators are of three general types:
(a) Internal (b) External and (c) Surface.

Internal vibrators are commonly used on large works for plate surface compaction. External
vibrators are placed against the formwork and are only adopted for thin sections of members or

53
in place where internal vibrators cannot be used with ease. Surface vibrators are generally
employed in concrete road construction works.

2.13.3 Segregation

“Segregation is the separation of the coarse aggregate from the rest of the mix or the separation
of the cement-water paste from the aggregate”. Segregation generally indicates poor aggregate
grading or mix design. Segregation may occur in mixes, which are too wet or too dry.

Segregation can generally be reduced by altering the water or sand content or by using a finer
sand. Even with a mix of satisfactory design, segregation may be caused by mishandling during
transport, faulty placing, or over-compacting honey-combing which reduces the strength and
durability of the structures.

2.13.4 Bleeding

“Bleeding is a type of segregation in which mix water tends to rise to the surface of fresh
concrete, as solid constituents settle downwards, after compaction”. When bleeding occurs in the
top portion of a lift that portion should be removed before another is placed. It is an indication
that there is too much water or deficiency of fine material in the mix, or that too much tamping,
floating or trowling had been done. The result is a porous, dusty and weak (concrete) surface.
Bleeding makes weak joints between successive lifts in structural work. Bleeding can be reduced
by causing less water, a finer sand or by adding a finely ground inert material (stone just).

Small size of aggregate needs more water than big size and angular aggregate need more than
rounded aggregate. In other works, a concrete containing a finely graded aggregate will require
more water for a given workability than one containing an aggregate with a coarser grading.
Bleeding can be controlled by proper mix design. No more water should be used than that
required to produce a workable mix.

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2.13.5 Effects of admixtures

Poor workability caused by badly shaped aggregate or poor gradation can be improved by the
addition of an air-entrainment agent. The agent provides reduced segregation, lower bleeding
rate and easier finishing. Air entrainment is helpful not only when the aggregate is less
satisfactory; it is beneficial for the workability of concrete containing well-graded, well-shaped
aggregate as well.

Lean, harsh mixes can be improved by the addition of fines, such as pozzolanas, fly ash and rock
dust improve plasticity. Small additions of bentonite or diatomaceous earth may also be helpful.
Hydrated lime, added to the clean mix (10% to 15% by weight of cement) will also increase
workability.

2.14 Strength of hardened concrete

The strength of a hardened concrete largely depends upon the (i) water-cement ratio, (ii) the
quality and characteristics of cement, (iii) the degree of compaction obtained in the concrete, (iv)
curing and (v) the age of the concrete. The strength increases, as the concrete becomes older.
Generally speaking, strength is largely independent of the type of grading of the aggregate and
the mix proportions. These factors influence the water content required to produce a given
degree of workability and therefore affect the strength indirectly.

A round aggregate requires a lower water-cement ratio than does an angular aggregate to obtain
the same workability, therefore, a round aggregate gives a higher strength. Similarly a coarser
aggregate grading will permit a lower water-cement ratio than a finer grading for a given
workability and will thus give a higher strength. Greater strengths are also possible with rich
mixes or more thorough.

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Factors affecting strength

a) Water cement ratio


The ratio of the volume of mixing water to that of cement is termed as water cement ratio.
Water-cement ratio is a yardstick to obtain a concrete mix of desire strength. The lower the ratio
the greater is the strength of the mix. A rich mix of concrete gives a higher strength, because
more cement is used but it is on account of the fact that concrete can be used with a lower water
cement ratio.
b) Compaction
Compaction (consolidation) of concrete should proceed immediately after placing. The function
of consolidation of concrete is to expel the air bubbles in the mass and make it impermeable in
addition to its securing desired strength. The concrete mass should be compacted till the cream of
the cement starts appearing on the surface. Over compaction may lead to segregation of concrete
while under-compaction may leave air voids in concrete. As little as 5 percent voids in a volume
of concrete can reduce strength as much as 39 percent while 2 percent voids can reduce overall
strength more than 10 percent. Compaction may be done by hand or mechanical device.
c) Curing
Curing of concrete is one of the essential requirements of the process of concreting. Curing is the
process of keeping the set concrete damp for some days in order to enable the concrete gain more
strength. It has been established that the strength of concrete increases with the age provided it is
kept damp. During the process of curing, the concrete absorbs the water necessary for its
complete action to reach its required strength. The strength of concrete increases more rapidly in
the first few days after setting and afterwards, the rate of increase in strength goes on retarding.
The period for which the curing should be continued depends upon atmospheric condition such
as temperature, humidity and wind velocity. In general, the process of curing should be
continued for 7 to 10 days in cold weather, however, the concrete should be cured for at least 14
days as the rate of hardening of cement is low in such conditions. It has been discovered that
during the process of curing, increase in temperature increase the rate of strength if concrete.
This property is used in curing of small pre-cast members by stream. This enables the concrete to
gain required strength in less time.

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Materials affecting strength

1. Cement
Modern cements are made under close quality control and seldom cause poor concrete if handled
properly. Among reasons why cement might be at fault in poor concrete are, the presence of
moisture and carbon dioxide contamination caused by improper sealing of bags or excessive
storage time. Good cement is flour-like and contains no lumps that cannot be broken easily with
fingers.
Fineness and finish-grinding temperature of cement affects concrete strength. Finer grinding
increases cement strength development, especially at early stages. High early strength cement
produces concrete with greater strength at 7, 14, and 28 days than do the other (Neville 1995).
2. Water
If there is any doubt so as to the quality of the mix water to be used in concrete, it should be
tested in mortar cubes. Strength deficiency can be caused by as little as 0.2% organic material in
mix water. In general, if the water is considered drinkable, it can be used in concrete.
3. Aggregate
The potential strength of concrete is determined by properties of the aggregate as well as the
amounts used. Aggregate is usually stronger than the cement paste that surrounds. However,
some characteristics of aggregate i.e. particle shape, texture maximum size, soundness, grading
and freedom from harmful materials, affect bonding strength. Aggregate quality is probably
more influential to concrete durability, while shape and gradation are very important to strength.
Well graded aggregate containing many elongated pieces can be used in concrete, but it is not
economical. It requires extra sand, water and cement to make it workable. Strength generally
decreases as the amount of sand in mix increases beyond the level needed to fill voids in the
coarse aggregate because of increased water requirements and their effect on the water-cement
ratio.
4. Admixture
The effect of admixtures on concrete strength depends on the properties of the admixtures and
the characteristics of the concrete mix. There are admixtures that are designed to sieve in many
capacities, water reduces, accelerators, and air entrainers, for example.

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Calcium chloride is one of the most commonly used. It increased early strength during cold
weather and protects concrete from damage due to freezing by shortening the time needed for
hardening: however, it should never be considered as an antifreeze concrete. The amount of
calcium chloride used be limited to that necessary to produce the desired results. In any case it
should never exceeded 2% by weight of cement. Fly ash, up to 30% by weight of cement,
reduces compressive strength at 7 and 28 days but may increase it after three months. In
admixture such as a retarder can delay the setting of concrete. Retarders are often used when hot
weather causes early strength graining or early setting and reduction in slump to higher concrete
temperature.

2.15 Durability of hardened concrete

Durability of concrete refers to its ability to endure weathering action, attack by various chemical
substances, freezing and thawing, abrasion and many other Aside from architectural potential,
concrete is employed as a building material because of its strength and lasting qualities. These
qualities are incorporated into concrete by the use of suitable materials, good mix proportioning,
careful batching, mixing, handling and placing, adequate consolidation and sufficient curing.
Many of the conditions that cause concrete to lack durability are not immediately apparent. Some
of them are harmful materials in the aggregate that cause large deflections and cracking, use of
highly absorptive aggregate that expands when moist and exerts sufficient force to disrupt
concrete when frozen, and impure mixing water.

When concrete is placed in lifts it is essential that each lift be prepared properly before the next
one is placed. Improper clean up between lifts or construction joints contributes to weak,
permeable joints. Reinforcing steel must be well embedded in durable concrete to protect it from
corrosion. Quality concrete must be dense, made with sound aggregates and pure water, and
mixed in proportions suitable for the planned use. It must be placed and cured with utmost care.
Concrete handled in this way will give good service for many years.

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Weathering of hardened concrete
Weathering is defined as the inherent change of hardened concrete in terms of texture, strength,
colour and other physical and chemical properties due to action of the elements. All concrete
weathers but good concrete does so gradually and evenly. Gradual weathering shows up in
rounded edges and/or slight or erosion of the surface. This is a natural phenomenon that gives an
interesting appearance to the concrete. Sound concrete that will break clean (through both the
aggregate and paste) withstands weathering. Poor concrete that will break crumbly is subject to
accelerated weathering. Accelerated weathering shows up in cracks roughly parallel to the edges
of the concrete. These cracks are known as D-line cracks. They fill with calcium carbonate and
dirt. Sound concrete that will not subject to accelerated weathering depends on good mixture
proportioning, a low water-cement ratio, and good workmanship.

Permeability to liquids
If concrete were completely solid, it might be water tight: however, air voids are always present.
They make concrete permeable to outside influences. Materials in rain or ground water may
penetrate concrete with adverse effects.

Destruction from freezing and thawing in the presence of water and corrosion of reinforcement
subjected to moisture and air, are problems related to the permeability of concrete: permeability
is subjected to movement of water from one surface to the other, when there is difference in the
humidity on either surface.

Permeability is caused by pores in both the cement paste and the aggregate. Larger voids found
in poor quality concrete are caused by poor compaction and by bleeding. In every extreme case,
the voids may occupy as much as 10% of the volume of the concrete.

Fresh concrete is more permeable than hardened concrete. In fresh paste, the flow of water is
controlled by the size, shape and concentration of the original cement grains. Hydration reduces
permeability as gel fills the original water filled spaces.

59
In mature paste, permeability depends on the size, shape and concentration of the gel particles
and on whether or not, the capillaries in the cement paste stop. The permeability is lessened with
a high cement content in the concrete. This means less permeable concrete has a lower water-
cement content. Air entrainment reduces permeability because it reduces seggregation and
bleeding.

Effects of various substances on hardened concrete

(a) Acids
Some acids attack the cement paste in concrete causing disintegration at the surface or if they
enter in crack, causes internal damage. Some ores, coal or cinders are sources of mineral acids
when they become wet. Concrete used in contact with such materials must be protected.
Unprotected concrete subjected to acid funes in the atmosphere may be dissolved into a soft
mass. This sometimes occurs in chimneys, steam railway tunnels, and other industrial situations.

Concrete in food processing plants is attracted by bacteria and fungi, that grow at floors and
walls. These growths cause damage by mechanical action and by secretion of organic acids.
Antibacterial cement is available. The active ingredient in this cement is usually Assenic or
Copper. This type of cement is used in food plants, kitchens, dairies and pharmaceutical plants as
well as show rooms, boat houses and swimming pools.

(b) Sulphate and chlorides


Salts in solution can react with hardened cement paste. Ground water may contain dissolved
mineral salts like alkalies, magnesium and Calcium sulphates. Sulphates react with calcium
hydroxide and calcium aluminate hydrate. The products of the reaction (gypsum and calcium
sulfoaluminaate) require a wider space than the reactants they replace resulting in expansion and
disruption of the concrete. Sulphare attack produces a whitish deposit. Damage usually starts at
the edges and corners, with progressively spalling and cracking. Eventually the entire concrete
mass is reduced to a soft state.

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Calcium chloride is a commonly used deicing agent when applied to ice or snow; it lowers the
freezing point of the frozen material creating a salt solution. Temperature is high, sulphur
compounds contained in the effluent can be reduced to hydrogen sulphate by anaerobic bacteria.
When hydrogen sulphate is dissolved in moisture, this film, on the exposed surfaces of concrete,
produces sulphate acid, strong enough to attack lime compounds in the concrete.

(c) Sea water


Sea water contains chemicals such as chlorides and sulphates. Crystallization of salts in the pores
of concrete may cause disruption from the pressure exerted by the salt crystals. This takes place
above the water level because crystallization occurs at the point of water evaporation.
Permanently immersed concrete is attacked less than that which is alternately wetted and dried,
and disintegration is more rapid in tropical climate than in temperate regions.

To protect against sea water attack, concrete should have well graded, first class, non-reactive
aggregate. Air should be entrained to increase workability and slump in a low water-cement ratio
mix.

2.16 Previous research

(a) Strength of cement & concrete

(i) As per A. M. NEVILLE (1995), the rate of hydration depends on the blaine values of the
cement particles, and for a fast improvement of strength more grinding is required. W.
H. PRICE (1995) also claimed the same.
(ii) F. M. LEA (1971) concluded that more finely the cement is ground, larger is the
strength, and chiefly the early age strength, it yields.
(iii) F. M. LEA (1995) conducted research on fineness versus tensile strength of cement
pastes. Tensile tests on neat cement pastes show that ahead of a certain limit, which lies
between I and 10 per cent residue on a 170-mesh, the strength lessens with finer
grinding, and a similar effect has occasionally been observed for the tensile and

61
compressive strength of mortars of dry consistency, i.e. with a water: cement ratio below
0.35.
(iv) KUHL (1931) and some others recommended that there exists a specific optimum limit
of fineness, such tests do not, however, provide any suitable measure of the influence of
blaine values on the strength of mortars and fresh concretes and for these there is, in
general, an improvement in strength as a given cement is more finely ground, at least as
far as present realistic limits of fineness are concerned.
(v) W. H. PRICE (1951), H. C. ENTROY (1964), and M. VENUAT (1965) developed
curves for 7 days, 28 days, 90 days, and 1 year compressive strength verses fineness of
cement (Wagner), independently. The effect of fineness (wagner) on strength changes
with the cement and concrete mix. An increase in specific surface from 1800 to 2500
cm2/g (Wagner, equivalent to 3200 to 4500 by air permeability method) enhances the
compressive strength at 1 day by 50-100 percent, at 3 days by 30-60 percent, and at 7
days by 15-40 percent. However, enhancement in fineness after about 5000 cm2/g (by
air-permeability apparatus) only causes a relatively small increase in strength at less than
1 day.
(vi) As per LOCHER, et al. (1966), the particle size fraction below 3  has been found to
have the dominated effect on compressive strength at 1-day while the 3-25  fraction has
key effect on the 28 day strength.
(vii) E. C. HIGGINSON (1970) claimed that
 28-days compressive strength of concrete increases with an increase in fineness. The
divergence in compressive strength due to variation in fineness of cement is
significantly less at 1 year’s age.
 For concrete containing no entrained air, there is a minor reduction in the static
modulus of elasticity at 28 day’s age, as the fineness of cement is increased. The
modulus of elasticity of concrete determined by sonic method decreases as the
fineness of cement increases.
(viii) SVINNING, et al. (2008) worked on forecast of compressive strength up to 28 days
from microstructure of Portland cement.

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(ix) ALEXANDER (1972) interrelated results from new research and from results published
in the last 40 years and with the help of regression analysis to fix the association between
strength, composition and fineness of cement.
(x) HARASTE AND BEJZJAK (1974) conducted a research on the possibility to measure
the effect of particle size distribution of cement on the strength of cement mortars by
considering all the particles in a set, under the belief that apart of the independent effect
of every particle in the course of hydration there is an instantaneous and central effect of
all the particles on the same physical property.
(xi) ONER (2003) worked on the effect of component’s fineness on compressive strength of
blast furnace slag cement. He accomplished that in the manufacturing of blast furnace
slag cement (BFSC), it is not only the particle size of the clinker-slag mix. but also of the
separate parts, which manage the choice of the mix. ratio for a target strength.

(b) Water demand of cement & concrete

(i) As per A. M. NEVILLE (1995), more the water cement ratio of the paste of standard
consistency, finer the cement is, but on the other hand an increase in the blaine value of
cement slightly increases the workability of a concrete mix. W.H. PRICE (1951) and US
BUREAU OF RECLAMATION (1956) also verified the same.
(ii) J. WUHRER, et al. (1950) accomplished that an enhancement in fineness may somewhat
increase the quantity of water required to give a neat cement paste of standard
consistence but, in contrast, lower slightly the amount needed to obtain a given
workability in a concrete mix.
(iii) As per E. C. HIGGINSON (1970), the workability of concrete may be increased by
increasing the cement fineness. For air–entrained concretes, the effect of fineness of
cement on workability is is not too much prominent. He also recommended that
increasing the fineness of cement from 2700 to about 4000 cm2/g, decreases the water
requirement of concrete. However, increasing the fineness of cement more than an certain
optimum limit increases the water requirement of concrete.
(iv) KWAN AND WONG (1995) worked on determining relations between packing density,
excess water and solid surface area on plasticity of cement pastes. As per results, increase

63
in packing density will increase excess water content and workability is governed by
extra water to solid volume and extras water to solid surface area ratios.

(c) Grinding of clinker

(i) JORGENSEN AND SMIDTH (2005) made a comparison between clinker grinding in
vertical roller mill and ball mill and found out that ball mill is economical in initial
cost and erection while vertical roller mill has low weight as compared to ball mill.
(ii) KATSIOTI, et al. (2009), studied categorization of a variety of cement grinding aids
and their influence on grinding behaviour and cement functioning.
(iii)LIDSTROM AND WESTERBERG (2003) studied a new technique “Sala Agitated
Mill” in wet grinding pattern and focused on the effect of fineness on compressive,
tensile, and bond strength of hardened concrete and found out that to get a certain
development in concrete properties, fine grinding has the potential to be an
environmentally and economically sound replacement to increased cement content.
(iv) OPOCZKY (1996) made a study of the grinding of composite cements produced from
clinker and two additional grinding additives and focused on strength, water demand,
and particle size distribution of complex cements.
(v) CHEN AND HUANG (2007) conducted empirical research on performances of dry-
grinding fine cement (DFC) of grouting. The measurement of its grinding effort and
simultated test for injectibility proved that this cement could be used to inject rock
mass with mico-fissures.
(vi) BANDOPADHYAY, et al. (1999) made a comparison between measurement of
cement fineness by Blaine permeability and laser Granulumetry and found out their
merits and demerits.

(d) Hydration studies

(i) HATZITHEODOROU, et. al. (2007) conducted series of experiments to study effect
of increasing temperature from 20 C0 to 50 C0 on heat of hydration of concrete.

64
(ii) KNAPEN, et. Al. (2006) made a comparison of solvent Exchange and Vacuum drying
techniques to remove free water from early age cement-base construction materials.
(iii) COLLIER, et al. (2008), studied the effect of different water removal techniques on
the composition and microstructure of hardened cement pastes.
(iv) IVINDRA, et. al. (2005) worked on study of blended cement hydration by isothermal
calorimetry and thermal analysis.
(v) LANGAN, et. al (2002) investigated the effect of silica fume and fly ash on heat of
hydration of Portland cement.

2.17 Concluding remarks

From economic, technological and ecological points of view, cement has an undisputed role to
play in the future of the construction industry. Therefore, the variation in cement characteristics
and their effects on concrete properties had been a major area of research in concrete technology
for last two decades. However, in the context of Pakistani cements, no study can be found in the
literature on the variation of cement characteristics and their effect on concrete production.
Therefore, a thorough research was required to investigate these aspects and the different
properties of cement and concrete discussed in this chapter need to be investigated.

65
CHAPTER 3

EXPERIMENTAL PROGRAMME

66
3.1 Introduction

This chapter provides the detail of experimental layout used in achieving the objectives stated in
chapter 1. The materials used and the description of different test methods are also given. The
methods adopted in preparing the test samples including the casting, curing and testing are also
described.

3.2 Preparation of test samples

The first target was to prepare cement samples with different values of fineness but uniform in
chemical composition and other parameters. It was planned to manufacture cement samples of
six different fineness values in the laboratory by grinding clinker collected from a selected batch
of each factory separately with 4% gypsum. The following steps were taken in this regard:

1) More than 100 kg of cement clinker of the same chemical composition was collected
from each factory while the plant was running smoothly. The clinker was brought to the
laboratory and stored temporarily in polythene bags.
2) The clinker was crushed into smaller sizes by passing through a Jaw crusher of larger size
in the laboratory.
3) The crushed clinker was further turned into semi-powdered form by passing through
other jaw crusher of smaller size.
4) Gypsum was also crushed into semi-powdered form by passing through the same small
sized jaw crusher.
5) The resulting clinker from step (3) was mixed with 4% Gypsum from step (4) and finely
ground at different fineness levels in the “Iron-Jar-Type Ball Mill” of laboratory. The
capacity of ball mill was 13 kg. The following weights were taken in each batch of
grinding:

67
CLINKER : 12.5 KG
GYPSUM (4%) : 0.5 KG
TOTAL : 13.0KG

6) During grinding of different batches, fineness was checked by Blaine’s air permeability
apparatus and grinding stopped at different desired levels. Prepared cement in this way
was then sealed in small polythene bags and marked accordingly.

3.3 Flowchart of the program of investigation

The flowchart of the program of investigation is shown in Fig. 3.1. As it can be seen from this
figure that the entire experimental program was divided into four stages. In the first stage, the
testing for physical properties of cement collected from five different factories was carried out.
In the second stage the testing for chemical and compound composition of cement was
undertaken. The stage 3 involved the testing for hydration of cement. In stage 4 testing on
concrete were carried out.

Stage 1: Stage 2: Stage 3: Stage 4:

Testing for Testing for chemical Testing for Testing on


physical and compound hydration of concrete
properties composition of cement
of cement cement

Fig. 3.1 Flowchart of the program of investigation

68
3.4 Testing for physical properties of cement

3.4.1 Fineness

A modification of the Lea and Nurse method, developed by Blaine, was used for measurement of
fineness of cement samples. The method is prescribed by ASTM C 204-94 and by EN 196-6:
1989. Here, the air does not pass through the bed at a constant rate but a known volume of air
passes at a prescribed average pressure, the rate of flow diminishing steadily. The time T for the
flow to take place is measured, and for a given apparatus and a standard porosity of 0.5, the
specific surface is given by

S = Ss√ T / √ Ts

S = Specific surface of the test sample cm2/g,


SS = Specific surface of the test standard sample used in calibration of the
apparatus cm2/g,
T = Measured time interval, s, of manometer drop for test sample
Ts = Measured time interval, s, or manometer drop for standard sample used in
calibration of the apparatus.

As SS and TS are constants for a given apparatus, Eq 3.—can also be written as

S = K√T where K = Ss / √ Ts

To calculate the specific surface values in square metres per kilogram, multiply the surface area
in cm2/g by the factor of 0.1.

69
3.4.2 Standard consistency

The standard consistency of fresh cement paste was determined in accordance with BS 4550
PART 3 using the Vicat apparatus. The procedure used is described below.

i) 125 gram of water was added to 500 g of cement in a mixing bowl, while taking care
to avoid leakage of water or cement.
ii) Mixing was started without delay and the time was noted to the nearest minute as ‘zero
time’.
iii) The mixer was stopped after 90 second for 30 second during which the paste sticking
to the wall and bottom part of the bowl was separated by means of a suitable rubber
or plastics scraper and was put in the middle of the bowl.
iv) The mixer was then restarted and was run for a further 90 seconds. In this way, the
mixing was done for a total duration of 3 minutes.
v) The plunger of the Vicat apparatus was lowered to rest on the base-plate and the
pointer was fixed for the scale to read zero. Then the plunger was raised to the uphold
position.
vi) The mould of the apparatus was packed with the paste. Just after levelling the cement
paste, the mould and the base-plate were shifted to the Vicat apparatus and positioned
centrally under the plunger.
vii) The plunger was lowered smoothly until it was in contact with the paste.
viii) In that position it was kept for between 1 second and 2 seconds in order to keep away
from initial velocity or forced acceleration of the moving parts.
ix) The plunger was then allowed to pierce vertically into the centre of the paste.
x) The scale was read at least 5 second after penetration had slowed down or 30 second
after the release of the plunger, whichever was earlier.
xi) The scale reading was noted, which indicates the space between the bottom face of the
plunger and the base-plate, together with the water content of the paste expressed as a
percentage by mass of the cement.
xii) The test was repeated with cement pastes of different water contents until one was
found to produce a distance between plunger and base-plate of 6 (±2) mm. The water

70
content of that paste was noted to the nearest 0.5% as the water content for standard
consistency.

3.4.3 Setting time

The setting times of fresh cement paste were recorded complying BS EN 196-3:2005 using the
Vicat apparatus. The procedure adopted is described below.

Initial setting times

i) The quantity of water required for standard consistence was added to 500 g of cement
and this was placed in the bowl of the mixer.
ii) Steps (ii) to (iv) described in the previous section were repeated.
iii) For initial setting time, needle of the Vicat apparatus was lowered to touch the base-
plate and the pointer was fixed on the scale to read zero. Then the needle was raised
to the uphold position.
iv) The mould of the Vicat apparatus was packed with the cement paste. After levelling
the cement paste, the mould and the base-plate were shifted to the Vicat apparatus
and positioned under the needle.
v) The needle was lowered slowly until it touched the paste.
vi) Steps (viii) and (ix) explained in the previous section were repeated.
vii) The scale was read when penetration had nearly stopped, or 30 seconds after the
release of the needle whichever was earlier.
viii) The scale reading was recorded, which indicates the space between the end of the
needle and the base-plate, together with the time from zero.
ix) The penetration was repeated on the same specimen at conveniently spaced positions,
not less than 8 mm from the rim of the mould or 5 mm from each other and at least 10
mm from the last penetration position, at conveniently spaced intervals of time, e.g. at
10 minutes intervals.

71
x) The time beyond ‘zero time’ and the time at which the distance between the needle
and the base-plate was 6 (±3) mm, recorded to the nearest minute, was the initial
setting time.
xi) The specimen was reserved for the determination of the final setting times.

Final setting times

i) Steps (i) and (ii) for the determination of initial setting times were repeated.
ii) The needle with attachment for final setting was lowered to touch the base-plate and
the pointer was adjusted for the scale to read zero. Then the needle was raised to the
uphold position.
iii) The mould of the Vicat apparatus was filled with the paste. After levelling the cement
paste, the mould and the base-plate were shifted to the Vicat apparatus and positioned
under the needle.
iv) The time at which the needle first penetrates only 0.5 mm into the specimen was
noted as the final setting time. This time was that at which the ring attachment first
failed to mark the specimen.

3.4.4 Soundness

Soundness/Expansion of the samples was carried out as per BS 4550 PART 3. The ‘Le Chatelier
Apparatus’ consisting of a small brass cylinder split along its generatix was used. In this
apparatus, two indicators with pointed ends are attached to the cylinder on either side of the split.
In this manner, the widening of the split, caused by the expansion of cement is greatly magnified
and can be easily measured. A neat cement paste of standard consistency was prepared and filled
in the cylinder placed on glass plate. The cylinder was covered after filling by another glass
plate. The whole assembly was then immersed in water at 20 (+1) oC for 24 hours. After 24
hours, the distance between indicators was measured. The mould was then immersed in water
again and brought to boiling in 25 to 30 minutes. After boiling for one hour the assembly was
taken out. After cooling, the distance between the indicators was again measured. The increase in
this distance represented the expansion of cement i.e. soundness.

72
3.4.5 Compressive strength

Compressive Strength Tests of samples were made as per BS: 4550: Section 3.4:1987. Nine
cubes, each with size: 2.78// (69.5 mm) x 2.78//(69.5 mm) x 2.78/(69.5 mm), were cast from each
sample. Standard “Leighton Buzzard” sand was used to make the cubes in 1:3 cement-sand mix
ratios. Cubes were compacted using a vibrating machine with frequency, 200 Hz, applied for two
minutes. Just after casting, cubes were placed in a “Humidity Chamber”, at 65% relative
humidity. After 24 hours, the cubes were remolded and further cured in a water bath. For each
sample of cement, compressive strength was tested at 3, 7, and 28 days. As there were five
factories and six test samples were prepared from each factory a total No. of (6 x 9 x 5) 270
cubes were cast.

3.5 Testing for chemical and compound composition of cement

XRF is an systematic method to find out the chemical composition of all kinds of materials
(Brouwer, 2003). The material can be solid, liquid, powder, filtered or other form. The method is
fast, exact and non-destructive, and usually requires only a minimum of specimen preparation.
Chemical composition of all samples was determined by XRF Cement Spectrometer/Cement X-
Ray Analyzer.

3.6 Testing for hydration of cement

Samples of different practical blaine values were collected directly from the plant of a
commercial factory. 5 samples of normal Portland cement were collected in this regard from the
sampling point of vertical roller mill of the plant on consecutive 5-days trial basis. Chemical
composition of samples was analyzed by XRF Cement Spectrometer/Cement X-Ray Analyzer.
Physical testing i.e., consistency, setting time, expansion, sieve analysis, compressive strength
tests were carried out for the collected samples. The fineness of samples collected in this way is
given as under:

73
Sample Blaine value (cm2/g)

A 3000
B 3100
C 3200
D 3300
E 3450

3.6.1 Heat of hydration

Heat of hydration of collected samples was determined calorimetrically as per BS 4550: Part 3:
Section 3.8 1978, based on calculating the difference in heat of solution between the unhydrated
and hydrated cements. It is expressed in kilojoules per kilogram (kj/kg) or kilocalories per
kilogram(kcal/kg) of anhydrous mass. The method when applied to cements other than Portland
cements require the determination of water content. For Portland cements, the procedure may be
simplified by replacing the determination of water content with loss-on-ignition in accordance
with of BS 4550: Part 3: Section 13 1970.

3.6.2 Thermal analysis

Thermo Gravimetric Analysis (TG) is a type of testing that is conducted on specimens to


determine the loss in mass with relation to a change in the temperature. Such analysis is based on
a high degree of accuracy in three measurements: mass, temperature, and temperature change. As
many mass loss curves look similar, the mass loss curve may require conversion before results
are interpreted. A derivative mass loss curve can be used to recognize the point at which mass
loss is most apparent. Again, interpretation is limited without further changes and deconvolution
of the overlapping peaks may be required.

The analyser usually has a high-precision balance with a pan (generally platinum) loaded with
the specimen. The pan is shifted in a small electrically heated oven with a thermocouple to
precisely determine the temperature. The atmosphere may be purged with an inert gas to avoid

74
oxidation or other undesired reactions. A computer is used to operate the instrument. Analysis is
carried out by increasing the temperature gradually and plotting weight against temperature. The
temperature in this method routinely reaches 1000 °C or greater. After the data is in hand, curve
smoothing and other actions may be done such as to find the exact points of inflection. In this
research, the TGA/DTA study was conducted with the help of “Simultaneous Thermal Analyser”
STA 449C Jupiter. Two important parameters were obtained from the TG curves. First, the water
bound to the calcium silicate hydrate (C-S-H) gel, defined as the mass loss from 100 oC to 150oC,
which can also be alternatively called as the amount of C-S-H produced. The second one is the
mass loss analogous to the decomposition of Ca(OH)2, which occurs between 400 oC to 520oC.
This mass loss is very near to the amount of water in Ca(OH)2 and, therefore, is proportional to
the concentration of Ca(OH)2 (Midgley, 1979).

Sample preparation

1) Cement pastes of standard consistency were prepared using collected samples for hydration
studies, explained in section 3.6. The pastes were stored in closed recipients until the moment of
testing. On respective day of testing, the hardened cement pastes were crushed and ground to
fine powders.
2) The prepared powders in this way were centrifuged three times for 20 minutes with acetone
i.e., organic solvent, to remove the excess water and to stop the hydration. At the end of every
cycle, acetone was removed and replaced by fresh one. Immediately after the last cycle, the
samples were dried at 40 C0 for 24 hours under vacuum with a pump with an ultimate vacuum of
10 millibar and stored in air tight plastic bottles (Collier et al. 2008).

3.7 Testing on concrete

Test samples of different blaine values prepared by laboratory grinding of clinker collected from
5 selected cement plants (already explained in Section 3.2) were used in concrete testing.

75
3.7.1 Materials Used

3.7.1.1 Coarse aggregate

Coarse aggregate were used in uniform grading conforming to BS 882:1992. Table 3.1 shows the
sieve analysis report of the coarse aggregate used in the research.

Table 3.1: Sieve analysis of coarse aggregates

SIEVE SIZE MASS PERCENTAGE CUMULATIVE CUMULATIVE


(mm) RETAINED RETAINED PERCENTAGE PERCENTAGE
(Kg) PASSING RETAINED
30 2.58 10.99 89.01 10.99
25 1.42 6.03 82.98 17.02
19 4.01 17.07 65.91 34.90
12.5 3.89 16.54 49.37 50.63
10 3.6 15.33 34.04 65.96
05 2.00 8.5 25.54 74.46
02 1.7 7.24 18.3 81.70
1.18 0.498 2.12 16.18 83.82
0.5 0.3 1.28 14.90 85.10
PAN 3.5 14.89 - -
Weight of the sample taken was 23.5 Kg

The following three sizes of crush collected from the sources at Margalla hills (Islamabad) were
used:
Batch 1 = Passing through 19.0 mm (¾ inch) & retained on 13.2 mm (½ inch) sieve.
Batch 2 = Passing through 13.2 mm (½ inch) & retained on 9.5 mm (3/8 inch sieve).
Batch 3 = Pan

The three batches were mixed in the ratio of 4:3:1 to get uniform grading as per standard
requirement.

3.7.1.2 Fine aggregate

Sand from Lawrencepur source was used in the research. Table 3.2 shows the sieve analysis
report for the same, conforming to BS 882:1992. Fineness modulus test was carried out
confirming the ASTM C127. Fineness modulus indicates relative fineness of aggregate. It is an
76
abstract or empirical number used to classify the concrete aggregates. It also gives an index of
average surface area of aggregates. A set of ASTM test sieves with pan and lid and other
accessories was used. Fineness Modulus found to be 2.86. The grading curve for fine aggregate
is shown in Fig. 3.2

Table 3.2 Sieve analysis of fine aggregates


Sieve Size Wt. of Material % age of Cumulative %age % age Passing
Retained Material Retained
Retained
No. 4 39 5.5 5.5 94.5
No.8 56 8 13.5 86.5
No.16 97 13.9 27.4 72.6
No. 30 137 19.6 47 53.0
No. 50 255 36.4 83.4 16.6
No. 100 105 15 98.4 1.6
Pan 10 1.43 99.82 0.0
Weight of the sample taken was 700 gm

3.7.2 Mix proportions

The concrete mix ratio was taken as 1:2:4 (1 part of cement, 2 parts of fine aggregate and 4 parts
of coarse aggregate) with water cement ratio as 0.65. This was taken because there is a common
practice in Pakistan to use this mix ratio in almost all the construction.

3.7.3 Workability of concrete

The workability of fresh concrete was measured using the slump test, as per BS EN 12350-
2:2000 and BS EN 12350-5:2000 respectively.

77
Fig.3.2 Grading curve for fiine aggregatte

The proccess used forr the slump test


t was as follows.
f Thee mould andd base plate w
were washedd and
the moulld was placeed on the ho
orizontal base plate. Thee mould wass packed witth three layeers of
fresh con
ncrete, each approximateely one-third
d of the heigght of the m
mould when fully compaacted.
Each lay
yer was com
mpacted with
h 25 strokess of the tam After the topp layer had been
mping rod. A
rammed, the surface of the co
oncrete wass striked offf by meanns of rollingg motion of the
compactiing rod. The mould was lifted from the concretee by lifting itt carefully inn upper direcction.
Just afterr removal off the mould, the slump drop
d was obbserved and recorded byy determininng the
differencce between th
he original height
h of thee mould andd that of the highest poinnt of the slum
mped
cone.

78
3.7.4 Compressive strength

The compressive strength test was conducted in accordance with BS EN 12390-3:2002 on three
cubes with the help of a compression testing machine. Just before the test, cubes were taken out
of the water tank and the surface was dried using a dry cloth. This was to make certain that the
cubes were tested at a Saturated-Surface Dry (SSD) state. The cube was placed in such a way
that the load was functional in perpendicularly to the direction of casting with a loading rate of
100 kN/min and the maximum load at failure was recorded.

79
CHAPTER 4

RESULTS AND DISCUSSION

80
4.1 Introduction
In this chapter the results are discussed under three sections, viz. variation in physical properties
of cement, variation in chemical and compound composition of cement and the effect of
variation in cement on properties of concrete.

Table 4.1: Results of physical testing of cement samples


Initial Final 3-Day’s 7-Day’s 28-Day’s
Factory Fineness Consistency Setting Setting Compressive Compressive Compressive
(cm2/G) (%) Time Time Strength Strength Strength
(minute) (minute) (Mpa) (Mpa) (Mpa)
1525 23 260 305 8.04 12.03 24.47
2065 24 250 295 20.76 30.39 39.41
A 2459 24 240 280 24.07 32.09 40.56
3048 24.5 205 250 31.49 38.61 48.54
3355 25 150 190 32.09 38.61 49.54
3741 25 155 190 34.70 37.11 49.64
1690 24.25 250 275 20.46 28.68 37.10
2084 24.5 235 260 27.18 34.90 44.33
B 2526 25.5 230 260 32.70 40.42 45.73
2912 25.5 220 245 35.61 42.92 49.64
3315 26 180 200 37.50 44.73 53.95
3773 26.5 150 180 36.81 43.43 54.56
1548 24.4 210 280 11.56 18.74 26.90
2048 25 205 260 23.33 32.10 41.66
C 2468 25.2 185 240 29.61 42.67 51.22
2964 25 155 200 32.90 48.64 58.79
3476 25.25 165 215 40.67 50.82 61.37
3883 25.75 160 205 41.87 51.13 62.22
1661 24.5 200 260 20.55 32.30 41.32
2028 25 225 285 26.97 36.30 44.63
D 2580 25 225 280 32.09 41.92 48.94
3033 25.5 155 200 36.41 43.63 51.04
3369 25.5 140 180 37.37 45.17 53.03
3674 26 130 165 38.71 46.38 54.42
1620 25 200 260 8.99 16.79 26.53
1945 24.5 190 255 12.40 22.03 32.46
2495 25 190 245 13.56 23.64 33.63
E
2860 25 175 240 19.02 25.20 35.13
3380 25.5 172 220 23.25 27.12 39.96
3727 26 150 165 24.45 29.35 41.94

81
4.2 Variation in physical properties of cement

The results of various physical properties of cement manufactured in laboratory by grinding


clinker from five different sources (named A to E) in Pakistan are summarized in table 4.1 given
below. However, in order to understand the trends in a better way, the relationships are
discussed next.

4.2.1 Relationship between fineness and standard consistency

The results of consistency test on samples from different factories are plotted in Figures. 4.1 to
4.5, separately. The “Coefficient of determination” (R2 value) varies from 0.7112 to 0.9585. All
graphs show an increase in the consistency with increase in fineness. Consistency indicates the
degree of density or stiffness of cement. It is the amount of water content required for a given
quantity of cement to get a cement paste of standard consistency. With the increase of fineness,
the specific surface of cement increases. As a result, more surface area is available for hydration
from the same weight of cement. So, more water will be required to produce the cement paste of
same standard consistency.

A comparison of trend lines drawn for different factories is drawn in Fig. 4.6. The comparison
shows that curves for factories A, B, and C are convex while that for factory E is concave
upward and only for factory D is uniform. It shows that increase in consistency for factories A,
B, and C decreases with increasing fineness while that for factory E increases. The different
trends obtained may be due to different sources of raw materials for different factories and
different controlling conditions in respective kilns.

82
27

26

R² = 0.9289

25
Consistency (%)

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.1 Relationship between fineness and standard consistency for cement samples of
factory A

83
27

R² = 0.9585
26

25
Consistency (%)

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.2 Relationship between fineness and standard consistency for cement samples of
factory B

84
27

R² = 0.7802
26

25
Consistency (%)

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.3 Relationship between fineness and standard consistency for cement samples of
factory C

85
27

R² = 0.9147
26

25
Consistency (%)

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.4 Relationship between fineness and standard consistency for cement samples of
factory D

86
27

26 R² = 0.7112

25
Consistency (%)

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.5 Relationship between fineness and standard consistency for cement samples of
factory E

87
27

R² = 0.9614

26 R² = 0.9197

R² = 0.7825

25
Consistency (%)

R² = 0.9098 R² = 0.9507

24
Factory A

Factory B

Factory D
23
Factory C

Factory E

22
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.6 Relationship between fineness and standard consistency of cement (comparison of
results from 5 factories)

88
In figure 4.7, an average trend of all the factories is shown. Although the correlation is not very
good (R2= 0.5543), the average trend is an increase in consistency with increasing fineness and
this increase in consistency ceases at higher values of fineness. The governing equation is found
to be:
Y = 0.0007 X + 23.115 ----------------------------------- (4.1)
Where Y stands for consistency (%) and X for fineness value (cm2/g).

27

y = 0.0007 X + 23.11
R² = 0.554
26
Consistency (%)

25

24

23

22
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.7 Relationship between fineness and standard consistency of cement samples from 5
factories

89
4.2.2 Relationship between fineness and setting time

Figures 4.8 to 4.12 show the effect of fineness of cement on setting time of cement for factories
A, B, C, D and E respectively. R2 value (Coefficient of determination) varies from 0.840 to 0.975
for initial setting time and 0.7626 to 0.8924 for final setting time. All graphs show a decrease in
setting time with increase in fineness. As with the increase of fineness, the surface area of the
cement grains increases, the surface available for hydration also increases. When water comes in
contact with this surface, the process of hydration is accelerated due to the increased surface area
and as a result, cement sets in less time. The curve for factories A, B, D and E are convex while
that for factory C is concave upward (Figures 4.13, 4.14). Here it shows that decrease in setting
time for factories A, B, D and E increases with increasing fineness while that for factory C
decreases. Also, results of factory D shows first an increase in setting time up to 2500 cm2/g,
then, a decrease.

360

Initial
320
R² = 0.8906 Final
Setting time (minute)

280

240

200 R² = 0.8825

160

120
1500 2000 2500 3000 3500 4000

FINENESS (cm2/g)

Fig. 4.8 Relationship between fineness and setting time for cement samples of factory A
90
360

Initial
Final
320

R² = 0.8924
280
Setting time (minute)

240

200
R² = 0.9049

160

120
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.9 Relationship between fineness and setting time for cement samples of factory B

91
360

Initial
Final
320

R² = 0.8323
280
Setting time (minute)

240

200

R² = 0.8137
160

120
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.10 Relationship between fineness and setting time for cement samples of factory C

92
360

Initial
Final
320
R² = 0.7626

280
Setting time (minute)

240

200

160 R² = 0.7018

120
1500 2000 2500 3000 3500 4000

FINENESS (cm2/g)

Fig. 4.11 Relationship between fineness and setting time for cement samples of factory D

93
360

Initial
Final
320

R² = 0.7778
280
Setting time (minute)

240

200

160
R² = 0.8871

120
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.12 Relationship between fineness and setting time for cement samples of factory E

94
280

R² = 0.9186
260

R² = 0.9759
240

220 R² = 0.8715

200
R² = 0.9262
IST (minute)

180

160 Factory A

Factory B
140
Factory D

120
Factory C
R² = 0.8406
100 Factory E

80
0 500 1000 1500 2000 2500 3000 3500 4000 4500

Fineness (cm2/g)

Fig. 4.13 Relationship between fineness and initial setting time of cement (comparison of
results from 5 factories)

95
320
R² = 0.932
300

R² = 0.9146
280

260
R² = 0.9339
240
FST (minute)

220
Factory A
200
Factory B
180
Factory D R² = 0.9555
160
Factory C
140 R² = 0.8791
Factory E
120

100
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.14 Relationship between fineness and final setting time of cement (comparison of
results from 5 factories)

96
The relationship between fineness and setting times for all the five factories are shown in Figs.
4.15 and 4.16. Figure 4.15 shows the initial setting times and Figure 4.16 shows that of final
setting times. It can be seen that “Coefficient of determination” is better for the final setting time
(= 0.7552) when compared to the initial setting time (= 0.6054). With the increase in fineness the
surface area per unit mass of cement increases. Since hydration starts at the surface of the
particles, it is the total surface area of cement that affects the rate of hydration and therefore the
setting time. Therefore, the setting time decreases with increase in the fineness.

After regression analysis, the governing equation are found to be:

 For Initial Setting Time

Y = - 0.037 X + 294.1 ----------------------------------- (4.2)

Where Y stands for IST (minutes) and X for fineness value (cm2/g).

 For Final Setting Time

Y = - 0.046 X + 362.1 ----------------------------------- (4.3)

Where Y stands for FST (minutes) and X for fineness value (cm2/g).

97
360

320
y = - 0.037 X + 294.1
R² = 0.605
280
Initial Settig time (minute)

240

200

160

120
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.15 Relationship between fineness and initial setting time of cement samples from 5
factories

98
360

320

y = - 0.046 X + 362.0
R² = 0.755
280
Final setting time (minute)

240

200

160

120
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.16 Relationship between fineness and final setting time of cement samples from 5
factories

99
4.2.3 Relationship between fineness and compressive strength

Figures 4.17 to 4.22 show the relationship between fineness of cement and compressive strength
of mortar cubes. Figure 4.17 & 4.18 shows that for 3 days, Figures 4.19 & 4.20 show for 7 days
and figure 4.21 & 22 show that for 28 days compressive strength. The results are in accordance
with the findings of previous researchers (Alexander, 1972; Naceri and Benia, 2006; Bentz et al.,
2008).

The increase of the fineness of cement resulted in an increase in the compressive strength . This
can be explained by the increase of the fast kinetics of hydration of the mineral C3S (tricalcium
silicate) and C2S (dicalcium silicate). These two phases are the two principal minerals which
ensure the development of the strength. The increase of the fineness of the cement clearly
improved the compressive strength of the concrete. This confirms the role of the granulometry
(mechanical activation or advanced grinding) in the fast and complete hydration of the cement.
The increase of the mechanical response as a function of the variation of the fineness
(mechanical activation) is different in different types of cement. This depends on the type and
percentage of the mineral addition (reactivity of the admixture) incorporated in the cement. Thus,
it can be concluded that the fineness of cement is a significant characteristic during the hydration
of the mix, more the particles are fine, more the cement surface in contact with water is large and
more the hydration is fast and complete (shortening of set times). The mechanism of increase in
compressive strength with an increase in fineness will be understood more precisely in the
hydration studies of cement (section 4.6).

Figures 4.17, 4.19 and 4.21 represents the comparison of trend lines of mortar compressive
strength attained from samples of five different factories for 3, 7 and 28 days respectively. Most
of the curves show that compressive strength of mortar cubes increases with increasing fineness
up to a certain fineness level and then this gain slows down in most of the cases and even
declines in some cases.

In figures 4.18, 4.20 and 4.22 an average trend of all the factories is shown for 3, 7, and 28 days
respectively. Coefficient of determination is better in case of 3-days compressive strength results
(R2 = 0.607). However, the average trend is an increase in compressive strength with increasing

100
fineness and this increase ceases at higher values of fineness. The linear regression equations are
given as follows:
Y = 0.01 X - 0.019 (for 3-days compressive strength) ------------- (4.4)
Y = 0.009 X + 10.42 (for 7-days compressive strength) ------------- (4.5)
Y = 0.01 X + 17.82 (for 28-days compressive strength) ------------ (4.6
Where Y stands for compressive strength (MPa) and X for fineness value (cm2/g).

45

R² = 0.9867
40
Factory A R² = 0.9956
Factory B R² = 0.9997
35 Factory D
Factory C R² = 0.9872
30 Factory E
Comp. Strength (MPa)

25
R² = 0.9667

20

15

10

0
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.17 Relationship between fineness and 3-days compressive strength of mortar cubes
(comparison of results from 5 factories)

101
45

40
y = 0.01 X - 0.019
R² = 0.607
Compressive Strength (MPa)

35

30

25

20

15

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.18 Relationship between fineness and 3 days compressive strength of mortar cubes
(cement samples from 5 factories)

102
60

Factory A
R² = 0.9974
Factory B
50
Factory D
Factory C
R² = 0.9952
Factory E R² = 0.9987
40
Compressive Strength (MPa)

R² = 0.9652

30
R² = 0.9462

20

10

0
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.19 Relationship between fineness and 7-days compressive strength of mortar cubes
(comparison of results from 5 factories)

103
60

y = 0.009 X + 10.42
R² = 0.453
50

40
Compressive Strength (MPa)

30

20

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.20 Relationship between fineness and 7 days compressive strength of mortar cubes
(cement samples from 5 factories)

104
70

R² = 0.999
60

R² = 0.9675

50
Compressive Strength (MPa)

R² = 0.968
R² = 0.9982

40 R² = 0.943

Factory A
30
Factory B
Factory D
Factory C
20
Factory E

10
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.21 Relationship between fineness and 28-days compressive strength of mortar cubes
(comparison of of results from 5 factories)

105
70

60
y = 0.01 X + 17.82
R² = 0.562

50
Compressive Strength (MPa)

40

30

20

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.22 Relationship between fineness and 28 days compressive strength of mortar cubes
(cement samples from 5 factories)

106
4.3 Variation in chemical and compound composition of cement

Chemical composition of all samples was analyzed by XRF Cement Spectrometer/Cement X-


Ray Analyzer. Their oxide and compound compositions are given in Table 4.2 & 4.3.

Table 4.2 Oxide and compound composition of cement from different factories

Fineness Chemical Composition (%)


Factory
(cm2/g) SiO2 Al2 O3 Fe2 O3 CaO MgO Na2O SO3 K2O TiO2 Mn2O3
2065 21.58 5.29 3.15 63.28 1.79 0.23 2.67 0.85 0.32 0.04
A 2495 21.48 5.26 3.13 62.85 1.77 0.24 2.60 0.84 0.31 0.05
3048 21.60 5.37 3.20 63.27 1.79 0.24 2.72 0.87 0.32 0.04
3355 21.54 5.33 3.16 62.85 1.80 0.24 2.64 0.86 0.32 0.04
3741 21.56 5.31 3.18 62.95 1.82 0.24 2.66 0.85 0.32 0.05
1690 20.34 5.28 3.01 62.10 2.64 0.28 2.46 0.98 0.34 0.04
2083 20.29 5.25 2.97 62.03 2.63 0.28 2.49 0.99 0.33 0.04
B 2556 20.32 5.28 2.99 62.17 2.62 0.29 2.46 0.99 0.33 0.04
2912 20.28 5.28 2.99 62.09 2.64 0.28 2.54 0.99 0.33 0.04
3315 20.29 5.26 3.00 62.04 2.62 0.27 2.51 0.98 0.33 0.04
3773 20.27 5.26 3.01 61.89 2.59 0.28 2.58 0.99 0.33 0.04
1548 20.72 5.52 3.28 63.55 1.50 0.28 2.69 0.93 0.33 0.04
2048 20.70 5.50 3.30 63.67 1.52 0.29 2.67 0.93 0.31 0.04
C 2468 20.76 5.54 3.32 63.45 1.50 0.28 2.55 0.92 0.34 0.04
2964 20.78 5.56 3.32 63.65 1.52 0.29 2.51 0.93 0.33 0.05
3476 20.76 5.54 3.28 63.55 1.50 0.28 2.46 0.93 0.32 0.04
3883 20.80 5.52 3.26 63.65 1.50 0.28 2.44 0.93 0.33 0.04
1661 21.36 5.15 3.34 68.75 1.69 0.28 2.31 0.74 0.32 0.03
2028 21.48 5.13 3.34 63.85 1.68 0.28 2.32 0.75 0.32 0.04
D 2580 21.32 5.12 3.31 63.89 1.67 0.28 2.28 0.75 0.32 0.03
3033 21.36 5.10 3.35 63.62 1.71 0.28 2.28 0.74 0.32 0.03
3369 21.32 5.10 3.34 63.48 1.72 0.28 2.28 0.75 0.32 0.04
3674 21.38 5.10 3.34 63.53 1.71 0.28 2.27 0.76 0.32 0.04
1620 20.85 5.64 3.65 62.42 2.44 0.28 2.18 0.85 0.34 0.04
1945 20.76 5.57 3.70 62.05 2.41 0.26 2.59 0.85 0.33 0.04
E 2495 20.89 5.55 3.69 61.89 2.41 0.34 2.58 0.84 0.33 0.04
2860 20.88 5.51 3.65 61.90 2.43 0.32 2.67 0.84 0.33 0.04
3380 20.87 5.53 3.63 61.68 2.47 0.31 2.87 0.84 0.33 0.04
3727 20.90 5.36 3.56 62.13 2.39 0.35 2.74 0.78 0.33 0.04

107
Table 4.3: Chemical composition of test samples prepared for hydration studies

Sr. Fineness Chemical Composition (%)


2
No. (cm /g) SiO2 Al2 O3 Fe2 O3 CaO MgO Na2O SO3 K2O CI LOI LSF SIM ALM C3S C 2S C3A C4AF
1 3000 21.52 5.97 3.38 62.66 2.36 0.36 2.17 0.78 0.003 1.55 87.98 2.30 1.77 40.41 31.21 10.10 10.28

2 3100 21.63 6.04 3.40 63.06 2.37 0.35 2.07 0.78 0.002 1.51 88.14 2.29 1.78 40.99 31.09 10.25 10.34

3 3200 21.29 5.54 3.73 63.92 2.35 0.29 1.82 0.73 0.00 1.48 91.36 2.30 1.49 50.67 22.81 8.37 11.34

4 3300 20.87 5.41 3.65 63.23 2.24 0.31 2.73 0.71 0.00 1.93 91.26 2.30 1.48 49.45 22.53 8.16 11.10

5 3450 20.37 5.17 3.45 62.95 2.13 0.29 2.50 0.71 0.00 3.53 93.61 2.36 1.50 54.66 17.16 7.86 10.

108
4.4 Effect of variation in fineness of cement on properties of concrete

The results of concrete testing are summarized in Table 4.3 given below. The nominal
concrete mix. ratio was taken as 1:2:4 and water cement ratio as 0.65 for all trials, as
mostly taken in the normal construction works in Pakistan.

Table 4.4: Results of concrete testing

3-DAY’S 7-DAY’S 28-DAY’S


FACTORY FINENESS SLUMP COMPRESSIVE COMPRESSIVE COMPRESSIVE
(cm2/g) (mm) STRENGTH STRENGTH STRENGTH
(MPa) (MPa) (MPa)
1525 14 3.19 6.89 14.21
2065 44 7.62 12.23 21.40
A 2459 61 9.48 15.29 21.51
3048 62 9.57 15.67 21.75
3355 62 9.67 15.86 22.17
3741 120 9.90 16.97 22.26
1690 1 4.45 7.68 14.64
2084 7 7.61 11.94 18.20
B 2526 20 11.38 18.01 21.24
2912 20 11.74 19.30 24.70
3315 20 13.35 23.33 29.92
3773 40 13.13 24.11 36.17
1548 25 10.63 10.63 19.70
2048 30 18.66 18.66 28.13
C 2468 40 20.27 18.89 24.54
2964 40 20.53 20.53 33.30
3476 40 22.53 22.53 33.26
3883 80 22.68 22.68 31.11
1661 2 14.49 16.93 19.81
2028 5 18.38 21.39 31.00
D 2580 8 18.80 24.76 32.22
3033 12 24.12 26.81 34.92
3369 20 25.30 29.21 38.66
3674 22 27.06 30.75 39.72
1620 11 6.45 11.19 13.78
1945 22 12.48 16.07 21.66
E 2495 33 14.74 19.80 26.69
2860 34 11.40 13.99 20.24
3380 36 17.98 21.09 29.26
3727 66 17.54 24.22 31.64

109
4.4.1 Workability

A concrete which can be quickly compacted, is said to be workable. Also workability


measures the ease of placement and the resistance to segregation. As per ACI definition,
“That characteristic of freshly mixed concrete or mortar, which measures the ease and
homogeneity with which it can be mixed, placed, consolidated and finished (ACI 318-
06)”. According to previous research (Kwan Wong 1995, Neville 1995, Higginson
1970Price 1951, U.S. Bureau of Reclamation 1956, and Wuhrer et al. 1950), the effect of
fineness on workability is controversial. However, our results show an increase in
workability with the increase in fineness. It can be better understood with the fact that the
increase in fineness is associated with increased cohesion and reduced bleeding. Also,
very fine cements produce a fat and sticky concrete.

As already mentioned, with increase in the fineness of cement, both consistency of


cement and workability of concrete increase. Increase in consistency means increase in
water demand to get cement paste of standard consistency while increase in workability
means increase in flowability at the same water/cement ratio. In other words decrease in
water demand to get the same degree flowable concrete. Apparently it looks to give a
controversial situation. But it can be more easily understood by considering that
workability of concrete determines the amount of work done to achieve a certain value of
compaction. When water is added, it wets the surface of particles and reduces the inter-
particle frictional resistance. When fineness of cement increases beyond a certain particle
size, the particles of cement itself starts acting as lubricants in the concrete. Therefore,
the particles flow and less effort/work is required for compaction of concrete i.e. the
water demand decreases to obtain the same degree of workability.

In case of consistency of cement, no work is done on the cement paste, instead water
addition in the cement converts it in the paste form and softness of this paste measured in
a standard manner gives the standard consistency. A certain quantity of water is required
to wet surface area of all particles in the cement sample taken. More the fineness, greater
will be the surface area of cement particles and thus greater water will be required to wet

110
this surface area. Hence, with increasing fineness of cement, water demand increases, i.e.
consistency increases which is one of our findings.

Workability of concrete was assessed by the slump test. Figure 4.23 represents a
comparison of curves for all factories. It can be noticed that for almost all the factories,
slump increases with an increase in fineness up to about 2500 cm2/g, after which the
slump remains constant up to about 3400 cm2/g. Then, if fineness is further raised, there
occurs a sudden rise in the slump (Fig. 4.23).

It is obvious that fineness has a pronounced effect on the water demand of concrete.
Figures 4.24 indicates that with an increase in fineness, the average trend is an increase in
slump (although correlation factor is very low) and ultimately in workability of concrete.

The governing equation is found to be:

Y = 0.02 X – 22.66 ---------------------------------- (4.7)

Here Y stands for Slump of concrete (mm) and X for fineness of cement (cm2/g).

111
120 Factory A

Factory B

Factory D
100
Factory C

Factory E
80
Slump (mm)

60

40

20

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500

Fineness (cm2/g)

Fig. 4.23 Relationship between fineness and concrete slump


(comparison of results from 5 factories)

112
120

100 y = 0.020 X - 22.66


R² = 0.355

80
Slump (mm)

60

40

20

0
1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.24 Relationship between fineness and concrete slump (cement samples from 5
factories)

113
4.4.2 Compressive Strength

Figures 4.25, 4.27 and 4.29 represents the comparison curves of fineness versus
compressive strength of concrete cubes for different factories at the curing age of 3, 7 and
28 days respectively. Figures 4.26, 4.28, 4.30 show the relationship between the fineness
and compressive strength of concrete. The same discussion as already given in section
4.2.3 for compressive strength of mortar cubes will also be applicable here. With the
increase in fineness, setting time decreases i.e., cement paste hardens in less time. As a
result, with increasing fineness, the compressive strength also increases.

Most of the curves show that compressive strength of concrete cubes increases with
increasing fineness up to a certain fineness level (i.e., 3200 cm2/g) and then this gain
slows down in most of the cases and even declines in some cases.

In Figures 4.26, 4.28 and 4.30, an average trend of all the factories is shown for 3, 7, and
28 days respectively. The Coefficient of determination in case of 3-days compressive
strength is greater (R2 = 0.521) as compared to 7 and 28 days compressive strength,
which is 0.505 and 0.481 respectively. However, the average trend is an increase in
compressive strength with increasing fineness and this increase ceases at higher values of
fineness.

The governing equations are found to be:

Y = 0.003 X + 1.454 (for 3-days compressive strength) ----------- (4.7)


Y = 0.005 X + 3.512 (for 7-days compressive strength) ----------- (4.8)
Y = 0.006 X + 8.034 (for 28-days compressive strength) ----------- (4.9)

Where Y stands for compressive strength (MPa) and X for fineness value (cm2/g).

114
30

Factory A
R² = 0.9549
Factory B
25
Factory C
Factory D
20 Factory E
Compressive Strength (MPa)

R² = 0.7435

15
R² = 0.9277
R² = 0.9854
10
R² = 0.9636

0
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.25 Relationship between fineness and 3-days compressive strength of concrete
cubes (comparison of results from 5 factories)

115
20

18 y = 0.003 X + 1.454
R² = 0.521
16

14
Compressive Strength (MPa)

12

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.26 Relationship between fineness and 3-days compressive strength of concrete
cubes (cement samples from 5 factories)

116
35

Factory A

30 Factory B R² = 0.9895
Factory D
Factory C R² = 0.9878
25
Factory E R² = 0.9311
Compressive Strength (MPa)

R² = 0.9221
20

R² = 0.9663
15

10

0
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.27 Relationship between fineness and 7-days compressive strength of concrete
cubes (comparison of results from 5 factories)

117
35

30 y = 0.005 X + 3.512
R² = 0.505
Compressive Strength (MPa)

25

20

15

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.28 Relationship between fineness and 7-days compressive strength of concrete
cubes (cement samples from 5 factories)

118
45

Factory A
40 Factory B
R² = 0.9078
Factory D
R² = 0.9977
35 Factory C
Factory E R² = 0.7883
Compressive Strength (MPa)

30

R² = 0.7412
25

R² = 0.8705
20

15

10
1000 1500 2000 2500 3000 3500 4000 4500 5000

Fineness (cm2/g)

Fig. 4.29 Relationship between fineness and 28-days compressive strength of


concrete cubes (comparison of results from 5 factories)

119
45

40
y = 0.006 X + 8.034
R² = 0.481
35
Compressive Strength (MPa)

30

25

20

15

10

0
0 1000 2000 3000 4000 5000

Fineness (cm2/g)

Fig. 4.30 Relationship between fineness and 28-days compressive strength of


concrete cubes (cement samples from 5 factories)

120
4.5 Grinding time for samples in laboratory ball mill

1. Figure 4.31 shows the variation of “Grinding Time” taken by ball mill for preparation
of test samples with increasing fineness for factories A, B, D and E respectively. R2
value varies from 0.990 to 0.999. All graphs show an increase in the grinding effort
with increase in fineness values.


2. All curves are somewhat flat at lower fineness levels and show a gradual steepness
towards increasing finesses indicating increasing grinding requirement and hence
increased cost. However clinker of factory B required more grinding as compared to
that of others (Figure 4.31) which may be due to different sources of raw materials for
different factories and different controlling conditions in respective kilns.

3. Factory C is not included in the comparison Figure, as its ball mill was of different
shape and size as compared to others.

4. The power consumed in case of commercial grinding of clinker in plants for an


average fineness value of 3000 cm2/g is approximately 35 kcal/ton. Presently the cost
per kcal consumption of power is about PKR. 8.5, resulting in a grinding cost of Rs:
297.5 per ton or Rs: 297.5 x 106 per million ton. It has been observed that with an
increase in fineness value more grinding is required resulting in more grinding cost
per million ton which becomes more and more at higher values of cement fineness.
This increase in grinding cost is augmented due to increased wear and tear of grinding
media and mill lining at higher values of fineness of cement.

121
1600

Factory A
1400

Factory B

Factory D
1200

Factory E
Grinding Time (min)

1000

800

600

400

200

0
1000 1500 2000 2500 3000 3500 4000

Fineness (cm2/g)

Fig. 4.31 Fineness versus grinding time for samples in laboratory ball mill
(comparison of results from 4 factories)

122
4.6 Heat of hydration

Heat of hydration, at 3-days age for all samples collected from vertical rolling mill of an
industrial plant with different blaine values, was measured as per BS 4550: Part 3:
Section 3.8. Results are given in Table 4.4 and plotted versus fineness values in Fig. 4.32.

Results show that with an increase in fineness of cement, more heat of hydration is
liberated, which indicates an accelerated hydration of cement and ultimately an increased
compressive strength. An abnormal value of heat of hydration is attained at 3200 cm2/g.
It will be explained in next section i.e., 4.7, in lieu of TG loss and compound composition
of cement samples.

Table 4.5: Results of 3-days heat of hydration tests on plant collected samples

Sr. SAMPLE FINENESS AGE HEAT OF


NO. (cm2/g) (days) HYDRATION
(kcal/kg)
1 A 3020 3 69.76
2 B 3130 3 71.91
3 C 3200 3 83.49
4 D 3300 3 75.99
5 E 3450 3 76.34

123
89

H.O.H (kilocal/kg) 86

83

80

77

74

71

68

65
2900 3000 3100 3200 3300 3400 3500 3600

Fineness (cm2/g)

Fig. 4.32 Blaine fineness values versus heat of hydration of plant collected samples

4.7 Hydration studies (DTA/TGA Tests)

Hydration studies were carried out by DTA/TGA tests at 3-days age for samples
collected from grinding mill of a plant. Reports of TGA/DTA tests are given in Figures
4.33 to 4.37. The values of TG loss thus attained along with onset and offset
temperatures, point of reaction, heat change are given in Table 4.5. TG values are plotted
versus Blaine values in Figure 4.38. The increase in 3-days (early) compressive strength
with increase in blaine values of cement was further evaluated by augmenting with the
help of allied techniques of Differential Thermal Analysis (DTA) and Thermo
Gravimetric Analysis (TGA), which helped to find out hydration behavior of cement at
different blaine values. DTA/TGA studies were carried out on samples after stopping
hydration at 3-days age by crushing them manually and then washing with acetone and
ultimately drying at room temperature.

124
Tablee 4.6: Resullts of DTA/T
TGA tests

Samp
ple Blaine Value 3-D
Days T.G. Temperaature P
Point of M
Max/M Heat
Loss (Co) R
Reaction in C
Change
m2/g)
(cm (%) Onset Offset (Co) (Co) µVs/mg)*

A 3000 0.77 439.9 471.1 444.0 459.5 --8.5225

B 3100 1.45 439.2 468.8 444.1 456.4 -11.3329

C 3200 2.23 431.6 473.5 439.7 458.5 -22.4219

D 3300 1.68 432.7 468.1 439.3 452.4 -16.2111

E 3450 1.69 437.9 472.2 443.5 458.2 -19.9011

* Miccro volts perr milligram

Fig.
F 4.33 DT ple blaine 30000 cm2/g
TA/TGA results – samp

125
Fig. 4.34 DTA/TGA results – sample bllaine 3100 ccm2/g

126
ple blaine 32200 cm2/g
TA/TGA results – samp
Fig. 4.35 DT

127
Fig. 4.36 DT ple blaine 33300 cm2/g
TA/TGA results – samp

128
Fig. 4.37 DT ple blaine 34450 cm2/g
TA/TGA results – samp

129
2.5

2
T.G. LOSS (%)

1.5

0.5
2900 3000 3100 3200 3300 3400 3500 3600
Fineness (cm2/g)

Fig. 4.38 Blaine fineness values versus TG loss at 3-days age

The chemical composition of cement was almost same with some exemptions. Hence the
only variable, which might appear in the hydration behavior, was blaine value (fineness).
In this regard, cement paste of standard consistency was made for all samples. After 3
days curing, the samples were ground and washed with acetone to stop their hydration.
Each sample was then subjected to DTA/TGA studies. In hydration of cement, the C3S
and C2S contents react with water to form Ca(OH)2.

C3S + H2O CSH + Ca(OH)2 --------- (4.11)


C2S + H2O CSH + Ca(OH)2 --------- (4.12)

130
The TGA/DTA tests showed that formation of Ca(OH)2 (related to TG loss) increased
with an increase in blaine value at 3 days age. The amount of calcium hydroxide released
at 3 days age is found lowest for cement A whereas highest at cement from source E. The
cement from source A releases less calcium hydroxide at 3 days age due to lowest value
of its Blaine. Gain in strength of cement depends on the fineness/blaine value of cement.
Higher the fineness of cement, greater will be the development of strength. This is clear
from the TG loss in all cement samples which increased when Blaine value was
increased.

For 3-days hydration, the amount of Ca(OH)2 is maximum for cement E (blaine value
3450 cm2/g) and minimum in case of cement A (Blaine value 3000 cm2/g). However,
values of 3-days compressive strength of cement mortar at 3200 cm2/g (sample C) and
3450 cm2/g (sample E) were found to be somewhat abnormal. For sample C value is
excessively large while for sample E, it is somewhat lesser.

Table 4.7: Summary of physical and chemical testing at 3-days age for plant collected
samples

SAMPLE BLAINE 3-DAYS T.G. C3S HEAT OF


VALUE COMPRESSIVE LOSS CONTENT HYDRATION
STRENGTH
(cm2/g) (MPa) (%) (%) (Kcal/Kg)
A 3020 19.06 0.77 40.41 69.76
B 3130 21.37 1.45 40.99 71.91
C 3200 27.13 2.23 50.67 83.49
D 3300 24.58 1.68 49.45 75.99
E 3450 22.78 1.69 54.66 76.34

As far as sample C is concerned, C3S content is also large as compared to samples A and
B. Thus C3S content dominates over increased fineness and results in high compressive
strength. The same is verified from high TG loss and Heat of Hydration values for sample
C given in Table 4.7.

In case of sample E, C3S and Heat of hydration values are highest as compared to other
samples but compressive strength value is found to be lesser which is contrary to our

131
previous argument. The physical appearance of the paste sample indicated small cracks
showing improper hydration. The same is also confirmed from low TG loss for sample E.
That is why the strength in case of sample E is lesser than sample D.

4.8 Comparison of plant collected versus laboratory ground samples

 In plant collected samples grain size distribution is narrow as compared to the


samples prepared in laboratory by grinding cement clinker with gypsum in phase
one.
 This is the reason that compressive strength in plant collected samples is
comparatively higher as compared to laboratory prepared samples.
 In case of plant collected samples blaine variation (3000 to 3450 cm2/g) is not too
wide as compared to laboratory prepared samples (1548 to 3883 cm2/g), as only
practical blaine values were available while collecting samples from plant.

132
CHAPTER 5

CONCLUSIONS & RECOMMENDATIONS

133
5.1 Conclusions

The following conclusions have been drawn from the results presented and discussed in
this thesis.

(i) The consistency of cement as well as compressive strength of mortar cubes increase
while setting time decreases with increasing fineness of cement.

(ii) The workability of concrete increases with an increase in cement fineness. However there
is no remarkable increase in the workability from 2600 to 3400 cm2/g.

(iii) The compressive strength of concrete increases with the increase in the fineness of
constituent cement provided other factors remain constant. However, this increase in
strength is prominent up to 3200 cm2/g. After 3200 cm2/g, rate of increase of strength is
slowed down apparent from curves of individual factories. The same is verified with the
help of DTA/TGA tests and Heat of Hydration tests also.

(iv) Increase in compressive strength with increasing fineness/blaine values, in case of plant
collected cement, is comparatively higher than that of lab cement. The is due to narrow
grain size distribution in case of industrial cement as compared to wider distribution in
laboratory ground cements.

(v) The effect of cement properties, investigated by using indigenous materials, on properties
of concrete are well in accordance with the previous research carried out internationally
on foreign cements.

134
5.2 Recommendations

Based on the research presented in this thesis the following recommendations are
presented for cement industry:
(i) As far as strength of cement is concerned, a fineness of 3200 cm2/g may be considered as
optimum value. Generally, for the fineness range of 1600 - 3200 cm2/g, increase in
strength is 78.8 % associated with an increase in grinding time/cost is 60 %. While from
3200 – 3700 cm2/g, grinding time/cost is 40 % while gain of strength is only 21.2 %.

(ii) This study shows that workability of concrete increases with cement fineness. However,
workability can also be improved by increasing water cement ratio. As the strength of
cement/concrete decreases with an increase in water cement ratio. So in order to have a
more workable concrete without compromising on strength, more fine cement may be
preferred rather than to increase the water cement ratio.

(iii) If workability is the prime factor on a project, it is recommended that fineness should not
exceed 2500 cm2/g because after this value there is no prominent increase in workability.
However, if fineness is raised above 3400 cm2/g, workability can be further improved but
with high grinding cost, thus, it will render the concrete uneconomical due to high
grinding cost. So, other techniques e.g., use of admixtures to improve workability, may
be practiced.

135
5.3 Recommendations for future research

(i) The cement factories covered in the research work belong to northern region of
Pakistan. The research work may be extended up to southern region also.

(ii) The following properties of concrete may also be investigated by varying


properties of cement:

(a) Dimensional stability


(b) Transport properties
(c) Durability
(d) Permeability
(e) Tensile strength
(f) Flexural/bending strength

(iii) Only normal strength concrete is discussed in the research work. High strength
concrete, which is commonly used in modern construction projects, may also be
included in the research.

(iv) Only Portland cement is focussed in the research work. Some other types of
cements may also be included in the investigation.

(v) Coarse aggregates from Margalla hills and fine aggregates from Lawrencepur site
were used throughout in the research. Future scholars are advised to use coarse
and fine aggregates from other sources also.

(vi) Future scholars are also advised to work on statistical modelling involved in the
cost comparison of increase in workability by increasing fineness or by using
admixtures.

136
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