Dissertation Mgeta 2018 Final

学校代码: 10491 研究生学号: 1201590078
中国地质大学
硕士学位论文
二氧化硅纳米粒子对提高油井水泥混凝土抗压
强度的影响
姓名: Mgeta Faustine Sabe

学科专业: 石油和天然气工程
指导教师: 教授 Gu Jun
培养单位: 地球资源
中国地质大学
武汉 430074 中国
日期: 2018年5月
School Code: 104971. Student ID: 1201590078
A Dissertation Submitted to China University
of Geosciences for the Master Degree in Oil and Natural Gas

Engineering
The Influence of Silica Nano-particles in

Improving Compressive Strength of Oil Well
Cement
Student Name: Mgeta Faustine Sabe

Major: Oil and Natural Gas Engineering
Supervisor: Professor Gu Jun
College: Earth Resources
China University of Geosciences

Wuhan 430074 P. R. China
Date: May 2018
The Originality Statement for Dissertation of China
University of Geosciences (Wuhan)
I solemnly declare that the dissertation I submitted "to the University of
Geoscience (Wuhan)" is my independent research which is achieved under the
guidance of supervisors and during my graduate student stage. In this dissertation,
there are not others’ works and publications except for the parts that are noted and
cited specially. I extend my gratitude to the persons who provide help for my
dissertation writing.
I commit that this dissertation I submitted conforms academic ethics and academic
standards, and I will undertake the legal liability and legal consequences resulting
from academic infringement of this dissertation.
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Date: ………………………………
China University of Geosciences (Wuhan) Graduate
Thesis Supervisor Commitment Statement
I solemnly promise that this post graduate master’s degree thesis in the
Influence of Silica Nano-particles in Improving Compressive Strength of Oil
Well Cements is the result of independent research conducted by the graduate
student at the China University of Geosciences (Wuhan) under my supervision.
A paper was independently completed by a master’s graduate student.
The dissertation submitted by a master’s graduate student did not violate academic
ethics and academic standards. There was no infringement, and I’m ready to bear
the related responsibilities and consequences.
……………………………..
Professor Gu Jun
(Supervisor)
Date:……………………….
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Author Introduction
Basic information
Name: Mgeta Faustine Sabe Nationality: Tanzanian Birth Date: 1985-04-06
Native Place: Nyamagana City: Mwanza
2015-2018: China University of Geosciences (Wuhan)
Program: Masters of Oil and Natural Gas Engineering
2007-2011: University of Dar es salaam (Tanzania)
Program: Bachelor of Science in Electromechanical Engineering
2006.7 – 2006.8: Butimba Teachers College
Program: Certificate of Education in Physics and Mathematics
Research program
2017-2018: China university of geosciences -Wuhan
Research Title: The Influence of Silica Nano-particles in Improving Compressive

Strength of Oil Well Cement
Role Played: Author
2010-2011: Innovation and Technology Center (INTEX)– Tanzania
Research Project Tile: Designing and Implementation of an Automatic Control System

for Controlling Grain Level in A Hopper
Role Played: Designer and Project Engineer

Dedication
I dedicate this work to my mother and fiancée. Thank you for all your
encouragement, support and love. And to my Father, who is no longer
with me, thank you for imparting your discipline and persistence toward
distinction within me which made me the man that I am today. This
detection would be worthless without all of your love.
摘要
具有纳米二氧化硅粒子添加剂的 G 类波兰水泥是由少量干重为 1.0％至 4.0％纳米二氧

化硅粒子与 G 类波兰水泥和其他水泥添加剂形成的混合物。此类水泥既可用于正常情况，
也可用于高温下，适用于深井。
本实验所用样品为水，G 类油井水泥和纳米二氧化硅粒子材料混合制成的水泥立方体。
使用水灰比相同的的水泥浆（w / c = 0.45），在 TG-3060 恒速搅拌器中搅拌水泥浆，然后
将混合均匀的水泥浆倒入 5cm×5cm×5cm 的模具中制备样品。本研究中使用的水泥添加剂
是质量分数为 1.2％的失水剂和 0.5％的分散剂。搅拌量是根据美国石油学会（API）水泥
和固井材料规范 1A 确定的。
在该研究中，通过添加不同百分比含量的 20-30nm 的纳米二氧化硅材料来研究强度。

用 0.0％，1.0％，2.0％，3.0％和 4.0％重量的二氧化硅纳米颗粒代替水泥。为此实验研究
准备了约 60 个样品，使用 5cm×5cm×5cm 尺寸的模塑材料来模拟水泥立方体。
为使水泥硬化并测量其抗压强度，将样品在 80℃温度下养护 3 天，7 天，15 天和 28

天。用万能试验机确定计算抗压强度所需的压缩载荷。最后，将压缩载荷除以立方体的表
面积以获得抗压强度。分别对含有和不含纳米二氧化硅的两种样品进行测试以观察二氧化
硅纳米粒子对水泥强度的影响。
i
实验结果表明，含纳米二氧化硅颗粒的样品在养护 3、7、15 和 28 天的抗压强度均高
于对照组(不含纳米二氧化硅)，但纳米二氧化硅含量分别为 1.0%和 4.0%的样品养护 7 天
后，抗压强度均低于对照组(不含纳米二氧化硅)。
经过 28 天养护的对照样品(不含纳米二氧化硅)和加入不同比例纳米二氧化硅的抗压
强度值最高，养护时间分别为 15、7 和 3 天时的抗压强度逐渐减小，养护时间为 3 天时的
抗压强度最低。
研究指出，在水泥浆体中添加一定量的纳米二氧化硅材料有助于提高水泥浆体的强
度，超过最大值后增加纳米二氧化硅材料的含量会导致水泥抗压强度减小。当质量分数为
4.0％的纳米二氧化硅颗粒掺入到水泥浆中时，可以观察到抗压强度降低的现象。
本试验中，达到最大抗压强度的最佳比例为固化 28 天后的 3.0wt.%纳米二氧化硅，

这表明随着养护时间的增加和一定量纳米二氧化硅材料的加入，水泥的抗压硬度得到了提
高。
结果表明，纳米二氧化硅材料的加入会提高水泥的抗压强度，因此，建议在水泥浆中
加入 3.0wt.%的纳米二氧化硅材料，养护 28 天，以此达到最大抗压强度。值得注意的是，
纳米二氧化硅颗粒百分比的小幅度调整可以引起抗压强度的剧烈变化。为根据要求调整水
泥强度，应对纳米二氧化硅的加入进行精确的控制。
关键词：纳米二氧化硅，纳米材料，抗压强度，养护时间。
ii
Abstract
The Portland cement Class G with silica nanoparticles additive applications is a mixture of small
amount of silica nanoparticles powder of about 1.0% to 4.0% by dry weight, with Portland
cement class G and other cement additives forming the balance of the mixture. The cement so
formed is suitable for use in deep petroleum wells, which require cement that can be introduced
under either normal or high temperature conditions.
This study makes use of the mechanical strength cement cubes made up by mixing of water, oil
well cement class G and silica nanoparticles materials. Cement pastes with the same water to
cementitious ratio is used (w/c= 0.45). The cement slurry was properly mixed in the TG-3060
Constant speed blender. The well mixed cement slurry was then poured into molds to form the
cubes of the size 5cm x 5cm x 5cm. The cement additives used in this study are 1.2 wt.% fluid
loss agent and 0.5wt.% dispersant. Mixing quantities were determined according to American
Petroleum Institute’s (API) Specification 1 A for Cements and Materials for Well Cementing.
In this study the strength is investigated using a number of samples containing different
percentage quantity of silica nanoparticles materials with Nano-size of 20-30 nm. The cement
was replaced by silica nanoparticles of 0.0%, 1.0%, 2.0%, 3.0% and 4.0% by weight. About 60
samples were prepared for this experimental study whereby the molding materials of 5cm x 5cm
x 5cm dimensions were used to simulate the cement cubes.
In order for the cement cubes to harden and gain its compressive strength, the samples were
cured at 80 ℃ temperature for 3, 7, 15 and 28 days. The Universal testing machine was used to
determine the compressive load used to calculate compressive strength. Finally, the compressive
load was divided by the surface area of the cube to obtain the Compressive strength. This test
was performed to both samples with and without silica nanoparticles to observe the influence of
silica nanoparticles on cement bonding strength.
The results of the experiment discovered that, the samples containing Nano silica particles
revealed higher compressive strength compared to the control samples (without Nano silica) for
iii
all curing time of 3, 7, 15 and 28 days excluding the case where Nano silica content were 1.0%
and 4.0% by weight after both being cured for 7 days which produced low compressive strength
compared to the control samples (without Nano silica).
The highest compressive strength values of the sample cubes were observed at the curing time of
28 days for both control samples (without Nano silica) and samples incorporating different
percentages of Nano silica particles while least values of compressive strength revealed at the
curing time of 3, 7 and 15 days respectively in which the lowest compressive strength was
recorded at curing time of 3days.
It was observed that, adding more percentages of Nano silica material to the cement slurry is
important in increasing strength of cement paste to a certain limit after that any increase in the
percentage of Nano silica material will cause to a decrease in the compressive strength of the
hardened sample. This phenomenon of decrease in compressive strength was been observed
when 4.0 wt. % of Nano silica particles was incorporated to the cement slurry.
The optimal percentages of Nano silica material which is required to attain a maximum
compressive strength for this experimental study was 3.0 wt.% after been cured for 28 days, this
indicates that hardness of the cement paste depends in increase in curing time and incorporation
of a certain amount of Nano silica materials for improvement of the compressive strength of the
hardened cement paste.
Nano silica materials was proved to influence the improvement of compressive strength of a
hardened cement paste when is added to the cement slurry, therefore for this experiment it is
recommended to incorporate an optimum of 3.0 wt.% of Nano silica materials in the cement
slurry and the sample should be cured for the age of 28days in order to achieve the maximum
compressive strength and it should be noted that small adjustment in the percentage of Nano
silica particles can cause to the intense changes in the compressive strength in which high level
of quality control should be reached in order to control these adjustment as required.
Key words: Nano silica, Nanoparticles, Compressive Strength, Curing Time
iv
Table of Content
摘要.................................................................................................................................................. i
Abstract .......................................................................................................................................... iii
Table of Content ............................................................................................................................. v
List of Figures .............................................................................................................................. viii
List of Tables .................................................................................................................................. x
Nomenclature ................................................................................................................................. xi
Chapter 1: Introduction ................................................................................................................... 1
1.1 Background ........................................................................................................................... 1
1.1.1 Nano silica Material........................................................................................................ 3
1.2 Research Problem Statement ................................................................................................. 4
1.3 Research Aims and Significance ........................................................................................... 5
1.3.1 General Objective of the Research ................................................................................. 5
1.3.2 Specific Objectives of the Research. .............................................................................. 5
1.3.3 Significance of the Research Study ................................................................................ 6
1.3 Structure of the Research Study ............................................................................................ 6
Chapter 2: Literature Review .......................................................................................................... 8
2.1 Oil Well Cementing Operations ............................................................................................ 8
2.1.1 Well Cementing Process ................................................................................................. 9
2.1.2 The Purposes for Well Cementing................................................................................ 10
2.1.3 Complications in Well Cementing ............................................................................... 12
2.2. Ordinary Portland Cement .............................................................................................. 14
2.2.1 Portland Cement Composition...................................................................................... 15
2.2.2 Portland Cement Clinker Stages ................................................................................... 16
2.2.3 Types of Portland Cements........................................................................................... 17
2.3 Cement Hydration Reaction ................................................................................................ 19
2.3.1 Hydration of Pure Clinker Stages ................................................................................. 20
2.3.2 Phases of Cement Hydration ........................................................................................ 22
v
2.3.4 Heat of Hydration ......................................................................................................... 25
2.3.5 Hydration Products ....................................................................................................... 25
2.4 Oil Well Cement.................................................................................................................. 28
2.4.1 Features of Oil Well Cements ...................................................................................... 29
2.4.2 Oil Well Cement Grades and Types ............................................................................. 29
2.5 Cement Admixtures............................................................................................................. 32
2.5.1 Cement Chemical Admixtures...................................................................................... 33
2.5.2 Cement Mineral Admixtures ........................................................................................ 39
2.6 Nanotechnology .................................................................................................................. 41
2.6.1 Pozzolans Materials ...................................................................................................... 42
2.6.2 Micro silica Particles .................................................................................................... 43
2.6.3 Nano silica Particles ..................................................................................................... 50
Chapter 3: Experimental Setup and Procedures............................................................................ 56
3.1 Introduction ......................................................................................................................... 56
3.2 Experimental Materials ....................................................................................................... 56
3.3 Experimental Instruments ................................................................................................... 57
3.4 Experimental procedures ..................................................................................................... 58
3.4.1 Preparation of Samples ................................................................................................. 59
3.4.2 Curing of Experimental Samples .................................................................................. 62
3.4.3 Compressive Load Test ................................................................................................ 63
3.4.4 Compressive Strength Calculations .............................................................................. 65
Chapter 4: Results and Discussions .............................................................................................. 66
4.1 Introduction ......................................................................................................................... 66
4.2 Compressive Strength Test Results ..................................................................................... 66
4.3 Compressive Strength Test Analysis................................................................................... 69
4.3.1 Influence of Nano Silica on Compressive Strength of Cement Paste .......................... 69
4.3.2 The Effect of Nano silica to the Compressive Strength of Cement Paste .................... 70
4.3.3 Summary of the Effects of Nano silica on Compressive Strength of the Cement Paste.
............................................................................................................................................... 77
4.3.4 Effect of Curing Time on Compressive Strength of Cement Paste .............................. 79
vi
4.3.5 Summary of the effect of curing time on the compressive strength of the cement paste.
............................................................................................................................................... 84
Chapter 5: Conclusions and Recommendations ........................................................................... 85
5.1 Conclusions from the Experimental Results ....................................................................... 85
5.2 Recommendations for the industry application ................................................................... 86
5.3 Recommendations for the future research study ................................................................. 87
Acknowledgement ........................................................................................................................ 88
References ..................................................................................................................................... 89
Appendices .................................................................................................................................... 95
vii
List of Figures
Figure 1-1: Shows a cross section of a well borehole ………………………………………….....2
Figure 2-1: shows a cased and cemented oil well: cement paste placement method…….……….8
Figure 2-2: Rate of heat evolution during hydration of Portland cement…………………….….11
Figure 2-3: Effects of Micro silica particles on compressive strength to water Cementous
ratio………………………………………………………………………………………………24
Figure 2-4: SEM of the interfacial transition zone between Cement Paste Mixture at 28 days for
(A) without micro silica, (B) with micro silica………………..…………………………………47
Figure 2-5: Flow Table Spread of Mortars Comprising 0% to 3.5% Nano silica
particles……………………………………………………………………………..……………52
Figure 2-6: Effects of Nano silica particles on heat hydration………..…………………………54
Figure 3-1: Experimental procedures plan flow chart……………………………..…………….59
Figure 3-2: The cement cube mold…………………………………………………...………….61
Figure 3-3: Slurry poured into the mold…………………………………………………...…….62
Figure 3-4: Fixing the mold………………………………………………………...……………62
Figure 3-5: Curing samples in water bath curing device and a cured cement cube……...………63
Figure 3-6: Schematic diagram of compressive force acting perpendicular to the surface area of a
cement cube……………………………………………………………………………..……….65
Figure 3-7: Shows a WDW-Y10A Electronic universal testing machine testing compressive load
of a cured cement cube………………………………………………………….……………….65
Figure 3-2: Shows a cured cement cube surface area dimensions……………………………….66
Figure 4-1: Shows the influence of Nano silica on compressive strength of cement paste…...…71
Figure 4-2: Shows the relationship between Nano silica and compressive strength of cement
paste for curing time of 3 days……………………………………………………………..…….72
paste for curing time of 7 days………………………………………………………..………….74
viii
paste for curing time of 15 days………………………………………………….………………76
paste for curing time of 28 days………………………………………………………………….77
Figure 4-6: Shows the relationship between curing time and compressive strength of cement
paste for a dosage of 0.0% Nano silica particles………………………………...………………80
paste for a dosage of 1.0% Nano silica particles……………………………………..………….81
paste for a dosage of 2.0% Nano silica particles…………………………………………..…….82
paste for a dosage of 3.0% Nano silica particles………………………………………...………83
paste for a dosage of 4.0% Nano silica particles………………………..……………………….84
ix
List of Tables
Table 2-1: Typical composition of Portland cement………………….……….…………………15
Table 2-2: Mineralogical composition of unhydrated cement……………….…………………..17
Table 2-3: Type of Portland cement……………………………….…………………………….18
Table 2-4: Major cement hydration products………………………………………………….....28
Table 2-5: Applications of API classes of cement…………………………………………….....31
Table 2-6: Typical composition of API classes of Portland cement………………..……………32
Table 3-1: Experimental Materials……………………………………………….……………...57
Table 3-2: Properties of nano-SiO2……………………………………………………………....58
Table 3-3: Experimental Instruments…………………………………………………………….58
Table 3-4: Shows the Mixing proportions for this experimental test……………………..….….60
Table 4-1:0.0% nano-SiO2 content experimental data……………………………………...……67
Table 4-2:1.0% nano-SiO2 content experimental data……………………………………...……68
Table 4-3:2.0% nano-SiO2 content experimental data…………………………………...………68
Table 4-4:3.0% nano-SiO2 content experimental data…………………………………………...69
Table 4-5:4.0% nano-SiO2 content experimental data…………………………………...………69
Appendix 1: Average Compressive strength for 3 days…………………………………………96
Appendix 2: Average Compressive Strength for 7days…………………………………….……96
Appendix 3: Average Compressive Strength for 15days………………………………………...97
Appendix 4: Average Compressive Strength for 28 days…………………………………….….97
x
Nomenclature
API American Petroleum Institute
CH Calcium Hydroxide
C-S-H Calcium Silicate Hydrate
HSR High Sulphate Resistant
ITZ Interfacial Transition Zone
MSR Moderate Sulphate Resistant
W/C water-to-cement ratio
AFm Alumina, ferric oxide, mono-sulfate
AFt Alumina, ferric oxide, tri-sulfate
ASTM American Society for Testing Materials
OPC Ordinary Portland cement
OWC Oil Well Cement
Al2O3 Aluminum oxide
CaO Calcium oxide
CO2 Carbon dioxide
C2 S Belite phase
C3 A Aluminate phase
C3 S Alite phase
C4AF Ferrite phase
Fe2O3 Iron oxide
H2S Hydrogen sulphide
NaCl Sodium chloride
NaOH Sodium hydroxide
Na2O Sodium oxide
SEM Scanning Electron Microscope
SiO2 Silicon dioxide (silica)
nano-SO2 Nano silica
xi
2018.5 China University of Geosciences (Wuhan) Master Thesis Mgeta Faustine Sabe
Chapter 1: Introduction
1.1 Background
Cementing is the most applied and beneficial method to produce a strength zone in contrast to
the physical and chemical forces in a well revealing the underground situation. Properties of the
cement located between the protective tubular (casing) and open hole have significant roles for
the lifespan of the well. Oil and Gas industry is still in evolution to improve the properties of that
strength zone. There are some constraints to control how this separating zone works. Those
constraints can be classified into four main divisions (Nelson, 1990).
First one is associated to the all parameters provided by cement sheath on reservoir, affecting the
well performance. Second one is considering parameters of design works for cement slurry to
preserve anticipated physical and chemical properties for each individual well condition. Third
one is taking numerous features of cementing job for different purposes including pre-job works,
like squeeze cementing, foamed cement or horizontal well cementing. Final key branch is
considering all cementing job assessment for short term and long term after the settlement of
cement slurry.
As declared above, first and second key branch and parameters defining key quantities to control
the cement reservoir connections and cement slurry design work. They are key issues for oil and
gas industry. After a conventional drilling operation, referring to the depth and casing design
parameters, each section will be absolutely isolated from the other sections. Not only from the
reservoir part but also cement slurry part would be hydraulically sealed. Zonal isolation
preserves the reservoir conditions including permeability for vicinity of wellbore but more
significant than zonal isolation preserves cement slurry contrary to undesirable fluid movement
from the reservoir.
1
Figure 1-3: Schematic Cross section of a well borehole.
Formation fluid invasion into cement slurries grants not only short-term complications like
losing suitable composition by shallow water invasions but also present long-term problems by
gas migration. There are a very large number of wells that leak or have sustained casing pressure.
In Central Europe and the Middle East there are hundreds of wells with reports of trapped
pressure that cannot be exploited off (Santra et al., 2007).
In USA and Canada there are thousands of wells leaking to the surface which can or cannot be
released to atmosphere. Moreover 25% of wells in Gulf of Mexico have assessable continued
casing pressures preserved (Cavanagh et al., 2007). Further clear way for preserving this fact that
25 % of primary cementing job catastrophes are because of gas immigration (Gonzalo, 2005).
2
Mostly fluid invasion into the cement slurry or into a cement sheath may occur because of
following conditions. Gas immigration behind shallow casing strings or behind long liners are
firstly distinguishing reasons can be followed by great annular volume leading problems to
transfer the outstanding drilling fluid (Brooks R. et al., 2008).
High shrinkage rates for setting cement together with a thick mud filter cake plays also a wicked
role and issuing channeling in the cemented section. “Gel” perception has been quantified to
understand the hydrostatic balance with respect to time and saved in mind at all times as a reason
for undesirable fluid invasion (Bahramian et al. 2007).
Furthermore, fluid loss worth of cement slurry and related parameters of slurry like relative
permeability of gas may define the purpose for gas immigration. Rheological properties of
cement slurry lastly can be specified as an undisputable fact when examining the possible
reasons of gas immigration. Lower Equivalent Circulation Density value is vital in order to
reduce the circulation pressure and to avoid annular fluid losses from the cement slurry.
There are adequately works to detect and to solve that undesirable fluid invasion problem. At the
recent day, drilling industry is highlighting the resolutions for gas immigration with increasing
frequency. The reason is the benefits of nearly 100 % gas producing reservoirs without any
continued casing pressures and reduced remedial cementing job costs.
1.1.1 Nano silica Material
Nano silica are the Nano-particles of silicon dioxide SiO2; it is very fine silica that has been used
for years as cement admixture both in the oil field and construction field. Since it tremendously
fine in nature and high reactivity pozzolanic material, Nano silica particles has been used to
enhance slurry impermeability and the mechanical properties of the hardened cement paste
(Mohammad M. C., et al 2012).
3
Consuming Nano silica particles in slurry composition enhanced rheological and mechanical
properties of cement slurry and set cement. The slurry design with low porosity and permeability
and high compressive strength, is appropriate in zones where the prospect of gas migration is
very high (Mohammad M. C., et al 2012).
Mostly, integration of silica Nano-particles in the cement slurry has been detected and
testified to comprise:
i. Early strength development;
ii. Increased long term tensile to compressive strength ratio;
iii. Viscosity improvement; and
iv. General raise in the early phase compressive strength.
Therefore, it is vital to be able to comprehend the impact of Nano silica particles on

enhancing bonding strength of cement paste mixture.
1.2 Research Problem Statement

Gas migration is one of the greatest upsetting complications is petroleum industry. It is described
as the outbreak of formation fluids into the annulus due to a pressure difference at the formation
face where fluids may travel to a lower pressure zone or possibly to the surface (Nelson &
Guillot, 2006).
Upsetting complications are topped by their complexity as many numerous factors affect the
process such as fluid density control, mud removal, cement slurry properties, cement hydration,
and interactions between the cement, casing, and formation. Because there is no other well that
has the same explanations that caused gas migration can diverge from one to another well.
Extensive research study has been done to understand this approach, resulting in numerous
concepts that describe the physical processes that can cause gas migration.
4
Several research studies have been done recently to examine the effects of integrating silica
nanoparticles to the cement slurry in order to describe its mechanical properties and cement
hardiness after cementation. An assessment of the literature describes that integrating silica
nanoparticles to cement slurry enhances its mechanical properties and hardiness. However,
insufficient of these studies have been done in China using local materials with silica
nanoparticles added.
The current development of oil and gas production in China desires advanced materials that
could solve coexisting well cementing complications and deliver new applications for better
practice of natural resources
1.3 Research Aims and Significance
1.3.1 General Objective of the Research
The objective of this work is to study the influence of adding Nano silica particles to the oil
cement slurry on enhancing its mechanical properties specifically compressive strength of a
hardened cement paste. Also, this study aims at providing cement slurry with mega high
performance to be used in some special applications.
1.3.2 Specific Objectives of the Research.
i. To examine the influence of Nano silica materials in improving compressive strength of

an oil well cement
ii. To determine the relationship between Nano silica materials content and compressive
strength of a hardened cement pastes.
iii. To determine the relationships between curing time of cement and compressive strength
of a hardened cement pastes.
5
1.3.3 Significance of the Research Study
Communications between Zones, gas movement, undesired fluid entry to the well bore, and
casing corrosion are samples of serious weaknesses resulting from poor cementing jobs. Both
private companies and academia are endlessly conducting research projects to enhance and
develop new cements and chemical additives that improve cementing of oil and gas wells in
numerous environments.
The results from this study will support to document and broaden our knowledge on the how
Nano silica particles improves compressive strength of oil well cement that results into
complications of fluid influx from the formation.
Because of its capability to improve cement properties and to Withstand cement strength and
durability in high and normal temperature applications has made Nano silica particles being a
promising mixture with cement.
Application of Nano silica particles to the designing of cement slurry can be beneficial
particularly in high pressure zones, where there is a risk of wellbore blow out.
1.3 Structure of the Research Study

Chapter one explains about the general introduction of this research study. It includes the
background of the study, problem statement, the objectives and significance of the study.
Chapter two covers the literature review on relevant areas including oil well cementing
operations , well cementing process and complications, the purposes for well cementing,
Portland cement, Portland cement composition, Portland cement clinker stages, types of
Portland cements, cement hydration reaction, hydration of pure clinker phases, Phases of
cement hydration , heat of hydration, hydration products, oil well cement, characteristics of oil
well cements , oil well cement grades and types, oil cement admixtures,
6
Chapter three lays out the experimental design and procedures followed in the study. It explains
the materials and equipment used as well as the experimental sample preparation process.
Chapter four presents the data obtained from the experimental study. It also provides the
discussions and data analysis of the research results.
Chapter five presents the conclusions reached at the end of the study. It also outlines the
recommendations made for future work on the influence Nano silica particles in improving
compressive strength of oil well cement
7
Chapter 2: Literature Review
2.1 Oil Well Cementing Operations

Cementing is the method of presenting cement to the annular gap between the well bore and
casing or to the annular gap between two consecutive casing strings. Two core roles of this
process are to restrict fluid movements between formations and to support the casing. There are
two vital cementing activities; liner cementing or cementing the casing, which is called primary
cementing and it is one of the greatest significant operations in oil and gas well development.
Figure 2-1: Showa cased and cemented oil well: cement paste placement technique
8
Squeeze cementing and plug cementing are the extra cementing operations signified as
secondary or remedial cementing. Cement also helps in the protection of casing corrosion and in
deep drilling operation in the protection of casing from loads. Materials of well cementing are
different from Portland cement used in civil engineering constructions. For oil well cementing
the commonly used ones are Portland category cements. The oil well cements, which can be used
both in offshore and onshore fields are exposed to wide ranges of temperatures and pressures.
2.1.1 Well Cementing Process
The process of well cementing comprises collecting information for cement job design,
designing the cement slurry, calculating the cement volume and cementing time necessities,
choosing cement placement practice, and engaging the cement. The quality of a cement job is
seriously reliant on on how good the cement job design was.
Information about wellbore configuration and environment are crucial to a cement job design as
they affect the cement slurry design and determine the cement placement technique to be
utilized. The wellbore configuration information includes measured depth, open-hole size, and
casing properties. These strongly influence the slurry volume required, hydrostatic pressure and
friction pressure (Agbasimalo, 2012).
Information about the wellbore situation contains the pore and fracture pressure profiles, type of
formation being cemented, temperature profile, presence of gas, and mud properties. All the
information recorded are processed earlier to cement slurry design. During slurry design
additives are involved to basic Class H or G cement to deliver the cement with the anticipated
properties.
The cement admixtures comprise of retarders, dispersants, fluid loss additives and viscosifiers.
Retarders extend the setting time of cement while dispersants (e.g. polynaphthalene sulfonate),
decrease the viscosity of the cement. The slurry design process is a complicated process
including admixtures that interact with the performance of each other.
9
Once the slurry design is obtainable and the cement volume and cementing time needed for the
cement job are calculated, the process of cement placement can be started.
Several primary cement placement practices like normal displacement method, stage cementing,
multiple string cementing etc. are existing. The cement placement practice selected for a cement
job depends on numerous factors like the purposes of the cementing, string category to be
cemented, and pressure profile of the well section (Chilingar et al 1989, Agbasimalo 2012).
2.1.2 The Purposes for Well Cementing
Cementing the liner for zonal separation is one of the utmost substantial factors for actual well
integrity. The cement placement, type of cement, cement admixtures and thickening time are
some of significant factors hindering the sealing ability of cement sheath. (Lafarge 2014), the
key roles of well cementing include:
i. Zonal Isolation: Well cement helps several functions in the drilling project. Furthermore,
among these is protection of the condition specifically the underground water tables.
ii. Hydraulic Seal: Oil and gas wells are drilled to changing depths in various positions and in
several harsh conditions around the world. A common characteristic in all these wells is well
cement. Well cement is used to form a hydraulic seal among the well liner and the underground
formation. This seal must be free of channels and impermeable to gases if the well is to reach its
supreme production ability.
Well cement separates and stops the production fluids and gases from inflowing the underground
water, thus protecting our water provisions.
10
Figure 2-2: Showa a technique of protecting underground water (Lafarge 2014)
iii Structural Support: Structural support is significant for the liner pipe and production pipes.
Well cement is used to form a sheath among the well bore and the liner pipe. A bond is formed
among the underground infrastructure and the pipe, attaching it in place and giving support for
the underground well structure. An appropriate cement bond protects the underground water
tables and eradicates the need for remedial cementing, thus causing in a well having a long-life
span.
11
iii. Longevity: Well cements are used to prevent the weakening of the underground liner and
production pipe strings. In several cases fluids which could cause corrosion are used to
stimulate the well production. Well cements protect the liners and production strings in
contrast to corrosion.
iv. Well Life Span: Well cements are vital to the long period well life. The durability of a well be
subject to on a good cementing job. A successful cement job is an essential condition to
overcome well integrity matters for long period productivity. Without well cements a costly
asset would very soon lose value.
2.1.3 Complications in Well Cementing
Ineffective cement job leads into failure of cement to achieve its basic functions and a secondary
cement job may be permitted. Even when a good cement job is accomplished, cement can still
fail in the long period due to numerous other features.
Subsequently, wellbore cement difficulties can be clustered into two:
i. Short span cement complications
ii. Long span cement complications
I. Short Span Cement Complications
a) Inadequate removal of drilling mud is the key source of the failure in cementing.
Sacks of the drilling mud and filter cake prevents the cement to form a strong bond with the
formation. There are numerous reasons for mud removal failure comprising poor wellbore
environment and inappropriate displacement mechanics.
12
b) Imperfect cementing due to casing eccentricity.
This happens when the liner is not well centered in the wellbore causing privileged flow of the
injected cement over the wider section on the liner - formation annulus. This leads in the smaller
annulus not being cemented. Appropriate string centralization can be vital to prevent this
problem. Centralizers are initially installed on liner string to deliver satisfactory standstill for
primary operation.
c) Invasion of formation fluids in cement setting.
Throughout the changeover from cement slurry to hardened cement, the cement loses some of its
capability to convey hydrostatic pressure due to pressure variations and this may allow gas
invasion into the wellbore from the formation through cracks that are established during cement
setting stage.
Flow happening before cement has set is a result of loss in hydrostatic pressure to the point that
the well is no longer overbalanced, the hydrostatic pressure is less than formation pressure
(Agbasimalo 2012).
d) Inadequate slurry Height.
Cement is lost in high permeable or highly fractured zones. This loss results into the reduction in
slurry volume. So, slurry cannot attain needed height and a lot of portion is left uncemented.
This is known as cement fallback in the annulus. The unprotected and uncemented area then
develops a weak point for the flow of hydrocarbons.
II. Long Span Cement Complications
a) Mechanical stress and strain on the cement due to pressure and temperature cycles
over the life of the well.
Altering of stresses in the wellbore may cause micro annuli, stress cracks or both causing to
continued liner pressure. Mechanical properties of liner and cement differ significantly. They do
not act consistently when exposed to changes of pressure and temperature. As liner and cement
13
enlarge and contract, the bond between the cement sheath and liner may fail causing a micro
annulus or flow path to develop.
b) Geochemical degradation of the cement over time due to acid and sulfate attack.
Geochemical downhole environments fluctuate from well to well. Some conditions are acidic
due to the presence of relatively high concentrations of H2S and CO2. These have been shown to
attack the cement affecting its mechanical properties.
Sulphates also exist in some wellbore conditions and these react with the cement to form
ettringite (hydrous calcium aluminium sulfate mineral) and gypsum. The ettringite and gypsum
have greater bulk volume than the cement from which they form (Tian & Cohen, 2000). This
causes compression of the surrounding sections of the cement bringing stresses in the cement
that result in cement cracking (Agbasimalo 2012).
2.2. Ordinary Portland cement
Portland cement is fine ash gotten from crushing clinker Portland cement and fewer quantities of
calcium sulfate and up to 5% minor constituent (fly ash. silica fume). Calcium, silica, alumina,
iron are the primary components of raw constituents for Portland cement. The raw materials are
mixture of argillaceous (alumina and silica) material like shale, clay, blast furnace slag and fly
ash and limestone (Bakker, 1983).
Portland cement is used in production of slurry, which is a composite material contains cement
and water. Slurry as a building material can be designed in any shape and when hardened can be
a structural material. Portland cement can be applied in mortars that comprises of sand and water
only for screeds, plasters and in grouts (Bakker, 1983).
14
2.2.1 Portland Cement Composition
Portland cement is a Clinker constitutes of calcium oxide (CaO), silicon oxide (SiO2), aluminum
oxide (Al2O3) and iron oxide (Fe2O3). Major components essential for the production of clinker
are normally obtainable in the mixture of limestone and clay. Limestone or marly limestone is
the foundation of CaO, while clay or marly clay is the foundation of SiO2, Al2O3 and Fe2O3.
These raw materials are mixed in a certain ratio to attain the needed final chemical composition.
Consequently, corrective constituents are occasionally added during the production process. Pure
limestone for increasing CaO content, quartz sand for increasing SiO2 content, bauxite for
increasing Al2O3 content and hematite or iron ore for increasing Fe2O3 content are distinctive
examples on the use of corrective constituents (Labahn, 1983). Table 2-1: shows typical
composition of Portland cement.
Clinker is formed by burning appropriately combined raw materials up to a temperature of 1450
ºC. The first formation of liquid stage signs the starting of the clinkering also known as sintering
period of clinker. After the sintering process, four major stages are formed which are Alite
(C3S), Belite (C2S), aluminate (C3A) and ferrite (C4AF). Numerous compounds which are alkali
sulfates, calcium oxide (CaO), magnesium oxide (MgO) and other oxides, may exist as minor
components.
Table 2-7:Typical composition of Portland cement (Neville, 2003)
Oxide Limit Value (wt, %) Average (wt, %)

CaO 60-67 65
SiO2 17-25 22
Al2O3 3-8 6
Fe2O3 1-8 3
MgO Less than 5 2
SO3 Less than 3 1
K2O+Na2O Less than 2 1
15
After the burning process if clinker is cooled gradually, some of the reactions which are already
formed in the kiln would be reversed. Nevertheless, if fast cooling is provided on hot clinker, the
solidification of the liquid stage is boosted which affects the crystallization state of clinker.
Quick cooling donates to the formation of clinker by declining the regression losses of C3S to
C2S during slow cooling and consequently advances the reactivity of clinker (Taylor, 1997).
2.2.2 Portland Cement Clinker Stages
Portland cement comprises of four main clinker stages which are C3S, C2S, C3A and C4AF.
C3S (alite): is the main mineral stage in Portland cement clinker with the chemical formula
3CaO·SiO2; it comprises of 50-70% of clinker. C3S is thermodynamically unstable below 1250
°C but can be conserved in meta stable state at room temperature by quick cooling (Taylor,
1997).
C2S (belite): is the second significant mineral stage in Portland cement clinker and
conscomprises of about 15-20% of clinker. The chemical formula of C2S is 2CaO·SiO2 and
usually existing in clinker as β polymorph.
At room temperature it is likely to change thermodynamically to the more stable γ polymorph,

but this form does not hydrate and should be dodged in Portland cement. Consequently, β
polymorph of C2S can be stabilized at room temperature over quick cooling (Labahn, 1983).
C3A (tricalcium aluminate): is the furthermost common mineral amongst aluminates and
comprises 5-10% of Portland cement clinker. The chemical formula of C3A is 3CaO·Al2O3 and
owns high degree of reactivity. Its hydration is very fast and unwanted flash setting may happen
if a setting control agent (normally gypsum) is not used (Domone & Illstone, 2010).
16
C4AF (Ferrite): comprises 10-15% of Portland cement clinker and doesn’t have an exact
chemical formula. The chemical configuration may fluctuate between C2 (A0.7, F0.3) and C2 (A0.3,
F0.7), nevertheless, more or less the constituent’s links to tetra calcium aluminoferrite (C4AF)
(Odler, 2004; Labahn, 1983).
Ferrite has little or insignificant input to the compressive strength of the hardened cement paste.
Its hydration is quick if a setting control agent (normally gypsum) is not used and gives its
precise color (grey) to clinker.
Table 2-8: Mineralogical composition of unhydrated cement
Oxide composition Cement notation Common name Concentration

(wt %)
3CaO·SiO2 C3 S Alite 50-70
2CaO·SiO2 C2 S Belite 15-20
3CaO·Al2O3 C3 A Aluminate 5 – 10
4CaO· Al2O3·Fe2O3 C4AF Ferrite phase 10 – 15
2.2.3 Types of Portland Cements
ASTM C150 defines cement types as;

I. Normal
II. Moderate sulfate resistance
III. High-early strength
IV. Low heat of hydration
V. High sulfate resistance
17
Sulfate resistant cement is used with the existence of alkali soil or threat of sulfate salts found in
ground water. This type of cement has a restriction on C3A and C4AF quantity which affects
sulfate resistance.
ASTM C 150 delivers eight types of Portland cement to encounter numerous physical and
chemical necessities for precise purposes.
Table 2-9: Type of Portland cement (Bakker, 1980)
Typical Potential compound composition, %

Type of Portland
Cement
Blaine
(ASTM C 150)
C3 S C2 S C3 A C4AF fineness
(m2/kg)
I 54 18 10 8 369
Normal
II
55 19 6 11 377
Normal, air-entraining
III
57 15 9 8 548
Early Strength
IV
42 32 4 15 340
Heat of Hydration
V
54 22 4 13 373
High sulfate resistance
18
2.3 Cement Hydration Reaction

The major ingredients of well cement clinker are tricalcium silicate (C3S), dicalcium silicate
(C2S), tricalcium aluminate (C3A) and tetracalcium aluminum ferrite (C4AF). The compounds
are anhydrous and react chemically with water making hydrated products.
In cement chemistry, hydration is the chemical reaction between anhydrous cement powder and
water. Freshly mixed slurry is in liquid form and has a plastic structure. As the reaction taking
place, the hydration products steadily bond together and turn into solid called hardened cement
paste. The development and kinetics of hydration are affected by a diversity of reasons (Odler,
2004):
i. Composition of the cement and existence of foreign ions
ii. Fineness of the cement
iii. Water to cement (w/c) ratio
iv. Curing temperature
v. Existence of chemical additives, i.e. Dispersants or retarders
vi. Existence of mineral additives, i.e. fly ash, micro silica, Nano silica
It is essential to look for the four principles clinker stages in the hydration of Portland cement
clinker. Generally, the reaction of hydration can be simplified as;
Clinker stage + water → hydrate stage + energy

(High in energy; (low in energy; (heat of hydration)
contain no water) contain water)
The equation above, the reaction of hydration is exothermic due to the high entropy energy of the
clinker stages
19
2.3.1 Hydration of Pure Clinker Stages
It is important to examine hydration of clinker stages distinctly due to the complexity of

hydration mechanism of Portland cement and to avoid from the effect of the new ions liberated
from the hydration of other phases (Odler, 2004).
1. Tricalcium Silicate (3CaO.SiO2). C3S is the utmost significant ingredient of Portland

cement clinker and usually accountable for the early strength growth. The hydration products
of C3S at room temperatures are; amorphous C-S-H with a CaO/SiO2 less than 3.0 and
calcium hydroxide as illustrated in the Equation 1.
3CaO·SiO2+xH2O = mCaO· SiO2·nH2O + (3-m) Ca (OH)2 (1)

tricalcium silicate calcium silicate hydrate calcium hydroxide
2. Dicalcium silicate (2CaO.SiO2=C2S): C2S is the second significant ingredient of Portland

cement and typically accountable for the definitive strength development. C2S hydration is
alike to C3S, nevertheless its hydration is slower, lower heat is produced and lower quantity of
CH is generated. The hydration products of C2S at ambient temperatures are; amorphous C-S-
H and CH as shown in the Equation 2.
2CaO· SiO2+xH2O = mCaO· SiO2 · nH2O + (2-m) Ca (OH)2 (2)

dicalcium silicate calcium silicate hydrate calcium hydroxide
3. Tricalcium Aluminate (3CaO.Al2O3): The hydration of C3A is very quick and produces
more heat related to C3S. In the absence of any admixtures C3A reacts with water to produce
gel like material on the surface of C3A. Far ahead, converts into meta stable intermediate
hexagonal crystal phases, C2AH8 and C4AH13.
20
Additional precipitation quantities of these crystals, changes them to cubic C3AH6. This is the
only thermodynamically stable calcium aluminate hydrate at ambient temperatures13oC. If the
temperature is more than 80 °C, C3AH6 can directly be produced in the hydration of C3A
(Odler, 2004).
3CaO· Al2O3+ Ca(OH)2+12H2O = 3CaO· Al2O3 · Ca (OH)2 ·12H2O (3)

tricalcium aluminate hydrated calcium aluminate
4. Gypsum is normally incorporated to the Portland cement to control the rate of reaction. In the
presence of gypsum C3A solubility declines and hydration slows down. C3A reacts with
gypsum in the presence of water to produce AFt stages (ettringite). AFt stages then react with
C3A to produce AFm stages depending on the gypsum to C3A ratio as illustrated in equation 4
(Day, 1992).
3CaO· Al2O3+3 (CaSO4·2H2O) +26H2O = 3CaO· Al2O3 · CaSO4 ·32H2O (4)

tricalcium aluminate gypsum hydrated calcium sulfoaluminate
(Ettringite)
5. The hydration products of ferrite are similar to C3A. The primary hydration rate of pure
C4AF is generally quicker than C3A but then slows down rapidly. In the absence of gypsum,
C2 (A, F) H8 and C4(A, F) Hx is produced and then converts to further stable iron comprising
hydrogarnet phase C3(A, F) H6.
In the presence of gypsum, AFt stage C6 (A, F) S3H32 is produced as a primary hydration
product (Chatterji &Jeffrey, 1962). Hydrogarnet stage is produced directly in the hydration at
elevated temperatures (Negro & Steffari, 1979). After all gypsum is spent AFt stage change to
AFm stages.
4CaO· Al2O3·Fe2O3 +10H2O + 2Ca (OH)2 = 6CaO· Al2O3 · Fe2O3 ·12H2O (5)
tetra calcium alumino ferrite hydrated calcium alumino ferrite
21
Insignificant components in Portland cement clinker are also affecting hydration. The greatest
important ones are; alkalis (Na2O and K2O), MgO, CaO and sulfates. Alkalis are harmful for
hardened cement paste and affect strength development of cement paste. It has a positive effect
on strength development at initial ages, but at future ages strength deterioration happens (Jawed
& Skalny, 1978).
Free CaO and MgO are exposed to high temperature greater than temperature 1400 °C in kiln
and result in crystal-like structures. The extremely crystalline CaO and MgO are much less
responsive with water. The late hydration of these minerals may cause volume unsteadiness in
the hardened cement paste. The reactions are illustrated in Equations 6 and 7. The solubility of
MgO in water is much less than that of CaO and consequently it is more harmful compared to
CaO (Mehta, 2006).
CaO + H2O = Ca(OH)2 (6)
MgO + H2O = Mg(OH) (7)
Sulfates in clinker react with CH to produce extra gypsum in cement paste.

Extreme quantities of gypsum donate to the formation of AFt phases which has also harmful
effect on hardened cement paste.
2.3.2 Phases of Cement Hydration
The hydration of cement is more complex than the hydration of individual clinker phases. It is
characterized by five stages (Odler, 2004).
In cementing operations, the utmost significant of these phases are phase one via phase three.
Phase one specifies the early mixability of the cement and is contained to primarily to the
aluminate and ferrite phase reactions. Phase two narrates to the pumpability time and phase 3
offers an indication on setting properties and gel strength development.
22
i. Pre-induction period (first minutes)
Instantly with the interaction of water, extremely soluble ionic species in cement dissolves into
liquid phase. Alkali sulfates dissolve in a few seconds and liberates K+, Na+ and SO4 ions.
Calcium sulfates dissolve until super saturation and liberates Ca2+ and extra SO4 ions.
In the pre-induction period, 2 to 10 % of C3S is hydrated. With the hydration of C3S, Ca2+ and
OH- are liberated and C-S-H precipitates on the cement powder. AFt phases formed and
precipitated on the cement surfaces with the dissolution of C3A and C4 (A, F) in Ca2+ and SO4
rich solution. Insignificant quantities of C2S hydrate at the pre-induction period.
ii. Induction (dormant) period (first few hours)
After rapid hydration at pre-induction period, hydration decelerates significantly. Ca2+

concentration in the liquid phase raises until it reaches to its serious supersaturation and then CH
begins to precipitate. AFt stages proceed to precipitate but SO4 remains persistent due to the
dissolution of additional calcium sulfates. This stage is vital in slurry technology because cement
paste is still workable.
iii. Acceleration stage (3-12 hours after mixing)
In this period C3S hydration increases and second phases C-S-H forms and certain quantities of
C2S donates to hydration. Crystalline CH (portlandite) precipitates and Ca2+ concentration in the
liquid phase slowly decreases. SO4 concentration in the liquid phase also decreases because of
the precipitation of AFt phases. This phase determines the setting time and early strength
development of cement paste.
iv. Deceleration period
In this period, hydration rate decelerates slowly, and SO4 concentration in liquid phase proceeds
to decrease. When SO4 in liquid phase is exhausted, AFt reacts with C3A and C4 (A, F) to
23
produce AFm. As a consequence of the deposition of further hydrates, strength of hardened

cement paste raises while porosity declines.
v. Steady State period
In this period, hydration rate is comparatively slow. Hydrated C-S-H develops denser and
portlandite crystals proceed to grow. The strength of hardened cement paste raises while rate of
heat generation and porosity declines. Nevertheless, the duration of this period is unlimited, total
hydration never achieved.
Figure 2-3: Rate of heat evolution during hydration of Portland cement (Mindess & Young,
1981)
2.3.3 Calcium Sulfate
The solubility of calcium sulfate depends on their form; gypsum is much lower than anhydrate,
and hemi hydrate has the uppermost solubility amongst them. At initial and middle periods of
hydration, calcium sulfate dissolves and reacts with aluminates and ferrite to produce AFt or
AFm stages (Nelson, 1990).
24
2.3.4 Heat of Hydration
Portland cement is a product that is designed at high temperatures and hence owns high energy
state. When cement hydrates, energy is discharged and turns to a low energy state. The rates of
heat discharge from hydration of the specific compounds can be used as guides of their
reactivity. The data from heat of hydration studies can be used for describing the setting and
hardening behavior of cement, or for forecasting the temperature increase.
2.3.5 Hydration Products
The main products of cement hydration are revealed in Table 2-4. Ettringite, 3CaO· Al2O3 ·
CaSO4 ·32H2O is also formed during cement hydration. During the reaction water is vanished to
formation by dehydration or evaporation when slurry is exposed to differential pressure and
temperature and hydrous compounds produce a meshing crystalline structure.
i. Calcium Silicate Hydrate
Calcium silicate hydrate (C-S-H) phase is produced as a hydration product of both C3S and β-
C2S. It is nearly amorphous in structure and dashes show that there is not any precise chemical
composition implied. On the total hydration of both C3S and β-C2S with stoichiometric
calculations, estimated constituents of the hydration product are expected to be C3S2H3. On
complete hydration of Portland cement, C3S yield 61% C3S2H3 and 39% CH, whereas β- C2S
yield 82% C3S2H3 and 18% CH. Consequently, final strength of the hydrated β-C2S is
predictable to be more than C3S (Mehta, 2006).
The chemical reactions between calcium and silicate ions in aqueous suspensions carry them
together to produce amorphous C-S-H gel and intermediate crystalline phases. There are 30 types
of C-S-H phases, the greatest important crystalline phases are; l.4nm tobermorite, jennite, C-S-H
(I) and C-S-H (II) (Taylor, 1997).
25
1.4 nm tobermorite has a layer structure and 1.4 nm designates the thickness of this coating. It is
obviously happening mineral and can be formed from CH and hydrous silica in aqueous
suspensions. After being heated to 55 °C, 1.4 nm tobermorite dehydrates and loses water and
changes to 1.1 nm tobermorite (Taylor, 1997).
C-S-H (I) is the defective form of 1.4 nm tobermorite and can be formed from CH and hydrous
silica in aqueous suspensions. Portland cement in the occurrence of reactive silica at higher
temperatures forms phases similar to C-S-H (I). It is more ordered than the C-S-H gel produced
in Portland cement pastes. Likewise, C-S-H (I) is a transitional product of hydrothermal
reactions at temperatures up to 180 °C and can be noticed in pastes made from alkali activated
slag (Taylor, 1997).
Jennite can arise as a natural mineral and has a layer structure comparable to 1.4 nm tobermorite.
The major difference is the OH- groups connected to the calcium atoms in the central region of
the specific layers. C-S-H (II) is the defective form of jennite and its Ca to Si ratio is advanced
than that of jennite. A compositional position, jennite and C-S-H (II) are nearer to C-S-H gel
than 1.4 nm tobermorite and C-S-H(I) (Taylor, 1997). The conditions with high Ca to Si in
suspension favor the formation of C-S-H (II) or jennite at high temperatures (Damidot and
Nonat, 1994).
There are four morphological types of C-S-H gel as examined by SEM analysis of cracked
surfaces of cement paste.
Type I is a fibrous material and formulates at early ages of cement paste being up to 2 μm long.
Type II C-S-H happening at normal early ages and formulates reticular systems or honey comb
like structures.
Type III is prominent in older pastes and contains of closely filled equant particles up to 300 nm
across.
Type IV is detected in older ages as inner product with featureless and immense structure
(Diamond, 1976).
26
ii. Calcium Hydroxide, Ca(OH)2
Calcium hydroxide (CH) crystals are formed from hydration of mostly C3S and β-C2S. It
comprises 20% to 25% of objects by volume in the hydrated cement paste. In the accessible pore
spaces, it tends to produce big hexagonal prism crystals. The strength influence of CH is very
low or insignificant equated to C-S-H and can be simply removed by the action of water.
Also, CH is not chemically stable. It can react with sulfates to produce gypsum which is harmful
in hardened cement paste.
iii. Calcium Sulfoaluminate Hydrates
Calcium sulfoaluminate hydrates (AFm and AFt) comprises 15% - 20% by volume of the
hydrated paste. As stated previous, in fresh cement paste gypsum reacts with alumina bearing
phase (C3A and C4AF) to formulate primarily AFt, then it finally converts to AFm by time.
Ettringite is by far the furthermost common AFt phase with needle shaped prismatic crystal
structures existing in hydrated cement paste. Huge development of ettringite seals the voids and
cracks of hardened cement paste. Failure of hardened cement paste caused by enlargement in the
presence of sulfate is due to the development of ettringite.
Monosulfate is the utmost common AFm phases in hydrated cement paste. It has a tendency to to
arise in the later stages of hydration. It formulates hexagonal plate crystals which are less
harmful linked to ettringite.
At ambient temperatures ettringite is extra stable than monosulfate and hence presence of
monosulfate in the cement slurry make it further vulnerable to sulfate attack (Kelly, 1960). Both
ettringite and monosulfate comprise negligible quantities of Fe3+ which can supplement
aluminum in the crystal structure (Mehta, 2006).
27
iv. Carboaluminate
The atmospheric CO2 or carbonates in the cement paste react with CH to form calcium
carbonate. Calcium carbonates can also be accessible in the existence of finely ground limestone.
Calcium carbonate is conveyed to react with the tricalcium aluminate to formulate high and low
arrangements of the carboaluminate, C3A • 3CaCO3 • 32H2O and C3A•CaCO3•12H2O
respectively. Calcium carbonates can act as a fractional supplement for gypsum in
sulfoaluminates (Jackson, 2004).
Table 2-10: Major cement hydration products (Agbasimalo, 2012)
Chemical formula Cement notation Common name Concentration

(wt%)
3CaO·2SiO2·3H2O C-S-H C-S-H 50-70
Portlandite
Ca(OH)2 CH 15-25
2.4 Oil Well Cement

In oil and gas industry, oil well cements are carefully chosen according to the API (American
Petroleum Institute) specifications. Because the situations to which Portland cement is applied in
wells can differ principally from those practiced in building applications.
API delivers eight classes of oil well cements which are selected from class A through H. These
eight classes are organized based on depths that they are located and the pressures and
28
temperatures to which they are applied. API classes A, B and C matches to ASTM types I, II and
III; ASTM types IV and V have no matching API classes B (Nelson, Erik, 1990).
2.4.1 Features of Oil Well Cements
One of the major features of the oil well cement is that it is resistant to high pressure and also the
high temperature. In some fields, oil wells are exposed to pressure of 20,000 psi and 500 ºF. The
raw materials which are essential for the production of oil well cement consist of limestone, iron
ore and coke (Nelson, Erik, 1990).
2.4.2 Oil Well Cement Grades and Types
Portland cement is the main cement used in wellbore building. It is used for primary cementing,
remedial cementing and plug and abandonment of wells (Nelson 1990). It is made by burning a
mixture of limestone and clay.
The slurry contains of Portland cement, water and diverse admixtures and then positioned into
the bore hole. Slurry properties are adjusted according to the borehole environments by
incorporating retarders and other admixtures. These compounds transform the physical
properties of the cement which comprise density, thickening time, filtration rate and viscosity.
American Petroleum Institute (API) classified cements into 9 classes from A to H and J. These
classes are well-defined according to the material used, depth, formation type and pressure
temperature environments. Cement is also gathered into 3 grades based on their sulfate resistance
ability: O (Ordinary), MSR (Moderate Sulfate Resistant) and HSR (High Sulfate Resistant),
which amongst these the O, Ordinary type is utmost usually used (Nelson, Erik, 1990).
Sulfate resistance level is based on the C3A (tricalcium aluminate) content, which effects the
longevity of cement under sulfate attack. Class A, G, and H cements have been used widely in
wellbores but Class G and H are the utmost frequently used today.
29
Class A:
Appropriate for use from surface to a depth of 1830 m (6,000 ft) and distinct properties are not
essential. It is prevailing only in ordinary type (O). (Comparable to ASTM C150, type I)
Class B:
Appropriate for use from surface to a depth of 1830 m (6,000 ft) when environments need
moderate to high sulfate resistance. Both moderate and high sulfate resistance types are
obtainable. (Comparable to ASTM C150, type II)
Class C:
Appropriate for use from surface to a depth of 1830 m (6,000 ft) when high early strength
environments are needed. Ordinary type, moderate and high sulfate resistant types are
obtainable. High early strength and quick hardening are features of class C which permits to be
used at advanced water levels associated to G, H classes. Class C cement is finer when
associated to other classes of cement and this class of cement has surface area of about 400- 500
m2/kg.
Class D:
Appropriate for use from depth of 1830 m to 3050 m (6,000 to 10,000ft) and also can be used at
normal high temperatures and pressures. Class D cement is existing in both HSR and MSR
grades and this type of cement has good pumpability.
Class E:
Appropriate for use from depth of 3050 m to 4270m (10,000 to 14,000 ft) under environments of
high temperatures and pressures. In both moderate and high sulfate resistance types are existing.
A retarder must be incorporated in the plant by the cement producer to regulate its thickening
time.
Class F:
Appropriate for use from depth of 3050 m to 4880 m (10,000 to 16,000 ft) under environments
of very high temperatures and pressures. Both moderate and high sulfate-resistant types are
existing. A retarder is incorporated in the plant by the cement producer to regulate its thickening
time.
30
Class G:
Appropriate for use as elementary cement from surface to a depth of 2438 m (8,000 ft) as
produced. It can be used at an extensive range of depths and temperatures with accelerators and
retarders. It is stated that no admixture except calcium sulfate or water, or both, shall be mixed
with the clinker during the production of class G cement. Class G is existing in HSR and MSR
grades and well-matched with many of admixtures.
Class H:
Appropriate for use as elementary cement from surface to depth of 2438 m (8,000 ft) as
produced. This cement can be used with accelerators and retarders at an extensive range of
depths and temperatures. It is stated that no incorporation of any admixture except calcium
sulfate or water, or both, shall be mixed with the clinker during the production of class H cement.
Only in moderate sulfate resistant type is existing.
This type of cement alike to class G but projected for higher density slurries.
Table 2-11: Applications of API classes of cement (Nelson E.B., 1990)
Mixing Slurry Well Depth Static

Classification Water Weight (ft) Temperature
(gal/sk) (lb/gal (ºF)
A (Portland) 5.2 15.6 0 to 60,00 80 to 170
B (Portland) 5.2 15.6 0 to 6,000 80 to 170
C (high early) 6.3 14.8 0 to 6,000 80 to 170
D (retarded) 4.3 16.4 6,000 to 12,000 170 to 260
E (retarded) 4.3 16.4 6,000 to 14,000 170 to 260
F (retarded) 4.3 16.4 10,000 to 230 to 320

16,000
G (basic) 5.0 15.8 0 to 8,000 80 to 200
H (basic) 4.3 16.4 0 to 8,000 80 to 200
31
Table 2-12: Typical composition of API classes of Portland cement (Nelson E.B., 1990)
API Compounds Fineness

Classes (Percentage) (surface area)
(sq cm/g)
C3S C2 S C3 A C4AF
A
53 24 8 8 1,600 to 1,800
B
47 32 5 12 1,600 to 1,800
C
58 16 8 8 1,800 to 2,200
D&E
26 54 2 12 1,200 to 1,500
G&H
50 30 5 12 1,600 to 1,800
2.5 Cement Admixtures

The cement slurry industry has extensively implemented the use of chemical and mineral
admixtures in cement slurry design. Harmonizing performance and cost, controlling application
specific properties, increasing durability, increasing sustainability, dropping maintenance costs,
and extending the service life of structures are amongst various increasing demands of current
day cement slurry designs (Skalny et al. 2002).
This has caused in chemical and mineral admixtures having an important role in developing
quality slurry that can perform well. Cement slurry being a complex material, there is overall
promise that its microstructure properties affect its majority properties and performance.
32
This is why emerging innovative foreign materials and additives that can positively and
economically change the microstructure of cement slurry to accomplish performance goals has
been the newest frontier in cement slurry design.
2.5.1 Cement Chemical Admixtures
Portland cement that is manufactured to be used in wells is planned to resist an extensive range
of numerous temperatures and pressures (Nelson & Guillot, 2006). The temperatures may differ
from below freezing to 350°C and the pressure from surface pressure to more than 29 000 psi.
Each well is dissimilar in both length and properties, sense that the cement is required to be able
to set at the correct location at the precise time and retain its integrity during the time for
abandonment (temporary or permanently) for the dissimilar wells.
In order for the cement accomplishes all of the necessities, admixtures are frequently
incorporated to the cement mixture. The admixtures may transformation the capabilities of the
cement and support to get an effective placement of the cement slurry under the different
environments.
There are over a hundred such admixtures existing currently, and they can mostly be classified
into eight groups; accelerators, retarders, extenders, weighting agents, dispersants, fluid loss
control agents, and lost circulation control agents and specialty additives. These eight groups will
be deliberated briefly as follows;
i. Accelerators
Accelerators are chemicals that can rise the strength growth and decrease the setting time of the
cement (Nelson & Guillot, 2006). They may be used to influence the delay in cement setting
caused by other admixtures. The greatest common inorganic salt to be used as accelerator is
sodium chloride (NaCl).
33
The diverse salts work as accelerators at different concentrations implying that for a certain
concentration, it may transform its properties to be unfavorable. An example is when a
concentration of 15% NaCl is used, it acts as an accelerator, but if the concentration surpasses
20% it will convert its properties and act as a retarder.
ii. Retarders
Retarders are used to delay the setting time of the cement (Nelson & Guillot, 2006). The process
of describing the consequence that the retarders have on the curing process is still not clear.
There have been anticipated numerous diverse concepts but still none of them can completely
describe the process. Four of the anticipated concepts have been shortly defined (Nelson &
Guillot, 2006):
Adsorption theory: The retarder adsorbs onto the surfaces of the hydration products, thereby
preventing interaction with water.
Precipitation theory: The retarder reacts with calcium ions, hydroxyl ions, or both in the
aqueous phase, creating an insoluble and impermeable layer around the cement grains.
Nucleation theory: The retarder adsorbs onto the nuclei of hydration products, striking their
upcoming development
Complexation theory: The retarder chelates the calcium ions, stopping the development of
nuclei (Nelson & Guillot, 2006).
nevertheless, the concepts are different, there may be seen a minor comparison in them;
dissolving and absorption of salts that stops the hydration process (Nelson & Guillot, 2006). The
greatest usually used retarders for well cements are the sodium and calcium salts of lignosulfonic
acids.
34
iii. Extenders
Extenders can have numerous roles such as reducing the density of a cement system, decreasing
the amount of cement per unit volume of set product, or both (Nelson & Guillot, 2006). The
decreased slurry density will lower the hydrostatic pressure during cementing and thereby avoid
lost circulation due to weak formations.
The extenders are separated into three groups; water extenders, low-density aggregates and
gaseous extenders. Water extenders are clays and other water viscosifying agents that permit
extra water to bind to the cement system. This supports to sustain consistent slurry and avoids
the creation of free water.
The low-density groups are aggregates with a density lower than Portland cement (3,2 g/cm3),
and are used in huge quantities to decrease the slurry density. Gaseous extenders are foamed
cements set using nitrogen or air that gives the cement a low density but good compressive
strength. Possibly the greatest significant group of extenders is pozzolans. Pozzolans may also
be known as alkali activated binders.
Pozzolans are siliceous or siliceous and aluminous material that owns slight or no cementitious
value but will in a finely divided form and in the existence of moisture, chemically react with
calcium hydroxide to form compounds owning cementitious properties (Nelson & Guillot,
2006).
During cement hydration calcium hydroxide will be liberated and removed by the water that
interact with the cement (Nelson and Guillot, 2006). This leads to a decrease in the compressive
strength. Though, when pozzolans are existing, they avoid the calcium hydroxide from escaping;
later, there is a build-up in the compressive strength.
35
There are two major classes of pozzolans; natural and artificial pozzolans. Natural pozzolans are
volcanic ashes and diatomaceous earth and artificial pozzolans include for example metakaolin
and fly ash.
In the recent years the interest in examining the effect of alkali-activated binders has improved.
Experimental researches on determining the reactivity of different raw materials have been done
(Buchwald et al 2013). In their test the released concentration of silicate and aluminate
monomers by alkaline solutions were determined.
They used five different raw materials; metakaolin, slag, fly ash, brick powder and thermal
activated clay. Their outcomes displayed that metakaolin liberated the maximum quantity per
weight of silicate and aluminate, followed by fly ash. Though, fly ash required additional time
before the monomers were noticeable in the solution due to the smaller surface area and
developed stability of the glassy phase in fly ash compared to metakaolin.
The quantity of released silicate and aluminate in the thermal activated clay and the brick powder
was almost the same.
This can be described by the nearly matching chemical and phase compositions of the two
materials. For the slag, the quantity given out was quite little, and did not change over the contact
time. It was also found that the strength rose, for all five materials, when the content of sodium
hydroxide increased. This displayed that the formation of calcium silica hydrate phases and
calcium aluminate hydrate phases leads to respectable strength performance.
iv. Weighting agents
In some wells there is a necessity to raise the slurry density to avoid a decline in the hydrostatic
pressure that may cause an unrestrained condition of a well (Nelson & Guillot, 2006). One way
to decrease the slurry density is to decrease the quantity of mix water. Additional way is
incorporating weighting agents.
36
These weighting agents should have a particle size distribution that is well-matched with the
cement, have a low mix water requirement, be well-matched with other cement admixtures that
may be present and be inert, due to cement hydration. The utmost common weighting agents are
ilmenite, barite and manganese tetraoxide.
v. Dispersants agents
Other cement pastes are highly viscous due to the high concentration of suspended particles and
solid volume fraction (Nelson & Guillot, 2006). Extremely viscous pastes may cause
complications during placement of the cement, particularly in long and inclined wells. To
decrease the viscosity of the cement paste, dispersants can be added. The utmost commonly used
dispersant in is polynapthalene sulfonate.
It is very price effective though, because of its toxicity to algae, it is not as much of used in
marine situations. Other commonly used dispersants are lignosulfonates and
hydroxycarboxylic acids. But there is a problem connected to these as well they have revealed
to have a retarding effect, meaning that they reduce the setting time of the cement.
vi. Fluid Loss Control Agents
In the process of cement placement, some of the aqueous phase from the cement paste will leak
to the formation and this is called fluid loss (Nelson & Guillot, 2006). It is significant to dodge
high fluid losses to stop well complications. One tricky may be that there is such high fluid loss
when pushing down the cement that the density of the slurry rises expressively, causing trouble
with pumping it more down to the right position.
The fluid loss might also convert the design properties of the cement pastes which may result to
poor sealing of the well. To stop these complications fluid loss control agents may be added to
the cement slurry. The exact processes that happen are not yet totally understood, though there
are some mechanisms that are known to arise. The particles in the fluid loss control agents can
decrease the filter cake permeability or raise the viscosity of the aqueous phase, or both.
37
The utmost commonly used fluid loss control agents are divided into two groups; finely divided
particulate materials and water-soluble polymers (Nelson & Guillot, 2006). The water-soluble
polymers that are used might be natural and synthetic. The greatest extensively used particulate
materials are bentonite, carbonate, carbon black, Nano-silica, asphaltene, and thermoplastic
resins. Nano-silica is used in this thesis.
vii. Lost Circulation Control Agents
Lost circulation is a tremendously complication when cementing (Nelson & Guillot, 2006).
When executing a primary cementing job there is often a need for remedial cementing due to the
lost circulation. Lost circulations frequently happen in weak, highly penetrable and cracked
zones.
To stop this, materials that bridge over fractures and blocks weak zones are incorporated. The
materials rise the resistance of the zone contrary to pressure. Regularly used bridging agents are
granular materials, such as gilsonite and granular coal.
If the cavernous zones are so huge that the bridging agents can’t stop lost circulation, thixotropic
cements are used. When thixotropic is used in the cement paste it will no longer be exposed to
shear and the paste will consequently yield a gel form and develop self-supporting. The
thixotropic cement will finally plug the lost circulation.
viii. Specialty Additives
There is silent numeral of materials that are not appropriate into the previously stated groups
(Nelson & Guillot, 2006). These materials are called specialty additives. These comprise
antifoam agents, fibrous materials that are used to upsurge the resistance to the stresses related
with perforating, hydraulic fracturing, and formation movement, radioactive tracing agents that
are used to calmer detect the plug and mud decontaminants that are used to decrease retardation
of the cement paste when mixed with drilling fluid.
38
2.5.2 Cement Mineral Admixtures
Mineral admixtures can be mixed effectively with Portland cements to raise the compressive
strength of a cement paste (Dyer 2014). Use of fly ash, silica fume, and other non-natural or
natural cementitious or pozzolanic admixtures are tactics for designing cement paste for
improving the hardness of the cement paste.
Coal burning power plants and metallurgical furnaces manufacturing iron, silicon metals, and
ferrosilicon alloys have been the main foundations of these mineral admixtures that would have
then been rejected as a waste by‐product (Mehta & Monteiro 2006). A few of these mineral
admixtures are shortly deliberated.
i. Fly Ash admixtures
It is a regularly silicate glass that forms from the condensation of molten coal ash accumulated
from the exhaust gases at coal‐fired power stations (Neville 1998). It is constituting of spherical
units generally less than 1 to 100 μm, with an average diameter reported as 20 μm (Mehta &
Monteiro 2006).
There is a high calcium form of fly ash categorized by ASTM C 618 as Class C that has lime
(CaO) content from 10% to more than 30% (Kosmatka & Wilson 2016). Class C fly ash is
measured moderately cementitious due to the reactive calcium content existing in its composition
commonly in the forms of tricalcium aluminate (C3A), anhydrite (CS), and tetracalcium
trialuminosulfate (C4A3S) (Mehta & Monteiro 2006).
There is also a low calcium fly ash, chosen as Class F by ASTM C 618 that is generally
siliceous. Class C fly ash when in conformance to ASTM C 618 has at least 50% of collective
content of silicon (SiO2), aluminum (Al2O3), and ferric oxide (Fe2O3). For Class F fly ash, that
condition is at least 70% (Kosmatka & Wilson 2016).
39
The valuable part of this mineral admixture is the pozzolanic outcome it has on the hydrated
cement paste. The silica reacts with the CH phase of the hydrated cement to produce secondary
C‐S‐H that binds up the calcium ions and brands them tougher for sulfates to extract except
where MgSO4 or acidic situations are met (Wee et al., 2000). Only class F fly ash is suggested
for sulfate resistance as the high calcium Class C diversity will help as another basis of calcium
ions for reaction in the existence of sulfate ions.
As described in contrast studies, use of high calcium fly ash can result to extra increase than that
detected with cement only samples (Ferraris et al., 2006). Low calcium fly ash incorporation will
also decrease the permeability of the paste due to its fine sized elements acting as filler and the
development of secondary C‐S‐H that will have a pore filling outcome (Dyer 2014).
The total CH existing in the matrix will also be decreased by substituting the cement used in the
mixtures, as fly ash is naturally used to substitute 25‐35% of the cement by mass (ACI
Committee 201 2008). There is also indication that a pozzolanic reaction enables additional
alumina to be absorbed in the C‐S‐H phase, consequently dropping its obtainability for ettringite
development (Dyer 2014).
ii. Ground Granulated Blast Furnace Slag
Ground granulated blast‐furnace slag is another by‐product of smelting iron ore for metal (Dyer
2014). Limestone is injected in the furnace to remove silicon, magnesium, and aluminum
impurities in the ore. Then the molded slag is quickly cooled to procuce glass granules that when
ground to a dust of 400 to 500 m2/kg Blaine fineness display good cementitious and pozzolanic
properties (Mehta & Monteiro, 2006).
The behavior of ground granulated blast‐furnace slag is similar to high calcium fly ash, although
the fly ash has been in concrete application much longer. Higher levels of cement replacement
and using ground granulated blast‐furnace slag with low Al2O3 content has shown to be more
effective at increasing compressive strength of cement paste since the total aluminates and CH
available for reaction are reduced through dilution (Dyer 2014).
40
Ground granulated blast furnace slag is regularly of finer particle size than the cement it is mixed
with. Consequently, it assists as filler and improves the grain size of the hydrate phases which
supports decrease permeability of cement paste (Dyer 2014).
iii. Silica Fume
Silica fume is an active mineral admixture. It is also a pozzolanic kind mineral admixture but
extra reactive than fly ash or ground granulated blast furnace slag due to its finer size. It
consumes the CH phase to yield secondary C‐S‐H which toughens and densifies the cement
paste.
2.6 Nanotechnology
Over the previous decades, nanotechnology, or the manipulation matter at the Nano scale level,
has directed to uprisings in physics, chemistry, biology, and other industries where new materials
and practices have been revealed (Sanchez & Sobolev., 2010).
An invasion of innovative and commercially existing Nano-materials has caused to a

transformed research struggle in testing their application in cement paste and understanding how
their operation of cement paste at the Nano-scale level can change the bulk properties as entire
(Singh et al., 2013).
There is convincing suggestion that ultra-fine particles, such as Nano silica, can advance the
plastic and hardened properties of the cement paste (Campillo et al. 2004). Nano silica can be
designated as a produced high purity, highly reactive siliceous pozzolan Nano-particle admixture
Quercia & Brouwers 2010).
41
2.6.1 Pozzolans Materials
Nano silica, owing ultra‐fine particle size and high silica (SiO2) purity, can be categorized as
extremely reactive siliceous pozzolan. Pozzolanic materials include a comprehensive collection
of natural or artificial materials that display pozzolanic activity.
Pozzolans are either silicious or aluminosilicieous materials that alone exhibit little to no
cementitious behavior, but when in the existence of moisture and calcium hydroxide (CH) in a
finely divided form, they will react with CH to form extra stable calcium silicate hydrate (C‐S‐H)
phases that possess cementitious properties (Neville 1998).
This brands pozzolans a necessary material because they can yield the CH phase or else has no
cementitious value to the matrix besides sustaining a high pH that retains the C‐S‐H phase stable
and react with it to form extra “glue” binder that toughens the paste and decreases its
permeability (Kosmatka & Wilson., 2016).
The reactive alumina if exist will react to formulate numerous calcium‐aluminate phases
comparable to the alumina phases (C3A and C4AF) natural to the cement. Generally, there are
three major benefits of using a pozzolanic material in cement paste from the nature and products
of the pozzolanic reaction (Mehta & Monteiro., 2006). Pozzolanic reactions are slower than
hydraulic ones, so mixtures with high pozzolan content release heat of hydration slower (Mehta
& Monteiro 2006).
This can be valuable if developing extreme inner temperatures due to hydration in mass paste
pours or high temperatures established during hot conditions pouring are concerns. If
temperatures develop that prevent ettringite from precipitating during the early stages of
hydration. The second advantage is the consumption of CH during the pozzolanic reactions, the
advantages of which are not only with sulfate resistance, but general decreases of susceptibility
to aggressive ions and acidic situations. The third advantage is the rises in strength and declined
permeability due to deposition of secondary C‐S‐H.
42
Raising the compressive strength of the cement paste makes it extra resistant to extensive
stresses from gas influx from formation. The secondary C‐S‐H precipitated from the pozzolanic
reactions and decreases permeability by filling up the pores, which improve the pore size
spreading and make the void system extra resistant to gas formation invasion (Mehta & Monteiro
2006).
2.6.2 Micro silica Particles
Nano silica particles are normally associated to micro silica (silica fume) materials in several
studies deliberated in the literature review due to their essential comparisons. At the beginning,
both on a chemical level are purely siliceous pozzolans. Both are silicon dioxide (SiO2) existing
in a spherical reactive non-crystalline form.
The major distinguishing aspect between both is their fineness and the related definite surface
area. Nano silica particles are commonly comprised of spherical particles less than 100 nm and a
nitrogen absorption measured surface area that frequently surpasses 80 m2/g (Campillo et al.
2004). Micro silica (Silica fume) materials are consisting of particles usually smaller than 1.0 μm
in diameter with an average particle size of 0.1 μm or less (Kosmatka & Wilson 2016; Holland
2005; ACI Committee 234, 2006).
Since micro silica particles regularly span the microscale range, this pozzolan is also denoted to
as silica fume. Most silica fume has a measured surface area of about 20 m2/g through the
nitrogen absorption method (Kosmatka & Wilson, 2016) which grades it amongst the extremely
active pozzolan admixtures (Mehta &Monteiro, 2006).
Micro silica materials are an industrial by‐product of electric arc furnaces used to produce silicon
metals and ferrosilicon alloys from high purity quartz and coal (Neville, 1998; Kosmatka &
Wilson, 2016). Hot gaseous SiO2 exiting the furnaces, oxidizes into SiO2 and as it cools it
condenses into the distinguishing ultra-fine amorphous silica materials that are then composed in
bag filters. In that amorphous glass form and fineness, the SiO2 materials are very active in a
situation conducive to pozzolanic reactions.
43
Micro silica materials are considered as appropriate materials for use in cementitious mixtures as
a pozzolan material desires to meet ASTM C 1240 standards where documented. Commercially
it is existing as an undensified powder; water-based slurry, or in a densified/compacted powder
form (Kosmatka & Wilson, 2016). Some cement producers also offer mixed cements where
silica fume could constitute 7‐12% of the binder content (ACI Committee 234, 2006).
Micro silica materials collected from electric arc furnaces that produce silicon metal regularly
features SiO2 content above 90% by mass and 99% percent purity is not ignored (Kosmatka &
Wilson, 2016). For micro silica materials collected from electric arc furnaces that produce
ferrosilicon alloys, the silica content directly correlates with the quantity of silicon in the alloy
produced and if the alloy formed comprises only 50% silicon, the by‐product silica fume will
probably not meet the 85% minimum condition by ASTM C 1240 (Kosmatka & Wilson, 2016).
i. Micro Silica Particles
Micro Silica particles have been around a lot longer than Nano silica particles. They were
initially collected for testing in 1947 in Kristiansand, Norway. Most of the research on micro
silica and its properties was done in Nordic countries and its first structural application was also
in Norway in 1971 (Kosmatka & Wilson 2016).
Enhancements in strength and detected longevity contrary to sulfate exposure equivalent to

sulfate resisting cement mixtures were amongst the first recognized advantages of silica fume
from the testing done in the 1950s (Hewlett & Massazza 2003). The US Army Corps of
Engineers initially selected to use silica fume for repairing the Kinzua Dam in Pennsylvania due
to its high abrasion resistance (Kosmatka & Wilson 2016).
44
ii. Effect of Micro Silica on Water Demand
Incorporating micro silica to a cement paste, due to its large specific surface area, expressively
rises the internal surface area of the mixture which rises its cohesiveness (Hewlett & Massazza
2003). This adhesiveness of the mixture naturally needs a rise of the slump to sustain satisfactory
workability through practice of chemical admixture. The high surface area of the pozzolan
causes an upsurge in water demand.
When the new mixture is disturbed, shaken, propelled, or worked in any way, the spherical micro
silica materials will grease the cement paste and aggregate, filling the mixture with greater
movement than cement only paste of similar slump (Hewlett & Massazza 2003).
iii. Effect of Micro Silica Particles on Setting Time
Since pozzolanic reactions delays than those of ordinary Portland cement and be subject to CH
liberated from setting of the paste to begin, the setting time of mixtures comprising micro silica
particles can hypothetically rise (Hewlett & Massazza 2003).
nevertheless, incorporation of micro silica has not been detected for the mostly smaller 5‐10%
dosages of micro silica used in exercise (Kosmatka & Wilson 2016). In testing on concrete
mixtures comprising 20% micro silica, a rise in setting time of 6‐20% was logged (Siddique &
Khan 2011).
iv. Effect of Micro Silica Particles on Heat of Hydration
The heat of hydration that a micro silica particle donates could be identical to or superior to that
of Portland cement depending on its amount and surface area (Kosmatka & Wilson 2016). A
mixture comprising micro silica particles planned for the similar compressive strength at 28 days
as one planned only with cement, would develop less heat of hydration than the latter. Micro
silica particles can speed up the hydration of ordinary (Siddique & Khan 2011)
45
Portland cement phases C3S, C2S, and C4AF due to its high surface area and pozzolanic
reactivity (Kurdowski & Nocuń‐Wczelik 1983).
In the presence of CH, micro silica starts melting to generate a situation where there is a super
saturation of silica in respect to a silica rich phase that starts establishing at the surface of the
micro silica particles (Siddique & Khan 2011). At that point, the moderately dissolved micro
Silica all assist as new topo chemical precipitation sites for extra C‐S‐H which speed up
hydration at all stages (Siddique & Khan 2011)
v. Effect of Micro Silica Particles on cement paste
Micro silica particles will rise the strength of cementitious mixtures, the extent of which depends
on the type of mix, cement type, micro silica amount, use of water reducing admixture, and the
curing approaches used (Hewlett & Massazza 2003).
Due to its fineness, large surface area, and extremely reactive amorphous nature, micro silica
particles can donate to the compressive strength early on as well (Kosmatka & Wilson 2016).
provided that good placement and curing methods are followed, the strength gains of
incorporating micro silica can be realized within the period of 3 to 28 days in cured samples
(Kosmatka & Wilson 2016).
Cement paste mixtures comprising micro silica benefits the conventional relation between water
to cement ratio (w/c) and strength but the arc shifts right in the direction of higher compressive
strengths for a given w/c as revealed in Figure 2‐4. Cementitious mixtures comprising micro
silica also see developments in tensile and flexure strength comparatively proportional to those
observed for compressive strength (Hewlett & Massazza 2003).
High strength micro silica confined cement paste has proved to improve abrasion and impact
resistance of cement paste and has been implemented for numerous such applications together
with the repair work at dams and channels (Hewlett & Massazza 2003). In Norway, high strength
(95 MPa) micro silica paste has become the favorite paving material for high wear surfaces and
46
has decreased the wear on roads where installed by a factor of 5‐10 in contrast to high quality
black top (Hewlett & Massazza 2003).
Figure 2-4: Effects of Micro silica particles on compressive strength to water Cementous
ratio
The way micro silica affects the hardened and longevity characteristics of cementitious
compounds is based on its physical properties on the microstructure of the paste and its chemical
properties as a pozzolan.
vi. Physical Effects of Micro Silica Particles
By decreasing bleeding of mix water due to its ultra-fine particles and high surface area, micro
silica stops separation and pouches of bleed water from creating under coarse aggregate and
rebar which can become weak spots and decrease bonding (ACI Committee 234 2006). As
deliberated in its effects on heat of hydration, due to its fine particle size, micro silica provides
47
nucleation sites where the hydrated cement phases and secondary C‐S‐H can precipitate. This
densifies the cement paste and quickens hydration (ACI Committee 234 2006).
This effect is not exceptional to micro silica but has shown to happen in other testing where inert
ultra-fine fillers such as CaCO3 formed a comparable effect. Micro silica improves the particle
filling of cement paste by occupying the pores in between cement grains (ACI Committee 234
2006). This particle filling effect needs that the surface forces of particles, which rises as particle
fineness enters the macro and Nano‐range, are decreased by a adequate amount of water
reducing admixture (ACI Committee 234 2006).
This scenario has been revealed in testing of mixtures with 5% or less micro silica cement
substitution by detecting an assessable reduction in water demand due to micro silica filling the
voids between the cement particles which would have then been occupied with water (Bache,
1981). The primary physical effect of micro silica on the microstructure of cement paste is its
densification and porosity decrease at the cement paste transition zone also stated to as the
interfacial transition zone since it also applies for other wall and barrier situations (ACI
Committee 234, 2006).
The interfacial transition zone is a zone closely 50 μm that formulates between the cement paste
and boundary situations, such as the aggregate. This zone is normally weaker in strength, shown
to be more porous, and exhibits poorer particle packing than that of the bulk cement paste (ACI
Committee 234 2006).
More of the CH phase precipitates in this region and it tends to precipitate in larger crystals that
are characteristically oriented parallel to the aggregate surface as shown in Figure 2‐2. The
effects of micro silica are apparent in the micro silica contained mixture also shown in the same
figure.
Without micro silica, the large CH phase crystals that precipitate in the interfacial transition zone
do not donate much to strength and create a weak zone since they are easily cleaved (Monteiro et
48
al. 1985). Numerous researchers have confirmed that micro silica can densify the interfacial
transition zone to a state of alike strength, permeability, and porosity to that of the bulk paste and
basically remove its role as the weaker link (ACI Committee 234 2006).
longevity of the cementitious composite is also substantially improved through the densification
of the interfacial transition zone meanwhile the more porous structure of the interfacial transition
zone substantially donates to the total ionic diffusivity and fluid permeability of the cement paste
matrix.
Figure 2-5: SEM of the interfacial transition zone between Cement Paste Mixture at 28
days for (A) without micro silica, (B) with micro silica
vii. Chemical Effects of Micro Silica Particles
The chemical effects of micro silica from its pozzolanic reactivity as discussed in the section on
Pozzolans. The pozzolanic reaction process of micro silica and its hydration in cement pastes is
generally designated through the gel model theory (ACI Committee 234 2006). Upon interaction
with water, micro silica is supposed to melt and transform into a silica rich gel that absorbs most
of the adjacent water. The gel then starts agglomerating between the grains of hydrating cement
and coats the hydrating cement particles as well.
49
The CH that starts precipitating out of the alite and belite hydration are reacted with at the
exposed surfaces of the silica‐rich gel to form secondary C‐S‐H that occupies the pores and inter
particle spaces left behind by the cement formed C‐S‐H. This chemical procedure of consuming
the CH phase and changing it to secondary C‐S‐H contributes to the physical mechanisms
designated in the former section towards generating a very dense paste (ACI Committee 234
2006).
2.6.3 Nano silica Particles
Nano silica particles are not a byproduct from industrial process as for the situation of silica
fume. It is produced and there are numerous approaches for its creation that produce Nano silica
of different nanoscale particle sizes and forms.
Outside of its relatively current application in cement paste, Nano silica has been used in other
industries such as ceramics, lens, glass, rubbers and paints (Campillo et al. 2004). It has been
used as an anti‐sliding agent, to achieve refractory behavior, thermal resistance, anti‐reflective
surface treatments, and more (Campillo et al. 2004).
Some of the approaches used to produce Nano silica are revised in this section. One method is
based on the sol gel process that can be done at room temperatures (Quercia & Brouwers 2010).
The process entails adding starting materials, often sodium silicate (Na2SiO4) mixed with
organometallics such as tetramethoxysilane CH3OSi(OCH3)3 or tetraethoxysilane Si(OC₂H₅)₄,
into a solvent and precipitating silica gel by converting the pH of the solution (Quercia &
Brouwers 2010).
The silica gel can then be filtered, dried, and burned to produce Nano silica in powder form, or
dispersed back into a solution typical of 20‐40% wt. solid SiO2 with a stabilizing agent such as
Na, K, NH3, or others (Quercia & Brouwers 2010). Nano silica can also be produced by
vaporization of quartz material at a temperature between 1500 and 2000 °C with an electric‐arc
50
furnace, which is the method most similar to how silica fume is collected (Quercia & Brouwers
2010).
The Nano silica particles are condensates of the SiO2 vapor that is oxidized in a cyclone. There is
also a biological method developed where Nano silica is produced using digested humus from
California red worms generating Nano silica ranging in size between 55 nm to 245 nm with an
88% process efficiency (Quercia & Brouwers 2010). The worms are fed rice husk or biological
waste material that naturally contains at least 22% silica.
There is a precipitation method for producing Nano silica that involves precipitating Nano silica
from a solution that uses precursors such as sodium silicates Na2SiO4, burned rice husk ash,
semi‐burned rice straw ash, magnesium silicate, and others. There is a newer method involving
the treatment of the mineral olivine (Mg+2 or Fe+2)2SiO4 with sulfuric acid H2SO4 through which
particularly fine Nano silica (6 to 30 nm) is precipitated (Quercia & Brouwers 2010).
i. Effects of Nano silica particles on Water Demand
Numerous lessons have showed that the incorporation of Nano silica particles, even in slighter
amounts than micro silica particles, has raised the water demand to retain a satisfactory
workability. This is directly credited to the high surface area of the nano-material, which is
frequently in surplus of 80m2/g (Singh et al. 2013; Tobón et al. 2010).
There is an observed decrease of spread, rise in the cohesion and higher measured rheological
yield stresses measured for cement paste containing increasing dosages of Nano silica (Luciano
Senff et al. 2009). In a rheological study where Nano silica particles of 9nm of 300m2/g present
in 30% wt. slurry was compared against micro silica with a specific surface area of 18.41m2/g,
plasticity was measured through a mortar flow table and rheometer (L. Senff et al., 2009).
51
Increases in torque measured with the rheometer and reduction in spread as measured on the
flow table were correlated to reductions in mixture plasticity and increases in viscosity.
Addition of Nano silica reduced plasticity more so and at a faster rate than micro silica at the
same amounts. Figure 2‐6 from the mortar spread testing done in that study indicated that as the
dose of Nano silica increased from 0 to 3.5%, the table spread reduced. This loss of workability
and rise in paste cohesiveness, even at small amounts, stems from the higher surface area
particles of Nano silica in contrast to micro silica.
Figure 2-5: Flow Table Spread of Mortars Comprising 0% to 3.5% Nano silica particles (L.
Senff et al. 2009)
ii. Effects of Nano silica particles on Setting Time
Small amounts of Nano silica have revealed to decrease setting times (Luciano Senff et al. 2009;
Zhang et al. 2012). In one study on slurry, just 2.5% Nano silica by weight of cement decreased
the setting time by 60% by shortening the dormant period (Luciano Senff et al. 2009). The
decrease in the setting time has been correlated to the extreme fineness of the Nano silica
52
particles and their associated high surface area that significantly exceeds that of microsilica as
well (Zhang et al. 2012).
In a study of using Nano silica on cement paste with approximately 50% slag, the 2% Nano silica
confined paste exhibited important decrease in early and last setting time in contrast to a slag and
cement control and a mixture with comparable 2% of micro silica which did not decrease the
setting time much from the control (Zhang et al. 2012).
iii. Effects of Nano silica particles on Heat of Hydration
In addition, quickening hydration the incorporation of Nano silica has revealed to rise the rate of
heat evolution and peak temperatures produced during the first 24 hours (Singh et al. 2013; Said
et al. 2012). Because pozzolanic reactions are generally slower and depend on the hydration of
the cement phases first to access reserves of CH, the acceleration of the hydration kinetics has
been mostly attributed to the ultra-fine nature of the nanoparticles and their associated high
surface area (Said et al. 2012).
Nano silica can also quicken the hydration of other mineral admixtures such as slag and fly ash.
The cumulative heat produced with Nano silica and other mineral admixtures will be higher with
increasing amounts of Nano silica (Zhang et al. 2012).
Figure 2-6: Effects of Nano silica particles on heat hydration (Zhang et al. 2012).
53
Note that as the Nano silica content increases from 0% to 2%, both peak 2 (cementitious
hydration reactions of silica and alumina phases) and peak 3 (pozzolanic reactions) shift to an
earlier age and the cumulative curves indicate the higher the Nano silica content, the more
cumulative heat is generated from the cementitious and pozzolanic hydration reactions combined
(Senff L. et al., 2009).
In cement only mixtures, the addition of Nano silica not only reduces the dormant period but can
accelerate the rate of reactions leading to a higher heat evolution peak, all due to the high
reactive surface area of its nanoparticles (Said et al., 2012).
iv. Effects of Nano silica Particles on Cement Paste
The particle filling effect of Nano silica, similar to that observed with micro silica, helps fill the
pores between the cement particles. This filling densification contributes to strength since it
decreases the capillary porosity of the hydrated paste (Singh et al. 2013).
The pozzolanic benefits of Nano silica are also accelerated due to the Nano-scale size of the SiO2
particles and their high surface area which enable additional silica and CH interaction. Well
detached Nano silica also contributes much extra C‐S‐H nucleation sites in between cement
grains that can densify the paste beyond what is possible with micro silica. The denser secondary
C-S‐H formed at the expense of CH leads to rises in strength at all ages (Kawashima et al. 2013).
For optimal strength contributing nucleation and paste densification effects to take place, good
dispersion of the Nano silica particles is important otherwise weak zones and voids could form
compromising strength and permeability (Li et al. 2004).
The microstructure and pozzolanic effects of Nano silica are conveyed to rise the compressive
and flexural strength in concretes, mortars, and pastes in many studies (Singh et al. 2013;
Sanchez & Sobolev 2010).
54
There is comprehensive variability in the reported scale of strength developments from Nano
silica application, anywhere from 20% to more than 60% which is likely due to the extensive
variability in Nano silica particle sizes that are tested, their technique of mixing and spreading,
and the cements and other mineral admixtures that Nano silica is mixed with.
Based on its characteristic physical and chemical behavior in cementitious composites, it is likely
that given equally good dispersion, Nano silica of finer average particle size and larger specific
surface area can result in larger gains in strength between two otherwise identical mix designs.
v. Effects of Nano silica Particles on Longevity
Nano silica Particles has demonstrated to signify a lot of the comparable chemical and physical
effects as micro silica although in many direct comparison cases, beyond what is attained with
micro silica at the same quantity. In many studies, slighter substitution often less than 6% by
cement weight, have demonstrated to be effective or more than higher amounts of micro silica or
other pozzolanic admixtures.
Nano silica particles have also demonstrated to quicken the pozzolanic reactions and advance the
performance of mixtures containing large contents of other mineral admixtures that it is
matching within testing. Those comprise fly ash and slag, both of which on their own regularly
come with the tradeoff of slower development of strength (Sanchez & Sobolev 2010; Singh et al.
2013).
In terms of longevity, Nano silica contained mixtures have exhibited decreases in permeability
and reduced chemical susceptibility to sulfates in large part due to the paste and Inter
Transitional Zone densifying effect mixed with a extra rapid pozzolanic consumption of CH.
55
Chapter 3: Experimental Setup and Procedures
3.1 Introduction
This chapter describes both specific techniques and the overall experimental strategy, showing
the materials and equipment used during the experiment.
3.2 Experimental Materials

The experimental materials for this work were mainly purchased from different Chinese
manufacturers and some were provided in the Drilling laboratory of China University of
Geosciences (Wuhan). These materials are shown in Table 3-1 while Table 3-2 shows the
properties of Nano silica used;
Table 3-1: Experimental Materials
Materials Source
API Cement Class G
Nanosilica (n-SiO2)
Dispersant Purchased
Fluid loss additive
Tape water Laboratory found
Cement cube mould
Cement cubes (5cmx5cmx5cm) Laboratory made
56
Table 3-2: Properties of nano-SiO2
Particle Surface- Density Purity

size volume (g/cm3) (%)
(nm) ratio
(m2/g)
2
160±20 <0.15 >99.8
3.3 Experimental Instruments

The experiments were performed using the instruments found in the laboratory. These
instruments are shown in Table 3-3;
Table 3-3: Experimental Instruments
Name of the instrument Instrument Equipment manufacturer

model
Electronic universal testing WDW-Y10A Jinan XinGuang experiment machine

machine manufacturing co LTD
Constant speed blender TG –3060 Shenyang tiger petroleum equipment

manufacturing co LTD
Atmospheric pressure curing TG –1280 Shenyang tiger petroleum equipment

box manufacturing co LTD
57
3.4 Experimental procedures

The experiment procedures of this experiment regarding the mechanical compressive strength
test have been categorized into three steps as shown in the figure 3-1.
The procedures will include; preparation of samples, curing of experimental samples in

Atmospheric pressure curing box and testing of mechanical compressive load/force acting
perpendicular to the surface area of the simulated cement cube sample and calculation of its
compressive strength.
Figure 3-1: Experimental procedures plan flow chart.
58
3.4.1 Preparation of Samples
i. Sample Mixing Proportion
This experiment makes use of the mechanical strength cement cubes made up by mixing of water
weighing 354g, oil well cement class G weighing 792g and Nano silica materials containing
different percentage quantities of nano-SiO2 with Nano-size ranging from 20-30 nm.
The cement is replaced by nano-SiO2 Nano-materials of 0.0%, 1.0%, 2.0%, 3.0% and 4.0 wt. %
by weight maintaining the total weight content proportion of oil well cement and Nano silica
materials weighing 792g keeping constant the ratio of water to cementineous material (oil well
cement + Nano silica materials) at 0.45 (w/c= 0.45) as illustrated on Table 3-4.
Mixing quantities were determined according to American Petroleum Institute’s (API)

Specification 1 A for Cements and Materials for Well Cementing.
Table 3-4: Shows the Mixing proportions for this experimental test
Batch Water Cement Nano silica Total W/C

(g) (g) (g) weight Ratio
(g)
NS 0% 354 792 0 792 0.45
NS 1% 354 784.08 7.92 792 0.45
NS 2% 354 776.16 15.84 792 0.45
NS 3% 354 768.24 23.76 792 0.45
NS 4% 354 760.32 31.68 792 0.45
59
ii. Preparation of Sample Cubes
The oil well cement slurry containing Nano silica materials, fluid loss agent and dispersant
additives is properly mixed in the TG-3060 Constant speed blender for about 5 minutes.
After the cement slurry being properly mixed in a blender and stirred well several times with a
stirrer bar to ensure that it has a good consistency, the well mixed slurry was then poured into
molds cube to form the cubes of the size 5cm x 5cm x 5cm as illustrated on the figure 3-2 to 3-4.
The cement additives used in this study are 1.2 wt. % fluid loss agent and 0.5wt. % dispersant.
About 60 samples were prepared for this experimental study whereby the molding materials of
5cmx5cmx5cm dimensions were used to simulate the cement cubes.
The reasons for adding fluid loss agent and dispersant additives to the cement slurry were to
remove bubbles created in the cement slurry by reducing viscosity of the mixture and enabling
homogeneity of the mixture which will influence good bonding of the mixture.
Figure 3-2: The cement cube mold
60
Figure 3-3: Slurry poured into the mold
Figure 3-4: Fixing the mold

61
3.4.2 Curing of Experimental Samples
In order for the cement cubes to harden and gain its compressive strength, the samples were
taken into water bathing curing device at 80 ℃ temperature.
The cement cubes where totally immersed and left in the curing device for 2, 7, 15 and 28 days
of curing and then taken out waiting to cool naturally at room temperature ready for compressive
load test as illustrated in figure 3-5.
Figure 3-5: Curing samples in water bath curing device and a cured cement cube
62
3.4.3 Compressive Load Test
Compressive load test is the measurement of the maximum amount of compressive load a
material can withstand before fracturing.
The cured cement cubes are taken to a WDW-Y10A Electronic universal testing machine for
compressive load test. When the compression load on a hardened cement cube reaches a certain
value, the sample cube is destroyed.
Carefully the compressive load/force (F) is recorded; this test was performed to both samples
with and without Nano silica for all 60 samples as illustrated in figure 3-6 to 3-7.
The Universal testing machine is used to determine the compressive load used to calculate
compressive strength.
The three cement cubes are tested for typical category and the mean compressive strength of
three cement cubes is considered as the compressive strength of the specified group.
Figure 3-6 shows the schematic diagram of compression force test at the cured cement cube
while figure 3-6 shows how the compression load test was carried out.
63
Figure 3-6: Schematic diagram of compressive force acting perpendicular to the surface
area of a cement cube.
Figure 3-7: Shows a WDW-Y10A Electronic universal testing machine testing compressive
load of a cured cement cube
64
3.4.4 Compressive Strength Calculations
The compressive strength (P) of the hardened cement cube is calculated based on the
compression load/force (F) and the cement cube surface area (A) perpendicular to the
compression force acting on it.
The compressive load (F) is divided by the surface area (A) of the cured cement cube in order to
obtain the Compressive strength.
The compressive strength (P) of the cement cube was calculated mathematically as follows:
F F
P= = (8)
A Length(L)×Width(W)
Where:
P = the compressive strength of a cured cement cube, Unit MPa
F = the compressive Load/Force of the cured cement cube, unit KN
A = the axial surface area of the compressed cement cube, unit cm2
Figure 3-4:Shows a cured cement cube surface area dimensions
65
Chapter 4: Results and Discussions
4.1 Introduction
This chapter is concerned with the presentation of results of the experiments carried out towards
the objective of the project. The results are supplemented with tables and figures in order to have
a better analysis of the results.
4.2 Compressive Strength Test Results

In this experiment, a compressive strength test was done for 60 samples of cement cube of 5cm x
5cm x 5cm dimensions for 2, 7, 15 and 28 day incorporating silica material Nano-particles of 0.0
wt%, 1.0 wt%, 2.0 wt%, 3.0 wt% and 4.0 wt%. the experimental results of the compressive
strength test are summarized in tables 4–1 to 4-5.
Table 4-1:0.0% nano-SiO2 content experimental data
Experimental Cement Curing Sample Compressive Average

Conditions Replacement Time ID Strength Compressive
(n-SiO2) (Days) (MPa) Strength (MPa)
NS01 20.16
3 NS02 27.00 22.35
Curing NS03 19.89
Temperature
80°C NS04 24.08
7 NS05 20.55 23.69
NS06 26.44
0.0%
NS07 18.51
Water/cement 14 NS08 23.84 24.84
ratio 0.45 NS09 32.17
NS010 23.36
28 NS011 27.93 26.08
NS012 26.95
66

NS11 26.18
3 NS12 22.51 24.84
Curing NS13 25.85
Temperature
80°C NS14 21.08
7 NS15 27.34 23.07
NS16 20.79
1.0%
NS17 27.75
ratio 0.45 NS19 25.62
NS20 27.65
28 26.12

NS21 23.10
3 NS22 25.13 24.06
Curing NS23 23.95
Temperature
80°C NS24 22.87
7 NS25 20.36 24.97
NS26 31.68
2.0%
NS27 28.40
ratio 0.45 NS29 28.49
NS30 28.12
28 NS31 31.57 30.89
NS32 32.92
67

NS31 27.40
3 NS32 27.35 26.82
Curing NS33 25.71
Temperature
80°C NS34 28.58
7 NS35 30.15 28.64
NS36 27.19
3.0%
NS37 29.64
ratio 0.45 NS39 30.94
NS40 33.07
28 NS41 36.53 35.73
NS42 37.59

NS41 20.23
3 NS42 23.18 23.01
Curing NS43 25.62
Temperature
80°C NS44 25.87
7 NS45 21.14 22.66
NS46 20.97
4.0%
NS47 27.41
ratio 0.45 NS49 23.27
NS50 24.56
28 25.87
68
4.3 Compressive Strength Test Analysis
4.3.1 Influence of Nano Silica on Compressive Strength of Cement
Paste
The results from the compressive strength test as illustrated in table 4-1 to 4-5 and figure 4-1
shows clearly that all the samples containing silica Nano particle materials reveals higher
compressive strength compared to the samples without Nano silica materials for the curing time;
3day, 7day, 15day and 28day excluding the case where Nano silica content are 1.0 wt.% and 4.0
wt% which produced less compressive strength than samples without Nano silica content at the
same curing time of 7 days.
For instance, the samples contain 1.0 wt.% of Nano silica had a strength of 23.07 MPa and the
sample contains 4.0 wt.% of Nano silica had a strength of 22.66 MPa while the sample without
Nano silica content revealed higher strength of 23.69 MPa at the same curing time of 7 days.
Mostly incorporation of Nano silica materials to the cement slurry has proved to improve the
compressive strength of the cement paste (Li et al., 2014; Jo et al., 2007; Porro et al., 2005;
Ozyldirim et al., 2010).
The strength improvement of the harden cement paste is mostly influenced by the Nano particle
size of the silica materials that packs the pores/voids of the cement slurry which enhances strong
bond compaction of the cement slurry particles leading to the increase of resistance to the
compression load (Li et al., 2014; Jo et al., 2007).
Another significant reason that defines the compressive strength improvement of the cement
paste when nano silica material is incorporated to the cement slurry is the influence of the silica
Nano particle materials stimulating the pozzolanic reaction caused by its large surface area (Jo et
al., 2007).
69
36 35.73
34
Compressive Strength (MPa)
32
31.15
30.89
30
28.64
DAY-3
28
27.32 DAY-7
26.82
DAY-15
26.08 26.12
25.87 DAY-28
26
25.31
24.84 24.84 24.97 24.82
24.06
24 23.69
23.07 23.01
22.66
22.35
22
20
0 1 2 3 4
Nanosilica Content (NS%)
.
Figure 4-1: Shows the influence of Nano silica on compressive strength of cement paste
4.3.2 The Effect of Nano silica to the Compressive Strength of
Cement Paste
The effect of Nano silica content has been observed in figure 4-2 to 4-5, to improve compressive
strength of the hardened cement paste when Nano silica material was incorporated to the cement
slurry. Describing the strength of the cement paste cubes prepared with different percentages of
70
Nano silica materials for the same range of particle size. The cement pastes cubes with higher
percentage of Nano silica material demonstrated higher compressive strength than their
corresponding samples prepared with low percentages of Nano silica materials (Said et al.,
2009).
i. Effect of Nano silica Content for Curing Time of 3 Day
At 3 day of curing samples under the same temperature condition of 80oC as illustrated from
figure 4-2 it was observed that, for addition of Nano silica of 1.0%, 2.0%, 3.0% and 4.0% by
weight the cement paste cubes revealed a compressive strength of 24.84MPa, 24.06MPa,
26.82MPa and 23.01 MPa respectively in which strength of the hardened cement paste cube
raised to 2.49MPa, 1.71MPa, 4.47MPa and 0.66MPa with respect to the control sample cube
which revealed a strength of 22.35MPa.
paste for curing time of 3 days
71
The highest compressive strength of 26.82MPa is observed to sample containing 3.0 wt.% of
Nano silica materials while less compressive strength is observed to the samples containing
1.0%, 2.0% and 4.0% Nano silica material
Furthermore, observations from figure 4-2 shows that adding more percentages of Nano silica
material is important in increasing strength of cement paste to a certain limit after that any
increase in the percentage of Nano silica material will lead to a decrease in the compressive
strength of the hardened cement paste.
The Addition of more Nano silica particles to the cement slurry beyond the limit has been
observed when 4.0% of Nano silica particles contained in the cement paste resulting in the
decrease of compressive strength of the cement paste to 23.01MPa after being cured for 3 days
ii. Effect of Nano silica Content for Curing Time of 7 Day
The compressive strength of the cement pastes cubes observed to increase with the addition of
Nano silica materials to the cement slurry under the same curing conditions of 80oC temperature
and curing time of 7 days as shown on figure 4-3.
A compressive strength of a hardened cement paste of 23.69, 23.07, 24.97, 28.64 and 22.66 MPa
is revealed when Nano silica particles of 0.0%, 1.0%, 2.0%, 3.0% and 4.0% respectively by
weight are added to the cement slurry.
The compressive strength of hardened cement cubes was observed to raise positively by strength
of, 1.28MPa (2.0%), 4.95MPa (3.0%) and 1.03MPa (4.0%) relative to the compressive strength
of 23.69MPa (0.0%) of a control sample which had zero percentages of Nano silica material and
decrease of compressive strength by 0.62MPa from control sample was observed to the sample
containing 1.0% of Nano silica material.
The observations from figure 4-3 also shows that, the highest compressive strength is recorded
at 28.64MPa to sample containing Nano silica material of 3.0% while least compressive strength
was observed to the sample containing Nano silica of 1.0%, 2.0% and 4.0% by weight.
72
Having high and low compressive strength when different amount of Nano silica material is
added to the slurry portrays that the optimal amount of Nano silica materials which is required to
attain the highest compressive strength of 28.64MPa is 3 wt.%.
Observations from figure 4-3 shows that adding more percentages of Nano silica material is
percentage of Nano silica material will lead to a decrease in the compressive strength of the
decrease of compressive strength of the cement paste to 22.66MPa after been cured for 7days.
73
iii. Effect of Nano silica Content for Curing Time of 15 Day
The compressive strength of the cement pastes cubes observed an early increase in strength with
the addition of Nano silica materials to the cement slurry under the same curing conditions of
80oC temperature and curing time of 28 day as shown on figure 4-4.
It is generally observed that there is a significant increase of compressive strength when Nano
silica material of 1.0%, 2.0%, 3.0% and 4.0% is added to the cement slurry compared to the
slurry without Nano silica particles which revealed a compressive strength of 24.84, 25.31, 27.32
and 31.15MPa, 24.82MPa respectively.
The compressive strength of the hardened cement paste was recorded to increase by 0.47, 2.48,
6.31MPa for the sample containing Nano silica particles of 1.0%, 2.0% and 3.0% taking
reference from the control sample cube which revealed compressive strength of 24.84MPa with
0.0% of Nano silica particles and the decrease of 0.02MPa is observed for the sample cube
containing 4.0% of Nano silica particles.
The maximum compressive strength is observed to be 31.35MPa at the hardened cement paste
containing 3.0wt.% of Nano silica particles relative to the samples containing Nano silica
particles of 0.0%(24.84MPa), 1.0%(25.31MPa), 2.0%(27.32MPa) and 4.0%. (24.82MPa).
Observations from figure 4-4 also shows that adding more percentages of Nano silica material is
decrease of compressive strength of the cement paste to 24.82MPa after been cured for 15 days.
74
iv. Effect of Nano silica Content for Curing Time of 28 Day
Figure 4-5 has the same characteristics with figure 4-4. A significant increase in compressive
strength was observed to be 26.08, 26.12, 30.89, 35.73 and 25.87MPa for the cement paste cubes
containing Nano silica particles of 0.0%, 1.0%, 2.0%, 3.0% and 4.0% obtained at the same
curing conditions and time i.e. 80oC curing temperature and 28 days of curing.
The compressive strength of the hardened cement paste was recorded to increase by 0.04, 4.81,
9.65MPa and decrease by 0.22MPa for the sample containing Nano silica particles of 1.0%,
2.0%, 3.0% and 4.0% relative to the control sample cube which revealed compressive strength of
26.08MPa.
75
The maximum compressive strength is observed to be 35.75MPa at the hardened cement paste
containing 3.0% of Nano silica particles with comparison to the samples that contains Nano
silica particles of 0.0%(26.08MPa), 1.0%(26.12MPa), 2.0%(30.89MPa) and 4.0%. (25.87MPa).
Observations from figure 4-5 also shows that adding more percentages of Nano silica material is
hardened cement paste. The decrease phenomenon of compressive strength of cement paste
when large dose of 4.0% Nano silica particles is incorporated to the cement slurry has been
observed to decrease to 25.87MPa after being cured for 28days.
76
4.3.3 Summary of the Effects of Nano silica on Compressive
Strength of the Cement Paste.
General analysis from figures 4-2 to 4-5 shows that there is a significant increase in compressive
strength with an increase in percentages of Nano silica particles to the cement slurry. These
unpredicted results portray that the optimal percentage of Nano silica materials which is required
to attain the maximum compressive strength of 26.82MPa (3 Day), 28.64MPa (7 Day),
31.15MPa (15 Day) and 35.73MPa (28 Day) is 3.0wt%.
The maximum compressive strength of the cement paste was observed to be 35.73MPa when
3.0wt.% of Nano silica particles was added to the cement slurry and cured for about 28 days.
The phenomenon of increasing compressive strength when large percentages of Nano silica
particles is added to the cement slurry indicates that adding more percentage of Nano silica
material is important in increasing strength of cement paste to a certain limit after that any
increase in the percentage of Nano silica material will cause to a decrease in the compressive
strength of the hardened sample.
This phenomenon of decrease in compressive strength to 23.01MPa (3Day), 22.66MPa (7Day),

24.82MPa (15Day) and 25.87MPa (28Day) is observed at 4.0 wt. % when more percentages of
Nano silica particles is added to the cement slurry.
The reason behind this scenario is the additional percentage of Nano silica material that could
lead to agglomeration of its particles under the current dispersion situation. This agglomeration
of Nano particles happens when adding excessive quantity of Nano silica material because the
large surface area of Nano particles has the tendency to increase attraction capabilities of each
other leads to the formation of weak clogs consequently decreasing the compressive strength of
the cement paste.
Similarly, these clogs occupy the pores of the cement slurry affecting the filling effect of Nano
silica materials for these pores and results to the decreasing of the bonding strength of the cement
slurry. In eliminating or reducing the effect of dispersion and agglomeration of the Nano silica
77
materials colloidal Nano silica should be added because in the colloidal solution Nano silica
materials tends to scatter throughout the solution (Hussein et al., 2010 & Porro et al., 2005).
Formation of agglomeration leads to the effective surface area that reacts to form small amount
of C-S-H gel which leads to the formation of weak clusters that do not support large strength
which leads to the decrease in the compressive strength of the cement paste sample.
Also, the decrease in compressive strength when 4% of Nano silica particles is added was
possibly caused by less mixing water enough to react with this large amount of Nano silica
particles which leads to the weakness in hydration process and C-S-H gel formation.
This explanation means that water to cement ratio (w/c) for this cement slurry needs to be
improved in order to achieve the required uniformity and workability in order to match the other
compressive strength results of other cement slurry incorporated Nano silica particles of 0%, 1%,
2% and 3% which achieved the anticipated trend.
It is remarkable that adding Nano silica particles in large percentage should go together with
enough amount of water in order to avoid cracking and decreasing of the strength (Jo et al.,
2007).
This phenomenon is not for this study because the ratio of water to cement (w/c) and dispersant
and fluid loss agent amounts are the same in all cement paste cubes to ensure that such variables
have a neutral influence on the results of these experiments.
Decision can be made that a slight adjustment in the dosage of Nano silica particles causes to the
intense changes in the compressive strength in which high level of quality control have to be
attained in order to control this adjustment as necessary.
78
4.3.4 Effect of Curing Time on Compressive Strength of Cement
Paste
i. Effect of curing time on compressive strength for 0.0 % Nano silica
Under the same curing conditions of temperature 80oC and Nano silica content of 0%, figure 4-6
shows a significant increase in compressive strength of 22.35, 23.69, 24.84 and 26.08MPa with
an increase in curing age of 3, 7, 15 and 28 days respectively.
A maximum compressive strength of 26.08MPa was attained in 28 days of curing while the
minimum compressive strength of 22.35MPa was observed in a curing time of 3 days
This indicates that, the sample cube tends to gain more strength as the curing time of sample is
increased; this trend of rising up compressive strength with respect to the increase in curing days
has been illustrated on figure 4-6. Therefore, this figure has proved that the increase in curing
time improves solidification and cementation of the cement paste cube.
Figure 4-6: Shows the relationship between curing time and compressive strength of
cement paste for a dosage of 0.0% Nano silica particles
79
ii. Effect of curing time on compressive strength for 1.0% Nano silica
Observation from figure 4-7 shows that there is a significant increase in compressive strength
with increase in curing time.
Despite of the decline phenomenon of a compressive strength of 23.07MPa occurred at the

curing time of 7 days but the increase behavior of the compressive strength with respect to the
increase in curing time has been observed because the maximum compressive strength of
26.12MPa revealed at curing time of 28 days.
This phenomenon also proves that, the increase in curing time leads to the improve of the
solidification and cementation of the hardened cement paste resulting to the raise in the
compressive strength of the Hardened cement paste sample.
80
iii. Effect of curing time on compressive strength for 2.0% Nano silica
Figure 4-8 has the same behavior with figure 4-6 because it has showed a significant increase in
compressive strength with increases in the curing time. The compressive strength of 24.06,
24.97, 27.32 and 30.89MPa shows a tendency of increasing with increases in curing time at the
sequence of 3, 7, 15 and 28days respectively.
The highest compressive strength of 30.89MPa was observed at the curing time of 28 days while
minimum compressive strength of 24.06MPa was revealed at the curing time of 3 days as
illustrated on figure 4-8
This phenomenon of compressive strength to increase with respect to the increase in curing time
proves the fact that curing time as significant effect in the gaining strength of cement paste.
81
iv. Effect of curing time on compressive strength for 3.0% Nano silica
Figure 4-9 also shows same behavior as figure 4-6 and figure 4-8 of having the tendency of
increasing in compressive strength with curing time.
The compressive strength of 26.82, 28.64, 31.15 and 35.73MPa was observed to increase
significantly with increasing in curing time at the arrangement of 3, 7, 15 and 28days
respectively.
Whereas the highest compressive strength of 35.73 was observed at the curing time of 28 days
while minimum compressive strength of 26.82MPa was revealed at the curing time of 3 days as
illustrated on figure 4-9
This phenomenon of compressive strength to increase with respect to the increase in curing time
proves the fact that curing time as significant effect in the gaining strength of cement paste
82
v. Effect of curing time on compressive strength for 4.0% Nano silica
The behavior happened on figure 4-7 also prevails on figure 4-10 of showing significant increase
in compressive strength with increase in curing time but later on a decline in compressive
strength of 22.66MPa was observed at the same curing time of 7days.
Also, the decline phenomenon of a compressive strength of 22.66MPa occurred at the curing
time of 7 days but the increase behavior of the compressive strength with respect to the increase
in curing time has been also observed, because the maximum compressive strength of 25.87MPa
revealed at curing time of 28 days.
This phenomenon also proves that, the increase in curing time leads to the improve of the
solidification and cementation of the hardened cement paste resulting to the raise in the
compressive strength of the Hardened cement paste sample.
cement paste for a dosage of 4.0% Nano silica particles.
83
4.3.5 Summary of the effect of curing time on the compressive
strength of the cement paste.
The experimental results show that the compressive strength from both samples with and without
Nano silica particles increases with the increase in curing time in a sequence of 3, 7, 15 and
28days which indicates that hardness of the cement paste depends on curing time as shown on
figures 4-6 to 4-10
Nevertheless, incorporation of Nano silica particles approach to the cement slurry revealed a fast
growth of compressive strength which makes Nano silica particles additive better in improving
compressive strength by forming a stable cement bond as it is cures more as shown on figures 4-
7 to 4-10 This behavior shows the significant effect of curing time on improving compressive
strength of a cement paste.
The compressive strength growth rate shows a significant increasing scenario as the curing time
increases, although the values of compressive strength when incorporated 1.0% and 4.0% of
Nano silica particles revealed an increasing behavior with curing time but declined effect of
compressive strength happened at the curing time of 7days as illustrated on figures 4-7 and 4-10
The highest compressive strength values of 26.08(0.0%), 26.12(1.0%), 30.89(2.0%),

35.73(3.0%) and 25.87(4.0%), MPa was observed at the curing time of 28 days incorporating
different percentages of Nano silica particles while less values of compressive strength revealed
to increase in the sequence of curing time of 3, 7 and 15 days respectively in which the lowest
compressive strength was recorded at curing time of 3days as shown on figures 4-6 to 4-10
35.73MPa being the maximum compressive strength recorded after being cured for 28 days
incorporating 3.0wt.% of Nano silica particles as shown on figure 4-8. These observations also
proved that curing time is more significant in rising compressive strength.
84
Chapter 5: Conclusions and Recommendations
5.1 Conclusions from the Experimental Results

On the basis of the results from the experiments, regarding the scope, materials, methods,
techniques and other parameters related with this study, the following conclusions and
recommendations can be drawn as follows:
• The samples containing Nano silica particles revealed higher compressive strength
compared to the control samples without incorporation of Nano silica materials for all
curing ages of 3, 7, 15 and 28 days excluding the case where Nano silica content were 1.0%
and 4.0% after both being cured for 7 days which produced low compressive strength
compared to the control samples. Nano silica cement slurry also exhibited relatively high
early compressive strength.
• The highest compressive strength values of the sample cubes were observed at the curing
age of 28 days for both samples with and without Nano silica content, incorporated at
different doses while least values of compressive strength revealed at the curing ages of
3, 7 and 15 days respectively in which the lowest compressive strength was recorded at
curing age of 3days.
• The optimal percentages of Nano silica material which is required to attain a maximum
compressive strength of 35.73MPa is 3.0 wt. % under curing age of 28 days.
• Adding more percentages of Nano silica material to the cement slurry is important in
increasing strength of cement paste to a certain limit after that any addition in dosage of
Nano silica material to cement slurry will cause to a decline in the compressive strength
of the hardened sample. This phenomenon of fall in compressive strength to 23.01MPa
(3Day), 22.66MPa (7Day), 24.82MPa (15Day) and 25.87MPa (28Day) has been
85
observed when 4.0 wt. % percentages of Nano silica particles is added to the cement
slurry.
• Slight adjustment in the dosage of Nano silica particles leads to an intense changes in the
compressive strength in which high level of quality control should be set in order to
control these adjustment as necessary.
• The compressive strength from both samples with and without Nano silica particles
portrayed a tendency of increasing with an increase of curing age in a sequence of 3, 7,
15 and 28days; this indicates that hardness of the cement paste depends on curing time.
5.2 Recommendations for the industry application
• Companies that produce special slurry are required to consider Nano silica in marketed
products upon wide testing.
• Extra quality control on both particle size and composition is required for the Nano silica
production.
• The water to cement ratio and Nano silica dosages quantity have to be controlled in each
blend in order to accomplish adequate mixing without deficiency or extreme quantity of
mixing water.
• Because insignificant amount of Nano silica may have intense effect on cement paste, it
is essential to implement severe quality control on all phases of slurry producers.
• Main players in the building materials industry have to put more resources to research
work on integrating nanotechnology in building ingredients.
86
5.3 Recommendations for the future research study
• Numerous proportions of Nano silica particles have to be tried for compressive strength
in order to get the best proportion to be incorporated to the cement slurry to attain the
uppermost compressive strength.
• Conducting wider scope studies on the effect of Nano-silica on cement slurry with
preliminary trials.
• New kinds of Nano particles might have superior outcome than Nano silica particles and
have to be integrated in future study such as nano-Fe2O3 and carbon Nano tubes.
• Codes of exercise have to be presented for testing building materials with Nano particles
to investigate by what method to select the appropriate ratio of Nano silica to be
incorporated in cement slurry and the suitable water to cement ratio and other additives
amount to be added in order to acquire the needed properties for respectively applications.
• More research studies have to be done on the side effects of Nano silica materials on
human health and by what means these effects can be reduced or eliminated.
• Viability researches need to be done in order to assess if it is profitable to incorporate

Nano particles to cement slurry to discover the likely potential applications for adding
Nano particles in slurry specifically and in building materials in at large.
87
Acknowledgement
I would like to thank almighty God for all of His guidance and love throughout my life for
serving me to overcome all the snags I came across over the course of this study.
This thesis would not have been possible without the help and support of my thesis supervisor
Prof. Gu Jun. I would like to express my deepest appreciation to him for his endurance,
supervision and considerate advice throughout the numerous phases of this work. His assistance
has been valuable on both academic and individual level, for which I am tremendously grateful.
I would like express my sincerely appreciation to the Ministry of Energy (Tanzania) in

collaboration with Chinese Scholarship Council (CSC) for the sponsorship of my Master’s
degree in China. My Master’s degree would have not been possible without these two
Authorities.
Moreover, I would like to recognize my laboratory mates both Chinese and foreign students
who were extremely helpful during all times of my experimental study. I am also appreciative to
my class and school mates for their guidance, support and inspiration during my stay in China
University of Geosciences (Wuhan).
A special thanks to Mr. Thomas Maagi Mtaki (PhD Candidate) for providing me with Nano
silica materials required for this study without forgetting his tremendous assistance in the
laboratory throughout my experiment without his help this work could not have been
accomplished.
Finally, I would like to express my sincere indebtedness to my lovely Mother and Fiancée who
gave me an unambiguous support throughout as always for which my mere expression of thanks
likewise does not suffice.
88
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Appendices
Appendix 1: Average Compressive strength for 3 days
Cement Replacement Average Strength (MPa) Average Strength increase
(n-SiO2) % (MPa)
0 - Control 22.35 -
1 24.84 2.49
2 24.06 1.71
3 26.82 4.47
4 23.01 0.66
Appendix 2: Average Compressive Strength for 7days
(n-SiO2) % (MPa)
0 - Control 23.69 -
1 23.07 -0.62
2 24.97 1.28
3 28.64 4.95
4 22.66 1.03
95
Appendix 3: Average Compressive Strength for 15days
(n-SiO2) % (MPa)
0 - Control 24.84 -
1 25.31 0.47
2 27.32 2.48
3 31.15 6.31
4 24.82 -0.02
Appendix 4: Average Compressive Strength for 28 days
(n-SiO2) % (MPa)
0 - Control 26.08 -
1 26.12 0.04
2 30.89 4.81
3 35.73 9.65
4 25.87 -0.22
96

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学校代码: 10491 研究生学号: 1201590078

姓名: Mgeta Faustine Sabe

A Dissertation Submitted to China University

of Geosciences for the Master Degree in Oil and Natural Gas

The Influence of Silica Nano-particles in

Student Name: Mgeta Faustine Sabe

China University of Geosciences

University of Geosciences (Wuhan)

I solemnly declare that the dissertation I submitted "to the University of

Geoscience (Wuhan)" is my independent research which is achieved under the

guidance of supervisors and during my graduate student stage. In this dissertation,

from academic infringement of this dissertation.

Thesis Supervisor Commitment Statement

China University of Geosciences (Wuhan)

I authorize China University of Geosciences (Wuhan) to preserve this dissertation

by means of photocopy, micro-printing, digitalization and other ways. China

University of Geosciences (Wuhan) has the right to submit this dissertation to

relevant state departments or institutions. This dissertation would be permitted to

university local network.

Name: Mgeta Faustine Sabe Nationality: Tanzanian Birth Date: 1985-04-06

Native Place: Nyamagana City: Mwanza

2015-2018: China University of Geosciences (Wuhan)

Program: Masters of Oil and Natural Gas Engineering

2007-2011: University of Dar es salaam (Tanzania)

Program: Bachelor of Science in Electromechanical Engineering

2006.7 – 2006.8: Butimba Teachers College

Program: Certificate of Education in Physics and Mathematics

2017-2018: China university of geosciences -Wuhan

Research Title: The Influence of Silica Nano-particles in Improving Compressive

Role Played: Author

2010-2011: Innovation and Technology Center (INTEX)– Tanzania

Research Project Tile: Designing and Implementation of an Automatic Control System

Role Played: Designer and Project Engineer

具有纳米二氧化硅粒子添加剂的 G 类波兰水泥是由少量干重为 1.0％至 4.0％纳米二氧

在该研究中，通过添加不同百分比含量的 20-30nm 的纳米二氧化硅材料来研究强度。

为使水泥硬化并测量其抗压强度，将样品在 80℃温度下养护 3 天，7 天，15 天和 28

本试验中，达到最大抗压强度的最佳比例为固化 28 天后的 3.0wt.%纳米二氧化硅，

Key words: Nano silica, Nanoparticles, Compressive Strength, Curing Time

Figure 2-2: Rate of heat evolution during hydration of Portland cement…………………….….11

Figure 2-6: Effects of Nano silica particles on heat hydration………..…………………………54

Figure 3-1: Experimental procedures plan flow chart……………………………..…………….59

Figure 3-2: The cement cube mold…………………………………………………...………….61

Figure 3-3: Slurry poured into the mold…………………………………………………...…….62

Figure 3-4: Fixing the mold………………………………………………………...……………62

Figure 3-2: Shows a cured cement cube surface area dimensions……………………………….66

Table 2-2: Mineralogical composition of unhydrated cement……………….…………………..17

Table 2-3: Type of Portland cement……………………………….…………………………….18

Table 2-4: Major cement hydration products………………………………………………….....28

Table 2-5: Applications of API classes of cement…………………………………………….....31

Table 2-6: Typical composition of API classes of Portland cement………………..……………32

Table 3-1: Experimental Materials……………………………………………….……………...57

Table 3-2: Properties of nano-SiO2……………………………………………………………....58

Table 3-3: Experimental Instruments…………………………………………………………….58

Table 4-1:0.0% nano-SiO2 content experimental data……………………………………...……67

Table 4-2:1.0% nano-SiO2 content experimental data……………………………………...……68

Table 4-3:2.0% nano-SiO2 content experimental data…………………………………...………68

Table 4-4:3.0% nano-SiO2 content experimental data…………………………………………...69

Table 4-5:4.0% nano-SiO2 content experimental data…………………………………...………69

Appendix 1: Average Compressive strength for 3 days…………………………………………96

Appendix 2: Average Compressive Strength for 7days…………………………………….……96

Appendix 3: Average Compressive Strength for 15days………………………………………...97

Appendix 4: Average Compressive Strength for 28 days…………………………………….….97

Figure 1-3: Schematic Cross section of a well borehole.

1.1.1 Nano silica Material