CHLORIDE INDUCED MASS LOSS INDEX OF CALCINED CLAY

CEMENT BLENDED CONCRETE

BY

PATRICK. O. VICTOR

MAT NO. UG/15/1555

A RESEARCH PROPOSAL SUBMITTED TO THE FACULTY OF

ENGINEERING, DEPARTMENT OF CIVIL ENGINEERING, NIGER

DETLA UNIVERSITY, WILBERFORCE ISLAND,

BAYELSA STATE.

SUPERVISED

BY

ENGR MAC -TELLI .H.

 CHAPTER 1
INTRODUCTION

1.1 Background to the Study

Civil engineering also known as construction engineering has been one of the oldest and most

lucrative field of study known to man, because it deals with the construction of shelter for mankind.

Due to technological advancement, job creation/industrialization, and population growth etc. the

need to progress from just construction of shelters arose; construction of complex structures such

as industries, access roads (rigid, flexible pavement and bridges), administrative buildings,

stadium, places of worship, dams and so on became a necessity. Concrete has never been an

environmental amiable substance neither for make nor for its use, or to dispose. Huge amount of

water and energy is being used to get the raw material to make concrete and excavating for sand

and other aggregates which cause ecological annihilation and air contamination. Concrete is also

an assertion to be the colossal cause of carbon emission in the earth’s atmosphere. Some assert

that concrete is accountable for up to 5% of the world’s cumulative carbon secretion which

contributes greenhouse gases. Mixing of water in cement and cement production generate a huge

amount of CO2 gases realizing in environment seriously detrimental ozone layer causing high

temperature increasing seasonal temperature variation. This paper is a probe with partial

replacement of cement by calcined clay in concrete collected from two cities. The work deals with

compressive strength, split tensile strength, water absorption. Data therefore presents over a

maximum curing of 15 days. The substitutions proportions used will be 4, 8, 12, 16 and 20% by

weight of cement.
1.2 Statement of Problem

The study Chloride Induced Mass Loss Index of Calcined Clay Cement Blended Concrete,

chloride induced mass loss index when calcined clay soil is used as partial replacement for fine

aggregate in concrete to determine flexural strength test. In line with the study, the researcher

found it difficult to get studies that have investigated flexural strength test of calcined clay soil as

partial replacement for fine aggregate in concrete. Also, financial constrail is one of the major

challenges faced by the research in process of carrying out the research work.

1.3 Aims and Objective of the Study

The aim and objective is to investigate the measurement PF forces or strength required to bend

calcined clayey soil and to determined the resistance of flexing or stiffness of a calcined clayey

soil.

1.4 Scope of the Work

The main purpose of this study is to determining the flexural strength test of calcined clay soil as

partial replacement for fine aggregate in concrete In order to know the various flexural strength of

different sample of calcined clay soil that will be produce at different temperatures been tested in

the department of civil engineering, construction material laboratory and also this test will be

achieved by a flexural strength testing machine in the construction material laboratory.

1.5 Method of the Work

Cement can be described as a material with adhesive and cohesive properties which make it

capable of bonding mineral fragment into a compact whole and solid in the presence of water.

Cement of 53 grade will be purchased and used in this experiment. The properties of the cement

used in the experiments.

Aggregates are as important as other constituents of concrete. They give body to the concrete,

reduce shrinkage and effect economy. One of the most important factors for producing workable

concrete is a good gradation of aggregate. Samples of the well graded aggregate containing

minimum voids require minimum paste to fill up the voids in the aggregates. Minimum paste

means less quantity of cement and less water, which is further meant increased economy, higher

strength, lower shrinkage and greater durability. Aggregate is divided into two types:

• Coarse aggregate

• Fine aggregate

River sand will be used as fine aggregate. The size of the sand used is 4.75 mm and down size.

The properties of (sand).

Calcined clay will be produce and soil sample obtained at depth below 1m from natural ground

level and prepared accordingly for various test that will be done for different standards .

Clay will be calcined from 500 - 1000 degrees celsius at 100 degrees interval.

Normal Drinking water is used in this Project.

Practical work will be carried out, cubes will be made from concrete mix grade with clay. Also,

curing for days will be done on these cubes to be there after taking to the construction materials

laboratory and their various flexural strength tested with the universal flexural testing machine.

1.6 Justification of the Work

Firstly, blended cement are cement in which the clinker is substituted with other materials in this

case study calcined clay soil been utilized as admixtures in Concrete. However, flexural strength

test of calcined clay soil as partial replacement for fine aggregate in concrete. Under flexural

strength testing, the material's ability to resist failure when there is bending and a load applied is
determined. ... Understanding a product's flexural strength is important as it will determine its

suitability, workability, strenght and disability for the individual application.

 CHAPTER 2
LITERATURE REVIEW
2.1 INTRODUCTION
Portland cement concrete is made with coarse aggregate, fine aggregate, Portland cement, water

and in some cases selected admixtures (mineral & chemical). Calcined clay is a popular soil

amendment used on baseball infields for water management and soil conditioning. Clay is heated

at a high temperature, about 1500 degrees Fahrenheit to expand the clay forming calcined clay. On

baseball fields calcined clay is used to fill in infield depressions caused by cleats and smooth the

surface to provide a true baseball bounce, which contributes to the safety of the field. Calcined

clay absorbs water that can help dry a field after a rainstorm, and firm the surface.

Versions of calcined clay include vitrified clay and finely ground calcined clay products. Vitrified

clay is similar to calcined clay but in the case of vitrified clay it is heated to over 2000 degrees

Fahrenheit. The end result is vitrified clay will absorb and hold water longer than calcined clay.

Many sportsfield managers will combine calcined clay and vitrified clay in various proportions.

During wet periods the proportion of calcined clay to vitrified clay will be higher to absorb water

quickly and during dry periods the proportion of vitrified clay will increase. During dry periods

the vitrified clay holds moisture longer allowing for a little more moisture on the infield surface

than calcined clay. Calcined clay can be ground into a finer product, almost like a powder. Finely

ground calcined clay like Rapid Dry can absorb water quickly. It is often used after a heavy

rainstorm to absorb puddles of water quickly on the infield. The disadvantage of the finely ground

materials is that once the infield dries out it becomes hard and dusty. The best all round material

for water management and infield conditioning for most conditions is calcined clay. Karl

Danneberger, PhD 2017.

However, some wastes are similar in composition to the natural raw materials used in the

construction industries. Thus, upgrading wastes to alternative raw materials is of technological,

economic and environmental interest. Mining and mineral processing wastes have traditionally

been discarded in landfills and often dumped directly into ecosystems without adequate treatment.

However, possible reuse or recycling alternatives should be investigated and implemented. Today,

the reuse and recycling of wastes after their potentialities have been detected is considered an

activity that can contribute to reduce production costs, provide alternative raw materials for a

variety of industrial sectors, and conserve public health. (Priyank Bhimani, 2013).

2.2 CEMENT AS A BINDER/CONSTRUCTION MATERIAL

2.2.1 HISTORY OF CEMENT
Whilst the details as to who first made, or used, whatever form of cement remains largely
uncertain, it remains a fact that the use of cement in construction is a very ancient practice.
Nevertheless, a general chronological sequence of developments can be described with
much of the following synopsis being derived from Hendrik G. van Oss (2005).

2.2.1.1 ANCIENT USE OF CEMENT

The earliest binder used in masonry construction was plain mud and mud binders are still
in use, mainly for adobe construction, in many parts of the world today. Bitumen was used
as a binder in some parts of ancient Mesopotamia. Some of the earliest use of true mortars
was in ancient Egypt, Greece, and Crete. In Greece and Crete, lime mortars were made, as
today, from the burning of limestone. In contrast, the Egyptians mainly used crude gypsum
mortars due to an inadequate presence of fuels; the conversion of limestone to lime requires
significantly higher temperatures than that of gypsum to plaster, although they had access
to abundant limestone and did make some lime mortars.
The ancient Romans learned about the various types of mortars from the Greeks, and then

improved the quality and methods of application of hydraulic mortars and made far more

extensive use of them. Most significant was the Roman use of pozzolan-lime cements
incorporating volcanic ash. A large amount of volcanic ash was quarried from the distal

slopes of Mt. Vesuvius near the village of Pozzuoli. This material became known as

pozzolana as credit to its origin of harvest as likewise the more general terms; pozzolan

and pozzolanic. Pozzolana has come to be applied to all volcanic ashes having pozzolanic

characteristics. A substance or material is said to be a pozzolan or hold pozzolanic

characteristics if it has little or no cementitious ability but when mixed with calcium

hydroxide or calcium oxide in the presence of water at room temperature, forms a stable

compound with reasonable cementitious ability (Walker and Pavia, 2011). Where

pozzolana was unavailable, the Romans made use of crushed tiles or potshards as an

artificial pozzolan.

The Roman pozzolan-lime cements were so strong that, in practice, the proportions of
aggregates in the mortars could be significantly increased over that used in unmodified
lime mortars. Roman engineers used pozzolan-lime mortars and concrete throughout the
Roman Empire, not only in a multitude of buildings but also in applications such as the
waterproof lining of aqueducts and the construction of sea walls for artificial harbors.

2.2.1.2 POST-ROMAN USE OF CEMENT

Following the fall of the Roman Empire, the hydraulic mortars and concretes made during
the first few centuries were of lower quality, owing to poor understanding of the techniques
of cement and lime manufacture or a lack of pozzolans in some places, or both. Regular
lime mortars appear to have fared better. However, sporadic interest remained in
reproducing the quality of the old Roman cements, and in the 18th century active research
was conducted in hopes to improve the quality of cements was becoming fairly widespread
in Western Europe.
A major breakthrough in the understanding of hydraulic cement resulted from the research

of John Smeaton following his being awarded, in 1756, the contract to build a replacement
lighthouse on the Eddystone Rocks, offshore from Plymouth, England. For this project,

Smeaton conducted experiments to make mortar that could withstand especially severe

marine conditions. Smeaton discovered that strong hydraulic mortar could be made from

calcining limestones that contained appreciable amounts of clay. He found that an even

better mortar could be made by combining this hydraulic lime with pozzolans. Hence, he

used a hydraulic lime-pozzolan mortar to build the new Eddystone lighthouse, which then

stood for 126 years before needing replacement. Smeaton published the results of his

research on hydraulic limes in 1791.

In 1796, a patent was granted to James Parker (Joseph Parker in some writeups) in England
for hydraulic cement made from argillaceous limestone nodules (septaria). Within a few
years, cements derived from a variety of argillaceous limestones were being marketed
under the misleading but persistent term Roman cement. The name was based on the claim
that the cement was as good as, and of similar reddish color to, the ancient Roman product,
but was despite the fact that the new material contained no pozzolana and was
compositionally quite unlike its namesake. Because the new cement (better termed natural
cement) possessed good strength and hydraulic properties and set and hardened fairly
quickly, its popularity grew rapidly, and natural cement remained the dominant cement
type produced in England and most of the rest of Europe until the mid-19th century.
Production of cement of any type came later in the United States than in Europe, with the
initial impetus being a need for waterproof mortars for the lining and lockworks for the
Erie Canal, New York. Construction of the canal began in 1817 and, in the following year,
deposits of argillaceous limestone suitable for the manufacture of natural cement were
discovered near the canal. Manufacture of natural cement began shortly thereafter. The
argillaceous limestone was locally called cement rock. The natural cement industry in the
United States grew steadily as cement rock deposits were subsequently discovered in
eastern Pennsylvania and elsewhere. Until the early 1870’s, the only cements made in the
United States were natural cements and slag-lime cements (chiefly based on quenched iron
furnace slag).
Natural cements in the United States and in Europe exhibited significant regional variations

in quality, owing to differences in processing methods and in the composition of the cement

rock raw material. Smeaton’s discovery of the importance of clay to the development of

hydraulic character in lime mortars inspired research into ways to improve the quality,

and/or reduce the variability, of natural cements. An ultimately more important avenue of

research was that into the making of so-called artificial cement. Probably the most

influential researcher in this area of investigation was the French engineer Louis J. Vicat.

His research was first published in 1818 and showed how, in the absence of argillaceous

limestones or cement rock, high quality hydraulic limes could be made with ordinary

limestone, provided that controlled amounts of clay or shale were added. A more

comprehensive review was published in 1828, and was translated into English in 1837

(Vicat, 1837).

2.2.1.3 PORTLAND CEMENT

The findings of Smeaton, Vicat, and other researchers appear to have been fairly well
disseminated, and a number of patents were issued in England and France for various types
of hydraulic limes and cements. In 1810, Edgar Dobbs received a patent in England for
cement that utilized clay, road dust (from limestone) and lime. The Dobbs patent expired
in 1824, and this may have inspired Joseph Aspdin, a brick mason and experimenter from
Leeds, England, to file later that year a patent for what superficially appears to be a similar
product. Aspdin’s December 15, 1824 patent “An improvement in the modes of producing
an artificial stone” (British patent 5022) was for a product that he called Portland cement.
This name alluded to Portland stone, a well-regarded, very tough, dimension stone quarried
on the Isle of Portland along the South Dorset coast. The Portland stone comparison also
had been used, much earlier, by Smeaton in extolling the qualities of his own cement.
Aspdin’s patent is interesting by modern standards in that it reveals remarkably little
specific information about the product or its manufacture.
The first portland cement plant was set up at Wakefield, England by Aspdin shortly after
receiving his patent. His son, William Aspdin, later set up plants on the Thames and at
Gateshead-on-Tyne. In the early years of the British portland cement industry the
expensive new cement found difficulty in capturing market share from the well-regarded
natural cements. Marketing of portland cement received a major boost in 1838 when it was
chosen for the prestigious project to construct the Thames River tunnel.
Early efforts by others to duplicate the quality of Aspdin’s portland cement were largely
unsuccessful and led to speculation that Aspdin’s patent lacked (perhaps deliberately)
critical details regarding the cement’s manufacture.
Early efforts by others to duplicate the quality of Aspdin’s portland cement were largely
unsuccessful and led to speculation that Aspdin’s patent lacked (perhaps deliberately)
critical details regarding the cement’s manufacture. The duplication efforts, however,
yielded by the mid-1840s important ideas as to what those missing details were, most
notably the need to heat the raw materials in the kiln to much higher temperatures than that
merely needed to calcine the limestone. Empirical evidence for this was the discovery that
over-burned, partially vitrified, material (hitherto discarded) from the kilns yielded better
quality cement; a rival cement maker, Isaac C. Johnson, is generally credited with making
public this need for high-temperature burning. It was eventually determined that the
improvement in cement quality was because of the presence of hydraulic dicalcium silicate
in the vitrified material (clinker) and, even more important, the presence of tricalcium
silicate (discussed in more detail later). There remains debate as to whether Aspdin’s
original portland cement contained either of these minerals or whether it was merely a well-
made hydraulic lime, relying on heat-activated clay pozzolans. It is now known that both
dicalcium silicate and (minor) tricalcium silicate were present in at least some of the later
portland cements made by Joseph Aspdin (Stanley, 1999; Campbell, 1999, p. 1-3), and
were certainly present in cements made by his son. Through trial and error, numerous
improvements to the manufacturing process and mineralogic composition of portland
cement were made in England and elsewhere over the course of the following decades.
Improvements still continue and there remains only superficial similarity between modern
portland cements and those manufactured in
the mid- to late-19th century. The portland cement name has been retained by the industry

largely because the modern material is still an artificial cement made from limestone and

argillaceous raw materials and because the name has an unrivaled cachet.

2.2.1.4 GLOBAL CEMENT CONSUMPTION REPORT

In the first half of the 20th century, world use of concrete, and hence production of cement,
grew erratically, experiencing major declines during the two World Wars and the Great
Depression. World hydraulic cement production did not appear to have reached 100 Mt/yr.
until 1948 (Hendrick G. van Oss, 2005). However, since World War II, cement production
has experienced steady, strong growth, with output in 2004 at about 2 Gt, as noted earlier.
Today, there are very few countries that do not have at least one cement plant. Much of
Asia’s overall growth has been by China. In 1950, China produced only about 2 Mt of
cement, whereas output in 2004 was about 950 Mt (Hendrick G. van Oss, 2005).
According to The Global Cement Report, 13th edition (2019), world cement consumption
is estimated to have expanded by 2.8% to 4.08bnt in 2019. The rise in demand is largely
accounted for by the expansion of the Chinese cement market in 2019, which reached an
estimated 2.28bnt, up 4.9% on the year before, and representing 56% of global
consumption. Excluding China, world cement consumption is estimated to have remained
at 1.81bnt, rising by just 0.3%, year-on-year.

2.2.2 TYPES OF CEMENT

When Portland cement, a generic material, is hydrated, cements differing in chemical
compositions may exhibit different properties and thus making it possible to choose
mixtures of raw materials for the production of cements with specific desired property.
 Cement Main constituents Limitations on non
designation clinker
Composition (#% by
mass)
Cement type permitted in EN197-7
CEM I Portland cement
CEM II Blastfumace slag 35%
Silica fume 10%
Natural pozzolan 35%
Pulverized-fuel Ash (siliceous and 35%
Calcareous) 35%
Burnt shale 35%
Limestone 35%
Composite (mix of above consituents) 35%
CEM III Bastfurmace slag cement 95%
CEM IV Pozzolanic cement 55%
CEM V Composite cement 50%
Cement type permitted in BS8500 (combinations manufactured in the cement plant)
CEM I Portland cement
CEM II Silica fume 10%
CEM III Blastfumace slag cement 80%
CEM IV Pozzolanic cement 55%
Cement type permitted in BS8500 (combinations manufactured in the mixer)
CII Limestone fines combination 20%
CII Pulverized-fuel Ash combination 35%
CIII Blastfurmance slag combination 80%
CIV Pulverized-fuel Ash combination 55%

Table 2.1 Cement types permitted in BS EN 197-1 and BS 8500 (Source: M. D. Newlands
et al., 2015)

2.2.3 CEMENTATION MECHANISMS, AND CHEMISTRY AND MINERALOGY OF

PORTLAND CEMENT
2.2.3.1 CEMENTATION MECHANISM
A number of binding mechanisms can occur in a mix of a cementing agent and aggregate
particles. Qualitatively, one can envision the ultimate strength of the cemented material
being due primarily to any or a combination of the mechanical strength of the hardened
cement paste itself, the degree to which the hardened paste physically interlocks with the
aggregate particles or chemically binds or otherwise reacts with the particles, the
mechanical strength of the aggregate particles themselves, and the degree to which the
aggregate particles and paste have been properly mixed. These cementation mechanisms
include;
1. Carbonation: Ordinary lime mortars rely on carbonation as their cementing
mechanism. In this process, lime (CaO) is formed by heating a source of calcium
carbonate (CaCO3) such as calcite to high temperatures. The resulting calcination
reaction to drive off carbon dioxide is simple:
CaCO3 + heat → CaO + CO2
The slow reversal of this equation effected by the lime’s gradual absorption of
atmospheric carbon dioxide results in the carbonation reaction for lime. The ultimate
strength of the lime mortar depends on the completeness of the carbonation; the
hydrated lime particles develop a shell of CaCO3 which, to one degree or another, slows
CO2 diffusion to the residual lime particle cores and thus slows further carbonation. But
when the carbonation process is complete, lime mortars can be quite strong.

2. Hydration: Cement hydration occurs when anhydrous cement is mixed with water
which then results in a number of exothermic chemical reactions that both take place
simultaneously and successively. After absorption of water on the surface of the dry
powder occurs, the dissolution of part of the inorganic phases begins. New silicate and
aluminate hydrated phases begin to precipitate from the solution on the existing grains,
thus favoring the further dissolution of the anhydrous phases through an incongruent
process. The hydrated phase is responsible for the binding characteristics of the cement
are an amorphous calcium silicate hydrate called C-S-H, having the properties of a rigid
gel. A secondary product of the hydration process is crystalline Ca(OH)2, portlandite.
The reaction of the silicate and aluminate phases with water is an exothermic process.
2.2.3.2 CEMENT CHEMISTRY
Generally, cement chemistry is denoted in simple stoichiometric shorthand terms for at
least the major constituent oxides. The chemical constituents of cement are presented in
the table below;
Table 2.2: Cement Chemistry

Oxide Shorthand Percentage by Percentage by

Formula Notation mass in clinker mass in cement

CaO C 65 63.4

SiO2 S 22 20.9

Al2O3 A 6 5.7

Fe2O3 F 3 2.9

MgO M 2 1.9

K2O + Na2O K+N 0.6 0.6

Other …… 1.4 3.6

H2O H 0 1

2.2.3.3 MINERALOGY OF PORTLAND CEMENT AND CLINKER

The major oxides in clinker are combined essentially into four cement or clinker minerals.
These minerals are denoted in simple stoichiometric shorthand as; C3S, C2S, C3A, and
C4AF. Their percent composition is shown in the table below;
Table 2.3: Mineralogy of portland cement and clinker
Description Shorthand Oxide Typical Days to 80%
Notation Formula Percentage hydration
Tricalcium silicate C3S (CaO)3SiO2 50-70 10
Dicalcium silicate C2S (CaO)2SiO2 10-30 100
Tricalcium aluminate C3A (CaO)3Al2O3 3-13 6
Tetracalciumaluminoferrite C4AF (CaO)4Al2O3Fe2O3 5-15 50
Gypsum CSH2 (CaO)(SO3)(H2O)2 3-7
The major functions of these oxides include;
1. Tricalcium silicate (alite); It hydrates quickly and imparts early strength and
setting.
2. Dicalcium silicate (belite); It hydrates slowly and is responsible for long-term
strength.
3. Tricalcium aluminate; It hydrates almost instantaneously and very exothermically.
It contributes to early strength and setting.
4. Tetracalciumaluminoferrite; It hydrates quickly and acts as a flux in clinker
manufacture and imparts its gray color.
5. Gypsum; Grounded with clinker to make Portland cement and can substitute
anhydride. It controls early set.Other (physical) properties of cement include;
Fineness, Soundness, Consistency, Strength, Setting time, Heat of Hydration, Loss
of Ignition, Bulk density, and Specific gravity.
6. Fineness: The particle size of cement is referred to as its fineness. The required
fineness of cement is achieved by grinding the clinker in the last step of the
production process of cement. The fineness of cement is considered a key property
as it is directly related to the rate of hydration of cement.
7. Soundness: The soundness of cement refers to its ability to not shrink upon
hardening. Good quality cement retains its volume after setting without delayed
expansion, which is caused by excessive free lime and magnesia. The unsoundness
of cement is tested for ensuring its soundness. These tests include; Le Chatelier test,
and Autoclave test.
8. Consistency: This is a property of cement which describes the ability of cement
paste to flow. It is measured by the Vicat test.
9. Strength: The strength of cement is arguably its most prominent characteristics
although it is directly related to other properties which include water-cement ratio,
curing conditions, size and shape of a specimen, etc. It is important to note that the
strength of cement mortar and cement concrete strength are not directly related and
 the former is merely a measure of quality control. Compressive strength test is the
most common strength test in which a test specimen is subjected to compressive
load until failure. Other strength tests carried out include tensile strength, and
flexural strength tests.
10. Setting Time: Cement sets and hardens when water is added. Depending on
multiple factors which include fineness, cement-water ratio, etc., the setting time
may vary. According to several standards, cement used in construction should have
an initial setting time that is not too low and a final setting time not too high. Hence,
two setting times are measured. These include initial set (this occurs when the paste
begins to stiffen noticeably and typically occurs within 30-45 minutes), and final set
(this occurs when the cement hardens and is able to sustain some load and typically
occurs below 10 hours after cast). The setting time of cement can also be an indicator
of hydration rate.
11. Heat of Hydration: The addition of water to cement results in hydration. The
hydration process results in the generation of heat which directly affects the quality
of the cement and is also beneficial in maintaining curing temperatures during cold
weather. On the other hand, when heat generation is high, especially in large
structures, it may cause undesired stress. The heat of hydration is affected the most
by C3S and C3A present in cement, and also by its water-cement ratio, fineness, and
curing temperature. The heat of hydration is
calculated by determining the difference between the dry and the partially hydrated cement.

12. Loss of Ignition: When cement samples are heated at 900 – 1000OC until a constant
weight is obtained, it results in weight loss which is calculated as the loss of ignition.
An increased loss of ignition indicates improper or prolonged storage during
transportation or transfer which might lead to pre-hydration and carbonation.

2.2.4 MANUFACTURING PROCESS

Portland cement manufacture is divided into two (2) major stages. These include;
manufacturing clinker, and fine grinding the clinker together with gypsum. Whilst certain
integrated plants are able to perform both steps, grinding plants make cement by grinding
clinker that was made elsewhere.

2.2.4.1 CLINKER MANUFACTURING PROCESS

Clinker manufacture involves two steps; appropriate raw materials must be quarried,
crushed, and then proportioned and blended into a kiln feed called the raw mix, and then
the raw mix must be converted into the clinker materials. The overall procedure involved
in manufacturing clinker is called pyro-processing; a thermochemical conversion because
it involves direct flame interaction.

1. Raw materials for clinker: The non-fuel raw materials for cement must yield the
oxides required for clinker in the appropriate proportions. These raw materials include
limestone, clay, shale, sandstone, and iron ore. Individual raw materials generally provide
more than one oxide. Primary raw materials are those that are always used in relatively
large quantities by a specific plant. To correct for minor deficiencies in one or more oxides
in the primary raw materials, accessory or “sweetener” materials, generally of high purity,
may be added. Certain oxides can also be partly supplied by the fuels; for example, the ash
in coal supplies a portion of the silica requirements for clinker, and the steel belts in waste
tires (a supplementary fuel) supply iron oxide. When a plant evaluates its raw materials,
consideration is given not only to each material’s potential contribution of major oxides
(CaO, SiO2, Al2O3, Fe2O3), but also to the content, if any, of undesirable trace elements
(e.g., excess MgO, alkalis, toxic species). Consideration also is given to the ease of
prepping the material (usually ease of crushing), and the material’s “burnability,” that is,
the heat energy required to break down the material to activate or make accessible its
component oxides. The major oxide requirement for clinker is CaO.
2. Pyro-processing: The heart of the cement manufacturing process is operated by a
kiln in which raw materials undergo pyro-processing to make clinker. The pyro-processing
stage of cement manufacture is an energy intensive stage. Pyro-processing takes places in
a rotary kiln; a technological advancement in the year 1873 to the previously employed
small vertical chimney-type kilns which were put out of commission as they were slow,
labor-intensive, and fuel inefficient relative to the demand of cement. The four (4) major
clinker line functions and their approximate range of temperature (OC) are; drying (<100 –
200), preheating (200 – 550), calcining (750-1000), sintering (1200 – 1450), and cooling
(<1450 – 1300). Each of these functions is performed sequentially in specific and
progressively hotter parts of the wet kiln.

2.2.4.2 CEMENT MILLING

In this stage of manufacturing cement, clinker is grinded together in a grinding mill. After
clinker has been cooled to about 100OC, it is then ready to be ground into finished cement
in a grinding mill or in more recent times, a ball mill. It is important to note that the fineness
of the cement depends on the rate at which clinker and gypsum are introduced, and the
grindability of clinker depends on its chemistry and on the conditions, it experienced in
burning and cooling. Hard burning and high melt content resulting from a low silica ratio
increases initial grindability since they result in a clinker with a low porosity.

Figure 2.1: Simplified flow sheet of cement manufacture (Source: Hendrick G. van Oss,
2005)
2.2.5 STRENGTH AND LIMITATIONS OF CEMENT
While portland cement may be popular in the global construction industry, it has been
deemed as harmful to the environment considering it emission of greenhouse gasses and
also the energy demand for production and hence interest has been placed in the
development and effectuation of alternatives binders in concrete (M.C.G. Juenger et al,
2010). Furthermore, Portland cement is not graded as an ideal binder for all construction
applications, as it suffers from durability problems in particularly aggressive environments.

2.3 INTRODUCTION TO SUPPLEMENTARY CEMENTITIOUS MATERIALS

2.3.1 ALTERNATIVE BINDERS
Concrete is a composite material which forms by bonding aggregates, and a fluid binder
which hardens over time. A few of such fluid binders include, cement; a hydraulic binder,
and lime binder which are commendable as regards their setting time and strength gain
rate. The most commonly used binder in concrete today is the Portland cement. However,
amidst its popular troubles of its high energy requirement in production, and high carbon
dioxide emission, cement concrete also suffers durability problems in particularly
aggressive environments. One of such attacks cement concrete is prone to in an aggressive
environment is Sulphate attack. Such attack can lead to strength loss, expansion, spalling
of surface layers and, ultimately, disintegration. Portland cement concrete can be attacked
by solutions containing sulphate ions, such as some natural or polluted ground waters. Soils
containing sodium, potassium, magnesium, and calcium sulphate are the main sources of
sulphate ions in groundwater (Jan Tragardh, 2007).

The reaction of cement with water leads to the formation of calcium silicate hydrate (C-S-
H) gel, Calcium Hydroxide Ca(OH)2, as well as Ettringite (C3A.3CaSO4.32H2O), (Adam,
2004). Ettringite, thaumasite (C3A.3CaSO4.32H2O), and gypsum are three mineral which
are found among the deterioration products of cementitious materials exposed to sulphate
attack(Jan Tragardh, 2007). Jan Tragardh (2007) further added that the formation of
ettringite is considered to be the prime cause of most of the expansion and disruption of
concrete structures affected by sulphate attack.
Hydrated cement is primarily composed of above 50% of C-S-H gel, 25-50% of Ca(OH)2,
and the remainder is composed of Ettringite and capillary pores, (Adam, 2004). While the
C-S-H gel is responsible for the hydration rate/strength gain of concrete, Ca(OH)2 is a
soluble filler that is mostly given off at the effect of loading.

Hydraulic cement + Water → C-S-H + C-A-H + CH

However, Ca(OH)2 is required by pozzolans to form a secondary C-S-H gel and hence
providing blended cement concrete with even more strength hence cement is said to be a
good receptor of pozzolan.

Pozzolan + CH + Water → C-S-H

Also, it is keen to note that the rate of deterioration and the durability of concrete is directly
related to its permeability which depends on the w/c ratio. In investigating the effect of
varying w/c ratios in concrete, it was noted that the specimens with decreased permeability
showed significantly improved performance much credited to the reduction of pore size
and the decreasing diffusion of sulphate ions into concrete’s micro structure. The
permeability of concrete’s microstructure is also affected by the fineness of the material
used in concrete.

Amidst the vast societal challenges faced by the construction industry, research into
alternative binders for concrete has gained a lot of interest due to the need to find a
construction material(s) that constitutes a sustainable and economical alternative to
ordinary Portland cement. The currently explored options due to the vast material available
include; Limestone calcined clay cement (LCC), Alkali activated materials (AAM),
Calcium sulphoaluminate cement (CSA), and Supplementary cementitious materials
(SCM).
2.4 CLAY

Clay is a type of fine-grained natural soil material containing clay minerals. Clays develop

plasticity when wet, due to a molecular film of water surrounding the clay particles, but become

hard, brittle and non–plastic upon drying or firing. Most pure clay minerals are white or light-

coloured, but natural clays show a variety of colours from impurities, such as a reddish or brownish

colour from small amounts of iron oxide. Clay is the oldest known ceramic material. Prehistoric

humans discovered the useful properties of clay and used it for making pottery. Some of the earliest

pottery shards have been dated to around 14,000 BC, and clay tablets were the first known writing

medium. Clay is used in many modern industrial processes, such as paper making, cement

production, and chemical filtering. Between one-half and two-thirds of the world's population live

or work in buildings made with clay, often baked into brick, as an essential part of its load-bearing

structure. Clay is a very common substance. Shale, formed largely from clay, is the most common

sedimentary rock. Although many naturally occurring deposits include both silts and clay, clays

are distinguished from other fine-grained soils by differences in size and mineralogy. Silts, which

are fine-grained soils that do not include clay minerals, tend to have larger particle sizes than clays.

Mixtures of sand, silt and less than 40% clay are called loam. Soils high in swelling clays, which

are clay minerals that readily expand in volume when they absorb water, are a major challenge in

civil engineering.

2.4.1 DEFINING MECHANICAL PROPERTY OF CLAY

The defining mechanical property of clay is its plasticity when wet and its ability to harden when

dried or fired. Clays show a broad range of water content within which they are highly plastic,

from a minimum water content (called the plasticity limit) where the clay is just moist enough to
mould, to a maximum water content (called the liquid limit) where the moulded clay is just dry

enough to hold its shape. The plastic limit of kaolinite clay ranges from about 36% to 40% and its

liquid limit ranges from about 58% to 72%. High-quality clay is also tough, as measured by the

amount of mechanical work required to roll a sample of clay flat. Its toughness reflects a high

degree of internal cohesion.

Clay has a high content of clay minerals that give it its plasticity. Clay minerals are hydrous

aluminium phyllosilicate minerals, composed of aluminium and silicon ions bonded into tiny, thin

plates by interconnecting oxygen and hydroxide ions. These plates are tough but flexible, and in

moist clay, they adhere to each other. The resulting aggregates give clay the cohesion that makes

it plastic. In kaolinite clay, the bonding between plates is provided by a film of water molecules

that hydrogen bond the plates together. The bonds are weak enough to allow the plates to slip past

each other when the clay is being moulded, but strong enough to hold the plates in place and allow

the moulded clay to retain its shape after it is moulded. When the clay is dried, most of the water

molecules are removed, and the plates hydrogen bond directly to each other, so that the dried clay

is rigid but still fragile. If the clay is moistened again, it will once more become plastic. When the

clay is fired to the earthenware stage, a dehydration reaction removes additional water from the

clay, causing clay plates to irreversibly adhere to each other via stronger covalent bonding, which

strengthens the material. The clay mineral, kaolin, is transformed into a non-clay material,

metakaolin, which remains rigid and hard if moistened again. Further firing through the stoneware

and porcelain stages further recrystallizes the metakaolin into yet stronger minerals such as mullite.

The tiny size and plate form of clay particles gives clay minerals a high surface area. In some clay

minerals, the plates carry a negative electrical charge that is balanced by a surrounding layer of

positive ions (cations), such as sodium, potassium, or calcium. If the clay is mixed with a solution
containing other cations, these can swap places with the cations in the layer around the clay

particles, which gives clays a high capacity for ion exchange. The chemistry of clay minerals,

including their capacity to retain nutrient cations such as potassium and ammonium, is important

to soil fertility.

Clay is a common component of sedimentary rock. Shale is formed largely from clay and is the

most common of sedimentary rocks. However, most clay deposits are impure. Many naturally

occurring deposits include both silts and clay. Clays are distinguished from other fine-grained soils

by differences in size and mineralogy. Silts, which are fine-grained soils that do not include clay

minerals, tend to have larger particle sizes than clays. There is, however, some overlap in particle

size and other physical properties. The distinction between silt and clay varies by discipline.

Geologists and soil scientists usually consider the separation to occur at a particle size of 2 μm

(clays being finer than silts), sedimentologists often use 4–5 μm, and colloid chemists use 1 μm.[2]

Geotechnical engineers distinguish between silts and clays based on the plasticity properties of the

soil, as measured by the soils' Atterberg limits. ISO 14688 grades clay particles as being smaller

than 2 μm and silt particles as being larger. Mixtures of sand, silt and less than 40% clay are called

loam.

Some clay minerals (such as smectite) are described as swelling clay minerals, because they have

a great capacity to take up water, and they increase greatly in volume when they do so. When

dried, they shrink back to their original volume. This produces distinctive textures, such as

mudcracks or "popcorn" texture, in clay deposits. Soils containing swelling clay minerals (such as

bentonite) pose a considerable challenge for civil engineering, because swelling clay can break

foundations of buildings and ruin road beds.

Clay minerals most commonly form by prolonged chemical weathering of silicate-bearing rocks.

They can also form locally from hydrothermal activity. Chemical weathering takes place largely

by acid hydrolysis due to low concentrations of carbonic acid, dissolved in rainwater or released

by plant roots. The acid breaks bonds between aluminium and oxygen, releasing other metal ions

and silica (as a gel of orthosilicic acid).

The clay minerals formed depend on the composition of the source rock and the climate. Acid

weathering of feldspar-rich rock, such as granite, in warm climates tends to produce kaolin.

Weathering of the same kind of rock under alkaline conditions produces illite. Smectite forms by

weathering of igneous rock under alkaline conditions, while gibbsite forms by intense weathering

of other clay minerals.

2.4.2 TYPES OF CLAY DEPOSITS:

Primary and Secondary. Primary clays form as residual deposits in soil and remain at the site of

formation. Secondary clays are clays that have been transported from their original location by

water erosion and deposited in a new sedimentary deposit. Secondary clay deposits are typically

associated with very low energy depositional environments such as large lakes and marine basins.

2.4.3 GROUPS OF CLAYS

The main groups of clays include kaolinite, montmorillonite-smectite, and illite. Chlorite,

vermiculite, talc, and pyrophyllite are sometimes also classified as clay minerals. There are

approximately 30 different types of "pure" clays in these categories, but most "natural" clay

deposits are mixtures of these different types, along with other weathered minerals. Clay minerals

in clays are most easily identified using X-ray diffraction rather than chemical or physical tests.
Varve (or varved clay) is clay with visible annual layers that are formed by seasonal deposition

of those layers and are marked by differences in erosion and organic content. This type of deposit

is common in former glacial lakes. When fine sediments are delivered into the calm waters of these

glacial lake basins away from the shoreline, they settle to the lake bed. The resulting seasonal

layering is preserved in an even distribution of clay sediment banding.

Quick clay is a unique type of marine clay indigenous to the glaciated terrains of Norway, North

America, Northern Ireland, and Sweden. It is a highly sensitive clay, prone to liquefaction, and has

been involved in several deadly landslides.

2.5 CALCINED CLAY

in this research calcined clay will be used to determining the flexural strength test of calcined clay

soil as partial replacement for fine aggregate in concrete In order to know the various flexural

strenght of different sample of calcined clay soil that will be produce at different temperatures

been tested in the department of civil engineering, construction material laboratory and also this

test will be achieved by a flexural strenght testing machine in the construction material laboratory.

Calcined clay is a popular soil amendment used on baseball infields for water management and

soil conditioning. Clay is heated at a high temperature, about 1500 degrees Fahrenheit to expand

the clay forming calcined clay. On baseball fields calcined clay is used to fill in infield depressions

caused by cleats and smooth the surface to provide a true baseball bounce, which contributes to

the safety of the field. Calcined clay absorbs water that can help dry a field after a rainstorm, and

firm the surface. Versions of calcined clay include vitrified clay and finely ground calcined clay

products. Vitrified clay is similar to calcined clay but in the case of vitrified clay it is heated to

over 2000 degrees Fahrenheit. The end result is vitrified clay will absorb and hold water longer
than calcined clay. Many sportsfield managers will combine calcined clay and vitrified clay in

various proportions. During wet periods the proportion of calcined clay to vitrified clay will be

higher to absorb water quickly and during dry periods the proportion of vitrified clay will increase.

During dry periods the vitrified clay holds moisture longer allowing for a little more moisture on

the infield surface than calcined clay. Calcined clay can be ground into a finer product, almost like

a powder. Finely ground calcined clay like Rapid Dry can absorb water quickly. It is often used

after a heavy rainstorm to absorb puddles of water quickly on the infield. The disadvantage of the

finely ground materials is that once the infield dries out it becomes hard and dusty.

The best all round material for water management and infield conditioning for most conditions is

calcined clay. Karl Danneberger, PhD 2017.

2.6 WATER DEMAND

The amount of water, an important constituent of concrete is critically considered before
concrete is casted. The water demand of concrete is factored in as the water to binder ratio
and is directly influenced by the fineness, and specific surface area of the binder employed
(Walker and Pavia, 2011). An increase in water demand would increase the workability of
the binder paste, and reduce its durability due to the initial spacing between the cement
grains and the greater volume of residual voids not filled by hydration products. Hence, a
pozzolan with a high demand of water would advertently result in lower strength gain and
density. According to Walker and Pavia (2011), the specific water demand of a pozzolan
(WDP) can be determined using the equation below;
(W – L × WDL)
WDP =
𝑃

Where;
WDP = Water demand of pozzolan
W = Total amount of water in mix (g)
L = Amount of lime (g)
P = Amount of pozzolan (g)
WDL = 0.862g

Figure 7: W/C ratio slump flow relationship (Source: Nikolas Kastrounis, 2014)

Figure 2.8: Relationship between Compressive Strength Water Cement ratio and Density
(Source: Nikolas Kastrounis, 2014)
2.6.1 SEA WATER ATTACK
The durability of concrete structures is affected by many environmental factors. A few of
the most frequent and detrimental processes are chloride and sulphate attack. According to
Merida and Kharchi (2015), sulphate corrosion occurs through the capillary pores of
concrete due to the concentration gradient and reacts with unhydrated components of the
hardened cement paste. In consequence, these chemical reactions may lead to expansive
reaction products such as ettringite. In turn, the ettringite may cause the overall expansion
of a structural element and its extensive damage progressing from the outer surface towards
the specimen inner core. This process may result in a gradual loss of concrete strength
accompanied by surface spalling and exfoliation.

Figure 2.9
Effect of Sulphate Attack on Compressive Strength (Source: Bahaa et al., 2008)

2.6.2 STRENGTH ACTIVITY INDEX (SAI)

The rate of strength development in concrete is of great interest to the construction industry.
As a result, concrete is expected to have achieved certain a certain strength at respective
curing ages dependent on the concrete grade employed. Strength activity index (SAI)
approach which specifies that a cement mix containing pozzolans as partial cement
replacement, cured for 28 days should be able to possess compressive strength results that
are equal to or greater than 75% of the control specimen containing 100% of cement as
binder (Walker and Pavia, 2011).
 Sample Type of Compressive stenght (Mpa) – strength Activity index (%)
fly ash 1-day 3-day 7-days 14-days 28-days 60-days 90-days

I - 11.4-100 15.8-10 21.9-100 27.0-100 30.2-100 32.1-100 32.8-100

II O 5.9-52 12.2-77 17.9-82 22.1-82 25.8-85 30.2-94 31.1-95
III F 12.6-111 15.8-100 23.4-107 30.6-113 35.4-117 39.6-123 42.5-130
IV CC 5.9-52 10.8-68 21.2-97 26.5-98 31.0-103 33.3-104 34.6-105
V CFC 12.1-106 17.3-110 25.9-118 29.2-109 32.9-109 35.6-111 36.3-111
VI CFF 12.8-113 19.8-125 27.3-125 30.1-114 35.5-118 39.1-122 41.0-125

Figure2.9: Compressive strength of mortar (MPa) and strength activity index (%) (Source:
Jaturapitakkul et al., 1999)
 CHAPTER 3
METHODOLOGY
3.1 RESEARCH MATERIALS
Below are materials used for the research work;

• Cement

• Sand

• Coarse aggregate

• Fine aggregate

• Clay

• Water

3.1.3 LABORATORIES TOOLS AND EQUIPMENT

To get achievable results the following tools and equipment were used;
• A well calibrated furnace with a thermocouple
• Sieve sets 45um,80um, 150um and 75um
• Electric sieve Shaker
• Weighing balance
• Polythene bag
• Buckets
• Shovel/ Spade
• Mould for casting
• Lubricant and hand paint brush
• Concrete mixer
• Cleaning rag
• Scoop
• Spanner for tightening and loosing of nuts
• Trowel
• Slump cone
 • Curing tank
• Polythene sheet
• Compressive testing machine/ test hammer
• Compacting bar

Method of the Work

Cement can be described as a material with adhesive and cohesive properties which make it

capable of bonding mineral fragment into a compact whole and solid in the presence of water.

Cement of 53 grade will be purchased and used in this experiment. The properties of the cement

used in the experiments.

Aggregates are as important as other constituents of concrete. They give body to the concrete,

reduce shrinkage and effect economy. One of the most important factors for producing workable

concrete is a good gradation of aggregate. Samples of the well graded aggregate containing

minimum voids require minimum paste to fill up the voids in the aggregates. Minimum paste

means less quantity of cement and less water, which is further meant increased economy, higher

strength, lower shrinkage and greater durability. Aggregate is divided into two types:

• Coarse aggregate

• Fine aggregate

River sand is used as fine aggregate. The size of the sand used is 4.75 mm and down size. The

properties of (sand).

Calcined clay was produce and soil sample obtained at depth below 1m from natural ground level

and prepared accordingly for various test that was done for different standards.

Clay was calcined from 500 - 1000 degrees celsius at 100 degrees interval.

Normal Drinking water is used in this Project.

Practical work was carried out with the materials listed above, cubes were made from concrete

mix grade with clay. Also, curing for days carried out on these cubes, then latter taking to the

construction materials laboratory and their various flexural strength tested with the universal

flexural testing machine was carried out.

3.1.1 Particle Size Distribution of Fine and Coarse Aggregate

The particle size distribution of a fine aggregate/coarse aggregate shows that the fine

aggregate/coarse aggregate falls under a Zone, which is suitable for concrete works.

3.1.2 Fineness

Fineness results are reported in terms of fineness in accordance to the specifications of BS: 12

(1978); homogeneity of the samples using the dry sieve analysis approach as specified by BS EN:

933-1 (1997) as well as percentage of fines. Results for the fineness experiments for calcined clay

3.1.3 Specific Gravity

In accordance to BS 4450-3; (1978) will be conducted on all the specimens and a possible

relationship with mechanical properties drawn

3.1.4 Slump (Workability)

In accordance to BS EN 12350-2; (2009) will be conducted on fresh concrete mixes containing

primary as well as hybrid samples as fine aggregate replacements to find and hence state the

optimum water content for each mix. These will further be compared to the results obtained for

samples containing 100% calcined clay as fine aggregate. Minimum water/fine aggregate ratio at

minimum slump will be detected and used as a means of establishing water/fine aggregate ratio

requirement for each concrete mix.

3.1.5 Compressive Strength

In accordance to BS EN 12390-3 (2009) will constitute the major mechanical test and findings of

this investigation. It will be the primary yardstick for measuring the calcined clay reactivity of the

primary as well as the fine aggregate specimens using the strength activity index (SAI) approach

and comparing same to results obtained on samples containing 100% sand as fine aggregate. Each

agricultural waste material processed under atmospheric temperature as well as under respective

calcination temperature concrete cubes for testing at ages 28 and 56days. The cube specimens shall

be of 150mm x 150mm x 150mm volumetric dimensions and will be subjected to submerged water

curing after 24hr of production until the day of testing. The compressive strength shall be

calculated as the ratio of the crushing load at failure (N) to the area of the cube being loaded.

Compressive Strength (N/mm2) = Load at failure (N)

Area under loading (mm2)