CHAPTER ONE

INTRODUCTION

1.1 Background of the study

Concrete is one of the most widely used manmade construction material in the world. Concrete is

a mixture of water, cement or binder, and aggregates (Akinkurolere et al; 2007; Neville and

Brook; 2008; Matthias; 2010).

Currently many developing countries of the world have taken a major initiative on developing

their infrastructures such as express highways, power projects and industrial structures etc. To

meet the requirements of globalization, in the construction of buildings and other structures,

concrete plays the rightful role and a large quantum of concrete is being utilized. River sand,

which is one of the constituents used in the production of conventional concrete, has become

highly expensive and also scarce. The environment is not spared as our rivers, streams and water

ways have been plundered and destroyed due to the activities of people extracting these fine

aggregate. In the backdrop of such a bleak atmosphere, there is large demand for alternative

materials from industrial waste.

Kaolin is in a layered silicate structure, with the layers binding with each other via the Van Der

Wal’s bond, among which O is bound firmly. Kaolin, when being heated in air, may experience

several structural changes, and when being heated to around 600oC, the layered structure of

kaolin is damaged due to dehydration to form a transient phase with a poor crystallinity i.e.

metakaolin. As the molecular arrangement of metakaolin is irregular in a thermodynamic met

stable condition, it is cementitious under an adequate excitation. With a high activity, metakaolin

can be used to manufacture cementitious materials and mix high-strength high-performance

concrete.

1
Metakaolin is the cementitious material used as an admixture to produce high strength concrete.

Metakaolin is the white powder of Alunumium silicate (A.2Si) by dehydrating kaolin (Al2O3

2SiO3.2H2O) at an appropriate temperature (700-900oC). Metakaolin is refined kaolin clay that is

fired (calcined) under carefully controlled conditions to create an amorphous aluminosilicate that

is reactive in concrete. Like other pozzolans (fly ash and silica fume are two common pozzolans),

metakaolin reacts with the calcium hydroxide (lime) byproducts produced during cement

hydration.

The provision of housing for all is a major problem facing both the rural and urban dwellers,

particularly in the developing countries. This is majorly as a result of rising cost of building

materials especially cement. The use of some form of cement to bind together stones, gravel and

other materials has been practiced from very early times. Cement is the most common type of

binding materials in general use around the world and it has been experiencing a steady rise in

cost due to high demand for the material (Caijun, 2001; Bentur, 2002).

The issue of impurities or undesired compounds within MK is a significant concern that has yet to

be adequately resolved. The conventional approach for eliminating undesired compounds from

MK involves calcination, although it may not be entirely effective in removing all such

compounds. Thus, prompt the need to look into effect(s) of Activated Carbon (AC) on pozzolanic

properties of MK. Previous research works indicated that AC has binding ability due to presence

of some functional ligands or metabolites, which could help in remediating some metals or

compounds from soil, water and any other medium. Due to its limited availability, using

commercial AC for research purposes is always costly. (Adetoro et al., 2024)

By the end of this study, it is anticipated that the CPSAC will be able to reduce or remove the

undesirable compounds or impurities from MK, leading to the production of MK with less or no

impurities, which will promote or improve the development of strength when used in concrete or
2
mortar at an early stage. Howbeit, determining the composite’s strength qualities is not the

study’s primary objective. The goal, then, is to specify blended cements or innovative cement

technologies that either significantly increase hydraulic efficiency, or directly replace cement with

pozzolans (Adetoro et al., 2024).

1.2 Aim and objectives of the study

1.2.1 Aim of the study

The aim of this research study is to assess strength performance of concrete production using

Metakaolin refined with 10% CPSAC.

1.2.2 Objectives of the study

i. To produce Carica Papaya Stem Activated Carbon (CPSAC)

ii. To produce and modified Metakaolin with 10% CPSAC

iii. To produce concrete using modified Metakaolin as partial replacement of cement.

iv. To assess the strength performance of the concrete produced with respect to curing age.

1.3 Problem of statement

The importance of concrete to the construction industries cannot be over emphasis, because large

volume of concrete is being used every day during construction processes. One of the constituents

in the production of concrete “cement” has become very expensive and scarce because of the high

cost of production. The compressive and flexural strengths of concrete depend on the properties

of the materials by which it is made. Such materials are the coarse aggregates, fine aggregates,

cement and quality and quantity of water used. In respect to this study, which is to compare the

compressive and flexural strengths of concrete made with ordinary metakaolin and metakaolin

modified with 10% CPSAC, are all geared towards finding an alternative replacement to cement

which is in constant use. Due to the massive infrastructural development going on in Nigeria.

Because of the depletion of cement, this work is trying to find a replacement which will be cheap
3
and affordable. Metakaolin is the material selected to be used in replacing cement because in term

of size, it has the same similarity as cement though finer. CPSAC is being used in the refining of

metakaolin because past research works showed its metal binding purification abilities.

1.4 Scope of the study

This project research is limited to the study of the effects of metakaolin refined with 10% CPSAC

on the compressive and flexural strengths of concrete.

1.4 Justification of the study

Metakaolin, which is derived from naturally occurring kaolin clay, has been used extensively in

replacement of cement in mortar and concrete making, but not much attention has been paid to

considering the effect of clay source on it reactivity. In addition, the delay in achieving strength of

pozzolan mixed concrete requires the use of innovative materials that improve strength

development at the early stage. Based on this fact one of the most effective ways to mix CPSAC

with the MK and check its effects. This saves cost and energy. (Raheem et al., 2021).

4
 CHAPTER TWO

LITERATURE REVIEW

2.1 Theoretical Background

2.1.1 Metakaolin

Metakaolin is a pozzolanic material which is manufactured from kaolin clay, after refinement and

calcination under specific conditions (temperature and time). It is quite useful for improving

concrete quality, by enhancing strength and reducing setting time, and may thus prove to be a

promising material for manufacturing high performance concrete (Li and Ding 2003). It differs

from other supplementary cementitious materials like fly ash, slag or silica fume, in that it is not a

by-product of an industrial process; it is manufactured for a specific purpose under controlled

conditions. It is produced by heating kaolin to temperatures of 550-600°C for periods ranging

from 1 hour to 12 hours. This heat treatment serves to break down the structure of kaolin.

The use of metakaolin as a partial cement replacement in concrete has received considerable

attention. Metakaolin is used as a supplementary cementitious material in concrete to reduce

cement consumption, to increase strength and the rate of strength gain, to decrease permeability

and to improve durability (Khatib and Wild, 1998; Aquino et al., 2001; Asbridge et al., 2001;

Boddy et al., 2001; Justice, et al., 2005)

2.2 Carbonization

The terms carbonization means to convert organic matter to elemental carbon at high temperature

in the absence of oxygen. This process drives off the volatiles matter to form char. The char

obtained normally has low surface area and adsorption capacity since the porous structure is not

well developed. Burchell, T. D. (1999).

All the carbon materials composed of the carbon element has unique bonding with other

elements and with itself. Depending on type of hybridization of the carbon atoms, the main

allotropic forms of carbon (Delhaes, 1998) are classified as diamond, graphite and fullerenes.

Diamond forms a cubic 3D structure (sp3 – based structure) in which each carbon atom

bonds with four other carbon atoms through sp3 σ bonds. The C-C bond length is 154 pm.

Diamond has the highest atomic density of any solid and is the hardest material with the highest

thermal conductivity and melting point. Graphite has a hexagonal layered structure (sp2 – based

structure) in which carbon atoms are bonded to neighboring carbon atoms by sp2 σ and

delocalized π bonds. Graphite has an even higher thermal conductivity than diamond and

exhibits a good electrical conductivity. Fullerenes are three dimensional carbon structures where

the bonds between the carbon atoms are bent to form an empty cage of sixty (C60) or more

carbon atoms. This is due to the re-hybridization, resulting in a sp2+ε form, which is intermediate

between sp2 and sp3 (Ebbesen and Takada, 1995).

The majority of carbons exhibit the allotropic forms, i.e. a sp2 – based structure. Based on

the degree of crystallographic order in third direction (c-direction), the allotropic form of

graphite can be classified into graphitic carbons and non-graphitic carbons (Franklin, 1951). Non-

graphitic carbons in turn divided into graphitizable and non-graphitizable carbons. A

graphitizable carbon is “a non-graphitic carbon which upon graphitization (heat treatment) is

converted into graphitic carbon”, while a non-graphitizable carbon is “a non-graphitic carbon

which cannot be transformed into graphitic carbon” by high-temperature treatment. Carbons

exhibit different structures depending on the size and such a wide variety of possible structures

gives rise to a large amount of different types of carbons.

6
2.3 Activated Carbon

The activation process creates or increases porosity on the activated carbon Surface. The two

main methods of producing activated carbon can either be physical (steam/carbon dioxide) or

chemical activation, both of which require the use of elevated temperatures. Chemical activation

is achieved by degradation or dehydration of the usually cellulosic raw material structure. Steam

activation, however, initially involves the removal of volatiles, followed by oxidation of the

structure’s carbon atoms. Activated carbon (AC) is a non-graphitic, non-graphitizable carbon with

a highly disordered microstructure. It is well known for high adsorption capacity due to its high

surface area and porosity Burchell, T. D. (1999).

Moreover, some alternatives materials have already been used as a part of natural sand e.g. fly

ash, slag limestone and siliceous stone powder were used in concrete mixtures as a partial

replacement of natural sand (Priyanka et al; 2012).

However, scarcity in required quality is the major limitation in some of the above materials.

Nowadays sustainable infrastructural growth demands the alternative material that should satisfy

technical requisites of fine aggregate as well as it should be available abundantly. Amnon et al;

(2006) studied the effect of high levels of fines content on concrete properties.

2.4 Preparation of Activated Carbon

Generally activated carbon can be prepared from various raw materials including agricultural and

forestry residues. Generally, most of the precursors used for the preparation of activated carbon

are rich in carbon (Prahas, 2008). Production of AC was achieved typically through two routes,

physical activation and chemical activation (Bansal, 1988; Encinar, 1998).

2.4.1 Physical Activation

7
Involves carbonization of raw material followed by the activation at high temperatures (between

800 and 11000C) in the presence of oxidizing gases like carbon dioxide or steam (Aworn, 2009;

Cabal, 2009; Cagnon, 2009; Petrov, 2008; Zabaniotou, 2008; Zhu, 2011). Physical activation is a

two-step process. It involves carbonization of raw material followed by activation at elevated

temperatures in the presence of suitable oxidizing gases such as carbon dioxide, steam, air or their

mixtures. Carbonization temperature ranges between 400oC to 800oC, and activation temperature

ranges between 800oC to 1100oC. Generally, CO2 is used as activation gas, since it is clean, easy to

handle, and it facilitates control of the activation process due to the slow reaction rate at high

temperatures.

2.4.2 Chemical Activation

Mixing of chemical agent with precursor and then followed by pyrolysis at moderate temperatures

in the absence of air. (Munoz-Gonzalez, 2009; Rosas, 2009; Soleimani and Kaghazchi, 2008;

2005; Zuo, 2009). Preparation of activated carbon by chemical activation is a single step process

in which carbonization and activation is carried out simultaneously. Initially the precursor is

mixed with chemical activating agent, which acts as dehydrating agent and oxidant. Chemical

activation offers several advantages over physical activation which mainly include:

i. Lower activation temperature (< 800oC) compared to the physical activation temperature

(800 – 1100oC) (ElHendawy, 2008)

ii. Single activation step

iii. Higher yields

iv. Better porous characteristics

v. Shorter activation times (Nowicki, 2006) the most commonly used chemical activating

agents are H3PO4, ZnCl2, H2SO4, NaOH, HCL and KOH. Typical preparation of

activated carbon involves carbonization of the raw material in the absence of oxygen, and
8
 activation of the carbonized product (AI-Duri, 1996; Ioannidou and Zabaniotou, 2007).

Chemical activation, on the other hand enjoys the benefit of development of better porous

structure in a single process route at low carbonization temperatures as compared to

physical activation.

2.5 Concrete

Concrete is an assemblage of cement, aggregate and water, hence it is a composite material. The

global consumption of cement is too high due to its extensive use in concrete. The demand for

cement is quite high in developing countries owing to rapid infrastructural growth which results

supply scarcity. Therefore, construction industries of developing countries are in stress to identify

alternative materials to replace the demand for cement. On the other hand, the advantages of

utilization of by-products or aggregates obtained as waste materials are pronounced in the aspects

of reduction in environmental load & waste management cost, reduction of production cost as

well as augmenting the quality of concrete (Lohani et al; 2012).

In this context, cement has been replaced by metakaolin, a by-product of kaolin clay, in other to

make a comparative analysis for different parameters which are tested in the laboratories in other

to determine the suitability of the replacement in accordance to the British Standard of

Specifications for its strength. Quarry dust has been used for different activities in the

construction industry such as road construction and manufacture of building materials such as

light weight aggregates, bricks, and tiles. Crushed rock aggregates are more suitable for the

production of high strength concrete compared to natural gravel and sand (Lohani et al; 2012).

High percentage of dust in the aggregate increases the fineness and the total surface area of

aggregate particles. The surface area is measured in terms of specific surface, i.e. the ratio of the

total surface area of all the particles to their volume. The main objective is to provide more

information about the effects of various proportion of dust content as partial replacement of
9
crushed stone fine aggregate on workability, air content, compressive strength, tensile strength,

absorption percentage of concrete. Attempts have been made to investigate some property of

quarry dust and the suitability of those properties to enable quarry dust to be used as partial

replacement material for sand in concrete (Celik et al; 1996). The use of quarry dust in concrete is

desirable because of its benefits such as useful disposal of by products, reduction of river sand

consumption as well as increasing the strength parameters and increasing the workability of

concrete (Jain et. Al; 1999). It is used for different activities in the construction industries such as

road construction, manufacture of building materials, bricks, tiles and autoclave blocks.

2.5.2 Historical Development of Concrete

Concrete is a manmade building material that looks like stone. It is used in building construction,

it consisting of a hard, chemically inert particulate substance, known as an aggregate (usually

made from different types of sand and gravel), that is bonded together by cement and water

(Bellis; 2013). The word “concrete” is derived from the Latin concretus, meaning “to grow

together.” Concrete is a composite material composed of coarse granular material (the aggregate

or filler) embedded in a hard matrix of material (the cement or binder) that fills the space among

the aggregate particles and glues them together. Alternatively, we can say that concrete is a

composite material that consists essentially of a binding medium in which are embedded particles

or fragments of aggregates. Depending on what kind of binder is used, concrete can be named in

different ways. For instance, if a concrete in made with non-hydraulic cement, it is called non

hydraulic cement concrete; if a concrete made of hydraulic cement, it is called hydraulic cement

concrete; if a concrete is made of asphalt, it is called asphalt concrete; if a concrete is made of

polymer, it is called polymer concrete. Both non hydraulic and hydraulic cement need water to

mix in and react. They differ here in the ability to gain strength in water. Non hydraulic cement

cannot gain strength in water, while hydraulic cement does.

BC, non-hydraulic cement concretes were used by the Syrians and spread through Egypt, the

Middle East, Crete, Cyprus, and ancient Greece, (Zongji Li; 2011).

However, it was the Romans who refined the mixture‟s use. The non-hydraulic cements used at

that time were gypsum and lime. The Romans used a primal mix for their concrete. It consisted of

small pieces of gravel and coarse sand mixed with hot lime and water, and sometimes even

animal blood. The Romans were known to have made wide usage of concrete for building roads.

It is interesting to learn that they built some 5300 miles of roads using concrete. Concrete is a

very strong building material. Historical evidence also points out that the Romans used pozzalana,

animal fat, milk, and blood as admixtures for building concrete. To trim down shrinkage, they

were known to have used horse hair. The Egyptians used gypsum instead of lime because it could

be calcined at a much lower temperatures (Zongji Li; 2011).

2.5.3 The Characteristics of Concrete

Concrete is used extremely widely in building and civil engineering structures, due to its low cost,

flexibility, durability, and high strength. It also has high resistance to fire. Concrete is a non-

linear, non-elastic and brittle material. It is strong in compression and very weak in tension. It

behaves non-linearly at all times. Because it has essentially zero strength in tension, it is almost

always used as reinforced concrete, a composite material. It is a mixture of sand, aggregate,

cement and water. It is placed in a mould, or form, as a liquid, and then it sets (goes off), due to a

chemical reaction between the water and cement. The hardening of the concrete is called curing.

The reaction is exothermic (gives off heat). Concrete increases in strength continually from the

day it is cast (Neville, A. M.: 2011)

11
2.6 Theoretical Review

MK is a kind of pozzolan that demonstrates enhanced cementitious behaviour. An amorphous

aluminate silicate is formed when KC is dehydroxylated at temperatures between 500 and 800°C.

KC is a naturally occurring granular white rock that is rich in hydrated aluminium silicate and is

characterized by the mineral kaolinite. Possible causes of its whiteness include a low iron

concentration and the presence of contaminants in its original formation. Because of the

proportions of its constituent elements - silicon dioxide, aluminium oxide and water - kaolinite

has a pseudo-flaky, earthy fracture pattern and is hexagonal. KC is found in some states of

Nigeria (including Abia, Bauchi, Borno, Delta,Edo, Ekiti, Kaduna, Kano, Kogi, Nassarawa,

Niger, Ogun, Oyo, Plateauand Sokoto), some other Africa countries, America, China, India etc.

The categorization of clay is based on the constituent minerals, which can be classified into 4

distinct classes: Kaolinite, halloysite, nacrite and dickite. The composition comprises additional

minerals, namely attapulgite, feldspar, bauxite, rutile, quartz, mica, illite and sillimanite. Previous

studies have focused on investigating the impact of MK and various substances, including blast

furnace slag, cement and lime powder, cement and coal bottom ash, eggshell powder, nanosilica,

sugar cane bagasse and millet husk ash, treated rice husk ash, and other materials, on the efficacy

of concrete. A comprehensive review of MK was published by Alumina particles extracted from

inexpensive kaolinite have been reported by using calcination at 700 °C with sodium chloride and

leaching with sulphuric and HCl acid. The above reviewed works and others showed that MK,

which is generated from KC found in nature, has been extensively employed as a cement

substitute in the production of mortar and concrete, although the impact of the clay source on

MK’s reactivity and pozzolanic properties has received little study. The issue of impurities or

undesired compounds within MK is a significant concern that has yet to be adequately resolved.

The conventional approach for eliminating undesired compounds from MK involves calcination,
12
although it may not be entirely effective in removing all such compounds. Thus, prompt the need

to look into effect(s) of Activated Carbon (AC) on pozzolanic properties of MK. Previous

research works indicated that AC has binding ability due to presence of some functional ligands

or metabolites, which could help in remediating some metals or compounds from soil, water and

any other medium. Due to its limited availability, using commercial AC for research purposes is

always costly. Therefore, the AC used in this investigation was derived from a locally available

agricultural biomaterial i.e. CPS. Literature is very scarce on the ability of AC to remove

impurities or undesired compounds from MK, though in the recent past, showed possibility of

treatment effects on reactivity of MK using AC (i.e. Azadirachta indica bark AC (AIBAC)) -

16.22% of AIBAC removed unwanted compounds from MK totally. AC produced locally from

agricultural biomaterials have the potential to be used in this study due to their accessibility, cost-

effectiveness, time effectiveness, simplicity of use, reusability and practical method. The

utilization of CPS exhibits potential in the elimination of undesired compounds from MK and

related pozzolans. These biomaterials possess low moisture and high fixed carbon contents,

rendering them effective adsorbents for remediation purposes.

The agricultural biomaterial (i.e., the CPS) and MK are readily available in the country. This will

promote waste to wealth policies, proper and agricultural waste management. Efforts are made in

this study to use AC from aged and unproductive CPS to remove some unwanted compounds or

impurities from MK during or after calcination process of the MK. Thus, it helps to look into

effect(s) of AC on chemical properties of MK. MK, which is derived from naturally occurring

KC, has been used extensively in place of cement in mortar and concrete manufacture, but not

much attention has been paid to considering the effects of the clay source on its pozzolanicity. In

addition, the delay in achieving strength of pozzolan mixed concrete requires the use of

innovative materials that will improve strength development at an early stage. By the end of this
13
study, it is anticipated that the CPSAC will be able to reduce or remove the undesirable

compounds or impurities from MK, leading to the production of MK with less or no impurities,

which will promote or improve the development of strength when used in concrete or mortar at an

early stage.

Tremendous efforts have been made by various researchers on positive exploitation of the

efficient

use of various agricultural and industrial by products (Ettu, et al., 2013; Ogunbode and Akanmu,

2012). The use of agro-waste such as fly ash, blast furnace slag and rice husk ash amongst others

in blended cement as partial replacement of cement offer clear environmental advantages since

they do not require production of clinker calcinations and mining of all sorts (Mohd and

Abdullah, 2009; Adesiyan, 2007; Salau and Olonade, 2011). Based on this background, the paper

therefore aimed to investigate Cassava Peel Ash Blended Cement (CPABC) on compressive

strength of concrete with the view of enhancing an ecofriendly construction material for

sustainable infrastructural development of the nation.

Long T Phan et al. (2000) A compilation of fire test data which shows distinct behavioral

differences between High-Strength Concrete (HSC) and Normal Strength Concrete (NSC) at

elevated temperature is presented.

Frais et al. (2000). The authors show the results of an investigation focusing on the effect of

Metakaolin (MK) on the micro-structure of MK-blended pastes. Pastes containing 0%, 10%, 15%,

20% and 25% of MK were prepared at a constant water/binder ratio of 0.55 and cured at 200ºC

for hydration periods from 1 to 360 days.

Xia Oquian and Zongjinli (2001) studied the stress–strain relationships of concrete containing 0%

to 15% of Metakaolin at an incremental rate of 5%. They concluded that incorporation of

Metakaolin up to 15% has increased the tensile and compressive strength and also peak strain is
14
increased at increasing rate of Metakaolin up to 15%. Incorporation of Metakaolin has slightly

increased the compressive elasticity modulus.

Bo wu, Xiao - Ping Su and Huili (2002) studied the effect of high temperature on residual

mechanical properties of confined and unconfined high strength concrete. They varied the

temperature from 100ºC to 900ºC. Also elastic modulus decreases sharply at the higher

temperatures.

Chi-Sun Poon et al. (2003) an experimental investigation was conducted to evaluate the

performance of metakaolin (MK) concrete at elevated temperatures up to 800ºC. Eight normal

and HSC mixes incorporating 0%, 5%, 10% and 20% MK were prepared.

Srinivasa Rao et al. (2004) investigated the effect of elevated temperatures ranging from 50 to

250oC on the tensile strength (splitting and flexural) of HSC made with Portland Cement (PC)

and Pozzolana Portland Cement (PPC), for application in the chemical and metallurgical

industries or thermal shielding of nuclear power plants. Tests were conducted on 150 mm

diameter cylindrical specimens and 100 mm x 100 mm x 500 mm beam specimens..

Abdul Razak et al. (2005) in this study, metakaolin (MK) and silica fume (SF) were used as

cement replacement materials at 5%, 10%, and 15% by mass. Water/cementitious materials

(w/cm) ratios varied from 0.27 to 0.33, and strength testing was conducted up to an age of 180

days.

Chi-Sun Poon et al. (2006) this study is to relate the mechanical and durability properties of high

performance metakaolin (MK) and silica fume concretes to their microstructure characteristics.

The compressive strength and chloride penetrability of the control and the concretes incorporated

with MK or silica fume (SF) at water-to-binder (w/b) ratios of 0.3 and 0.5 are determined.

Nabil M. Al-Akhras (2006) this study investigates the effect of metakaolin (MK) replacement of

cement on the durability of concrete to sulfate attack. Three MK replacement levels were
15
considered in the study: 5%, 10%, and 15% by weight of cement. The other experimental

parameters investigated in the study were: water to binder ratio (0.5 and 0.6), initial moist curing

period (3, 7, and 28 days), and curing type (moist and autoclaving), and air content (1.5% and

5%). After the specified initial moist curing period, concrete specimens were immersed in 5%

sodium sulfate solution for a total period of 18 month.

Bamonte et al.(2010) the present investigation deals with high temperature, in order to evaluate

the thermal diffusivity and the mechanical decay as a function of the temperature, since there is

still scanty information in the literature on the high temperature behavior of this family of

materials.

Rafat Siddique et al. (2010) an investigation dealing with the effect of metakaolin (MK) on the

near surface characteristics of concrete are presented in this paper. A control concrete having

cement content 450 kg/m3 and w/c of 0.45 was designed.

Dinakar et al. (2011) examined High Reactive Metakaolin (HRM) for high strength and high

performance concrete. According to him Supplementary Cementing Materials (SCMs) such as fly

ash, silica fume and GGBS are increasingly used in recent years as cement replacement material.

They help obtain both higher performance and economy

Beulah et al. (2012) this paper presents an experimental investigation on the effect of partial

replacement of cement by metakalion by various percentages, viz., 0%, 10%, 20%, and 30% on

the properties of high performance concrete, when it is subjected to hydrochloric acid attack.

Vikas Srivastava et al. (2012) this study deals with the addition of some pozzolanic materials, the

various properties of concrete, viz., workability, durability, strength, resistance to cracks and

permeability can be improved.

In this present work is to find the mechanical properties of partially replaced cement with

Metakaolin at 0%, 10%, 15%, 20%, 25% and 30% for M15 grade of concrete. To evaluate
16
compressive strength and Flexural strength at 10% replacement by exposing to temperature of

550oC to 600 oC.

2.7 Compressive Strength

Compressive strength is often measured on a universal testing machine; these range from very

small table top systems to ones with over 53 MN capacity. Measurements of compressive strength

are affected by the specific test method and conditions of measurement. Compressive strengths

are usually reported in relationship to a specific technical standard. By definition, the ultimate

compressive strength of a material is that value of uniaxial compressive stress reached when the

material fails completely. The compressive strength is usually obtained experimentally by means

of a compressive test. The apparatus used for this experiment is the same as that used in a tensile

test. However, rather than applying a uniaxial tensile load, a uniaxial compressive load is applied.

As can be imagined, the specimen (usually cylindrical) is shortened as well as spread laterally. A

Stress–strain curve is plotted by the instrument and would look similar to the following: true

stress-strain curve for a typical specimen. The compressive strength of the material would

correspond to the stress at the red point shown on the curve. In a compression test, there is a linear

region where the material follows Hooke's Law (Elayesh; 2009).

2.8 Flexural strength

Flexural strength is the ability of a beam or slab to resist failure in bending, it is a measurement

that indicates the resistance of a material to deformation when placed under a load (Kala; 2013).

Flexural strength is very important because it gives two useful parameters which includes the first

crack strength, which is primarily controlled by the matrix, and the ultimate flexural strength or

modulus of rupture, which is determined by the maximum load that can be attained (Elayesh;

2009).

17
 CHAPTER THREE

MATERIALS AND METHODS

3.1 Materials

This study used CPS, KC and the reagents, which were distilled water and Hydrochloric acid

HCl. Equipment used were muffle furnace (5X1-1008 model), oven (Uniscope- SM9053 model),

mechanical grinding machine (Controls - EN12390-2 model), Scanning Electron Microscope

(SEM - Joel - JSM - 7600F model), Rigaku X-ray diffractometer (Rigaku miniflex and diffraction

model), Herzog Gyro-mill (Simatic C7-621 model), mechanical sieve shaker (Controls -

15DO410 model), sieve and weighing balance. The apparatus employed in the experiment

included a beaker, funnel, measuring bottle.

Figure 3.1: Carica Papaya Stem

3.2 Methods

3.2.1 Development of Carica Papaya Stem Activated Carbon (CPSAC)

Development of Catica Papaya Stem Activated Cartion (CPSAC) the CPS sample was collected

from the Federal Polytechnic teaching and research farm, Ado Ekiti Nigeria. The coordinates

point of the sampling are latitude 7°59'00* N and longitude 5°30'00* E, the collected CPS sample

was sliced into pieces and then cleaned it wash distilled water to get rid of dirt and other
18
impunities, after that, it was pounded and immediately it was grinded and washed after that it was

then sun dried for some days. CPS samples were now carbonized in a muffle furnace (5X1-1008

model) for 35-40mins, at a set temperature of 550 0-6000C, it was brought out of the muffle

furnace Gallenkomp England (SXL-1208 Model) thereafter 750ml of hydrochloric acid was

diluted with distilled water and soak for 2hours then washed with distilled water 3-5 times using

white handkerchief until they attained a pH of 7.0. The washed sample were air dry for some

hours.

Figure 3.2: Activated carbon

3.2.2 Development of Metakaolin (MK)

Development of kaolin (KC) was collected from Ikere - Ekiti, Nigeria. The coordinates of the

sampling point are Latitude 7'4757* N and Longitude 4929* 03* E. The KC samples obtained

were placed in airtight bags and transported to the laboratory.

MK is made by heating the dried KC inside muffle furnace at a temperature of 550 0C to 6000C up

to 37minutes and allowed to cool before being kept inside desiccator.

Preparation of Metakaolin & CPSAC

i. CPSAC – CPS carbonized at 600 °C & activated with HCl acid.

ii. Metakaolin - Kaolinite carbonized at 700 °C

3.3.1 Chemical Activation

Chemical activation is typically employed when wood products are used as raw materials. It

allows both pyrolysis and activation to be integrated into a single, relatively lower temperature

process in the absence of oxygen. Chemical agents such as phosphoric acid, zinc chloride and

pota dehydrating and stabilizing agents that enhance the development of porous structure in the

activated carbon. The process can be summarized by the flow chart below

Raw
material Activation
Activated
preparatio (Cheminal) Cooling
Carbon
n

Figure 3.2: The Process of Chemical Activation

Chemical activation is usually avoided in industrial applications due to environmental concerns

and the costs involved in the treatment of materials with chemicals. Chemical activation offers

several advantages since it is carried out in a single step combining the carbonization and

activation process, performed at lower temperatures, produced a much higher yield than the

20
physical activation, and therefore resulting in the development of a better porous structure.

However, there are also some disadvantages such as corrosiveness of the process and the washing

stage.

3.4 Factors affecting activated carbon production

3.4.1 Raw Material

Most organic materials rich in carbon that do not fuse upon carbonization can be used as a raw

material for the manufacture of activated carbon. In the selection of raw material for the

preparation of porous carbon, several factors are taken into consideration, these include;

i. High carbon content

ii. Low inorganic content (i.e. low ash)

iii. High density and sufficient volatile content

iv. The stability of supply in the country

v. Potential extent of activation

vi. Low costs

vii. Low degradation upon storage

Lignocelluloses materials constitute the more commonly used precursor and account for around

45% of the total raw materials used for the manufacture of activated carbon. Low content in

organic materials is important to produce activated carbon with low ash content, but relatively

high volatile content is also needed for the control of the manufacturing process. Raw materials

such as coconut shells and fruit stones are very popular for many types of activated carbon

because their relatively high density, hardness and volatile content are ideal for the manufacture

of hard granular activated carbon. Coconut shells together with peach and olive stones are used

commercially for the production of micro porous activated carbons for a very wide range of

applications.
21
3.4.2 Temperature

Temperature especially the final activation temperature affects the characteristics of the activated

carbon produced. Generally, for commercial activated carbon, it is usually conducted at

temperature above 800oC using steam or carbon dioxide. As reported by several authors,

activation temperature significantly affects the production yield of activated carbon and also the

surface area of activated carbon. The temperature used as low as 200 oC and up to a high of

1100oC. The optimum temperatures have been reported to be between 400 oC - 600oC by most of

the earlier researchers irrespective of the time of activation and impregnation ratio for different

raw material.

The increasing of the activation temperature reduces the yield of activated carbon continuously.

This is expected since an increasing amount of volatiles is released at increasing temperature from

600oC- 900oC. The decreasing trend in yield is paralleled by the increasing activation temperature

due to the activation reaction. These phenomena are also manifested in the decreasing volatile

content and increasing fixed carbon for increasing activation temperature. It was also suggested

previously that, the percentage of volatile matter decreased with an increase of carbonization

temperature and the variation of this parameter was maximum between 200 oC-800oC due to rapid

carbonization occurring in this region. It was also unsuitable to prepare activated carbon when

carbonization temperature was more than 800oC since the successive decreased in volatile matter

is minimal above this range. This was accompanied with an increase of fixed carbon and ash

content which may be attributed to the removal of volatile matter in the material during

carbonization process thus leaving behind more stable carbon as forming minerals. Another

notable feature that showed the effect of activation temperature on the activated carbon is the

BET surface area. As the activation temperature increased, the BET surface area also increased.

22
This may be attributed to the development of new pores as a result of volatile matter released and

the widening of existing ones as the activation temperature became higher.

3.4.3 Activation Time

Besides activation temperature, the activation time also affects the carbonization process and the

properties of activate carbon. From previous studies, the activation times normally used were

from 1 hour to 3 hours. As the time increased, the percentage of yield decreased gradually and the

BET surface area also increased. This result is possibly due to the volatilization of organic

materials from raw materials which result in formation of activated carbon. The extent of decrease

in product yield is observed to be reducing when excessive activation occurs.

3.3 Treatment of samples

(Using experimental design)

i. CPSAC (0 - 25%) + Kaolin (100% - 200g) – Calcined (700 °C)

ii. CPSAC (0 - 25%) + MK (100% - 200g) – Soaked in water (24 hrs.), thereafter oven dried

at 110 °C

3.4 Concrete production

Concrete is a composition materials which consists of aggregates, cement and water used in

construction. The aggregates are generally sands, river sand, or crushed rocks. The cement

commonly used is Portland cement and other materials such as fly ash and slay cement serve as

binder for the aggregates. Water is then mixed with this dry composite, which reacts with the

cement through a chemical process called hydration. Through this reaction, the composite

eventually solidifies and hardens, creating a robust, compacted stone-like material known as

concrete. Concrete is the backbone for infrastructural development of whole world as it is an

indispensable part of the fabric of modern society used for everything from road pavements to

high risen building structures. Concrete is plastic and malleable when newly mixed, yet strong
23
and durable when hardened. Concrete has advantageous properties such as good compressive

strength, flexural strength, high mould ability, plastic and malleable when fresh and durable,

impermeable and fire resistant when solidified. These qualities explain why concrete can be used

to build skyscrapers, bridges, sidewalks, highways, houses, retaining structures, stadiums and

dams. Therefore, there is an increasing demand for concrete on the daily basis and an increase in

the price of the materials.

Concrete has some undesirable properties such as low tensile strength, low ductility, heavy weight

and low energy absorption. These disadvantages have motivated the civil engineers to make use

of the conventional reinforcement to increase the tensile strength and ductility. Concrete is

however characterized by failure, the nearly complete loss of loading capacity, when once failure

has occurred.

3.4.1 Fine Aggregates

The fine aggregates (river sand) that was used for this project is locally sourced. Fine aggregates

are the essential ingredient or component in concrete that consists of natural sand or crushed store.

The quality of fine aggregates density strongly influences the hardened properties of the concrete.

The concrete or mortar mixture can be made more durable, stronger and cheaper if the selection

of fine aggregate was done based on grading zone, particles shape and surface texture, abrasion

and skid resistance and absorption and surface moisture.

24
 Plate 3.2 Fine aggregate (River Sand)

3.4.2 Cement

Cement in general is termed as Portland cement (PC) and is used as a perfect binding material

across the world. It is also commonly available for general use around the globe, as an ingredient

to mortar, stucco and grout. Cement is manufactured from limestone by grinding, calcining, then

grinding to produce a fine powder, which is in turn mixed with gypsum to retard setting time. The

basic cement clinker is a hydraulic mass composes two third mass of calcium silicate (Cao.SiO 3)

and the rest consist of aluminum and iron associated and other materials, with the ratio of C ao to

Sio3 to be not less than 2% and magnesium oxide not more than 5% by mass. These are the norms

proposed by German standards, published in 1909. The reacted mass (calcined mass) basically

forms nodules-like materials of approximately one millimeter diameter, which acquires the

properties of binding, and in other to increase the rate of reaction of binding, surface area is

increased by grinding in a ball mill. According to ASTMC 150, the cement possesses the

properties of hardening as well as water resistance. The nature of hardening retards when

grounded calcium silicates present in multiple forms. Nature is gifted with limestones and is

extensively available as a natural resources by way of rocks. During the advent of technological

development cement has been considered to be the best materials to be used in construction.

25
Through the present of iron oxide and aluminum oxide appears as fluence are responsible for the

strength of cement.

3.4.3 Water

In many specifications, the quality of water is covered by a clause saying that water should be fit

for drinking. Such water is very rarely contained dissolved solids in excess that affect the strength

and reliability of the concrete. Water is crucial ingredient of the concrete as it actively participates

in the chemical reaction with cement and results in solidifying of the concrete. The water that was

used for this project research was portable water. The portable water used was confirming to the

requirements of IS 456-2000. However, drinking water may be unsuitable as mixing water. When

the water has high concentrations of sodium or potassium, sea water (or any water containing

large quantities of chlorides) tends to cause persistent dampness and efflorescence such water

should not be used in concrete production. For instance, in the case of reinforced concrete, sea

water increases the risk of corrosion of the reinforcement, especially in tropical countries. Hence

the quality water helps to form the strength giving cement gel or thickening. It is necessary to

consider the purity and quality water during concrete production, generally, water satisfactory for

mixing is also suitable for curing purposes.

3.4.4 Mixing Design

Prepared volume of cement was added to required mass of the source material (modified

metakaolin and metakaolin or calcined kaolin clay) with fine aggregate (River sand) and water

were mixed thoroughly with spade as shown below. Size of mould = 100mm by 100mm by

100mm = 0.1mx0.1mx0.1m

26
Figure 3.3: Mixing and Casting of Concrete

The mixed aggregate with spade was cast using hand trowel to fill the iron mould of 100mm by

100mm by 100mm for cubes concrete and 400mm by 100m by 100m for flexural concrete on the

surface. The mixed was tamped 25 blows to ensure a good concrete compaction. The compacted

concretes in the mould were left for 24hours before demoulding.

The specimen was cured in a clean water under the shade for 3, 7, 28, 56 and 90 days

respectively. On maturity of the prescribed days, the specimen was removed and allowed the

water to dry at least to maintain reasonable stability before test.

3.5 Test on specimen

3.5.1 Compressive test

Compressive test was carried out at Afe Babalola University, department of civil engineering

laboratory. The compressive strength test was carried out using an electronically or digitally

operated compressive test machine with capacity of 2000KN and loading rate of 14,500N/mm 2.

The test specimen or samples were placed in the hydraulic testing frame and a force was applied

until the specimen crushed. The prism halves were centered laterally to the platens of the

machines within +- 0.5mm and longitudinally, so that the end face of the prism overhangs the
27
platens by about 10mm. therefore, the maximum force applied, and the dimensions of the

specimen were then recorded and compressive strength calculated. Hence compressive strength

may be defined as the measured maximum resistance of a concrete specimen to axial loading.

Figure 3.4: Compressive machine

3.5.2 Flexural strength test

Flexural strength test is a standard test for modulus of nature, it is based on two crucial properties,

the elastic modulus of the material and the moment of inertia (function of geometry). Flexure or

bending is commonly encountered in structural elements such as beams and slabs which are

transversely loaded. Flexural strength is a measure of the tensile strength of OPC concrete. In

other words, it is a measure of a resistance against failure in bending. Although the probability of

the structures being flexure deficient is low, failures have occurred due to a variety of factors,

errors in design calculations and improper detailing of reinforcements, construction fails or poor

construction practices, changing the function of a structure from a lower service load to a higher

service load, seismic and wind action, reduction or total loss of reinforcement steel area causing

the corrosion in service environment. Corrosion is caused by destructive attack of chloride ions
28
penetrating by diffusion or other penetration mechanism from the outside, by incorporation into

the OPC concrete mixture, by carbonation of the cement cover, or their combination (Cabrera

1996). Carbonation of concrete penetration of acidic gases into the concrete causes of

reinforcement corrosion. Nevertheless, there are few factors related to the concrete quality, such

as water/ cement ratio, cement content, impurities in the concrete ingredients, presence of surface

cracking, etc. and others related to the external environment, such as moisture, bacterial attack,

stray currents, etc. which affect reinforcement corrosion (casiro 1997). Uncontaminated cover

concrete provides a physical barrier that prevents the direct exposure of the steel surfaces to the

outside environment.

Hence flexural concretes were crushed at Afe Babalola University, Department of civil

engineering laboratory. The recorded values and flexural strengths were calculated

Figure 3.5: Flexural machine

29
 CHAPTER FOUR

RESULT AND DISCUSSION

4.1 Compressive strength test results for Concrete produced with ordinary Metakaolin

The test results of Compressive strength for 3 days, 7 days, 28 days, 56 day and 90 days on

produced concrete using ordinary metakaolin (i.e. 0%AC + MK) are presented in Figure 4.1. It is

observed that Concrete produced with 5% AC + MK increases all through, 10% AC + MK

increase in 3 to 56days and declined in 90days, 15% AC + MK increases all through the curing

age days and 30% AC + MK increased with increase in curing age. Though the one produced

with 15% AC + MK also increased with curing age, but reached maximum strength at 56 days

curing age.

0%AC +MK
6
Compressive Strength

5
4 5%
(N/mm2)

3 10%
2 15%
30%
1
0
3 Days 7 Days 28 Days 56 Days 90 Days
Curing Age

Figure 4.1: Compressive strength of the Produced Concrete using ordinary Metakaolin (i.e. 0%

CPSAC + MK)

4.1.1 Compressive strength test results for Concrete produced with 10% CPSAC +

Metakaolin

The test results of Compressive strength for 3 days, 7 days, 28 days, 56 day and 90 days on

produced concrete using ordinary metakaolin (i.e. 10%AC + MK) are presented in Figure 4.2. It is
30
observed that Concrete produced with 5% AC + MK increases all through, 10% AC + MK

increase in 3 to 56days and declined in 90days, 15% AC + MK increases all through the curing

age days and 30% AC + MK increased with increase in curing age. Though the one produced

with 15% AC + MK also increased with curing age, but reached maximum strength at 90 days

curing age.

10%AC +MK
8
7
Compressive Strength

6
5 5%
(N/mm2)

4 10%
3 15%
2 30%
1
0
3 Days 7 Days 28 Days 56 Days 90 Days

Curing Age

Figure 4.2: Compressive strength of the Produced Concrete using ordinary Metakaolin (i.e. 10%

CPSAC + MK

4.2 Flextural strength for zero (0%) Metakaolin

The test results of Flexural strength for 3 days, 7 days, 28 days, 56 day and 90 days on produced

concrete using ordinary metakaolin (i.e. 0%AC + MK) are presented in Figure 4.3. It is observed

that Concrete produced with 5, 10, 15 and 30% AC + MK increased with increase in curing age.

Though the one produced with 15% AC + MK also increased with curing age, but reached

maximum strength at 28 days curing age.

31
 0%AC +MK
2.5

2
Flexural Strength 5%
(N/mm2) 1.5
10%
1 15%
30%
0.5

0
3 Days 7 Days 28 Days 56 Days 90 Days

Curing Age

Figure 4.3: Flexural strength of the Produced Concrete using ordinary Metakaolin (i.e. 0%

CPSAC + MK

4.2 Flextural strength for zero (10%) Metakaolin

10%AC +MK
2
1.8
1.6
Flexural Strength

1.4
1.2 5%
(N/mm2)

1 10%
0.8 15%
0.6 30%
0.4
0.2
0
3 Days 7 Days 28 Days 56 Days 90 Days

Curing Age

Figure 4.4: Flexural strength of the Produced Concrete using ordinary Metakaolin (i.e. 10%

CPSAC + MK

32
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