CHAPTER 2

Review of Related Literature

It was proven by different studies that geopolymer concrete is a new potential

construction material and has the possibility of partially replacing ordinary concrete

or may become a full replacement if studied thoroughly with continuous research.

2.1 Geopolymers

The term geopolymer was proposed by Davidovits in 1978 which synthesizes

a solid aluminosilicate source of geological origin or in by-product materials (i.e. coal

fly ash, blast furnace slag, calcined clays, and natural pozzolans) by alkaline

activation subjected to higher temperature. This process is called geopolymerization

and that is where the aforementioned term above originated. This class of materials

are members of inorganic polymers and its chemical composition is similar to natural

zeolitic materials, but consists of an amorphous, three-dimensional structure (Palomo

et.al, 2009).

The solid aluminosilicate to be used in producing a geopolymer must be rich

in silica and alumina but low in calcium. Therefore when mixed with a hydroxide and

silicate solution, the aluminosilicate will be reactive not just because of the high

content or presence of silica and alumina but also it dissolves easily and rapidly than

crystalline ones (Xu & van Daventer, 2000). The alkaline liquids to be needed are

from soluble alkali metal cations that are usually sodium or potassium based. In the

process of geopolymerization, the most common alkaline liquid combination used is

sodium hydroxide or potassium hydroxide and sodium silicate or potassium silicate

(Komnitsas, 2007).
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2.2 Geopolymer Concrete

Concrete is the most globally used material second to water and in the process

it is using Ordinary Portland Cement (OPC) as the primary binder material that is

imperative considering its high emission of carbon which leads to environmental

degradation. Therefore, the construction industry is now focusing on new ways to

replace ordinary Portland concrete and this research trend is now directing towards

more eco-friendly concrete such as geopolymer and recent studies focused on the use

of fly ash for its abundance to be used for the geopolymerization. Fly ash based

geopolymer concrete has shown promise and has been gaining attention from the

construction industry because recent studies have shown it has excellent short and

long term properties (Ghosh, Kumar A, Kumar S, 2013). Its properties includes high

compressive strength, it undergoes very little drying shrinkage, low creep and has an

excellent resistance to sulphate attack especially if it is heat cured (Wallah, Rangan,

2006). Moreover, geopolymer concrete technology has the possibility to reduce the

carbon emission globally which helps to support the advocacy of sustainable

development and may aid in the growth of the concrete industry.

2.3 Fly Ash

According to the American Concrete Institute (ACI) Committee 116R, fly ash

is defined as “the finely divided residue that results from the combustion of ground or

powdered coal and that is transported by flue gasses from the combustion zone to the

particle removal system” (ACI Committee 232 2004). Fly ash is a by-product of coal

obtained from the thermal power plants which resulted from the combustion of a

finely ground coal which is used as fuel to generate electricity. They are typically
 12

spherical and finer than the Portland cement and lime that ranges from less than 1 µm

to no more than 150 µm in diameter.

The chemical composition of fly ash should be of higher proportion of

alumina and silica to become a good aluminosilicate source material to have enough

potential of being reactive to alkaline solution thus producing an effective geopolymer

in terms of its binding capacity. The major influence on the fly ash chemical

composition comes from the type of coal considering combustion. The combustion of

sub-bituminous coal contains more calcium (a key factor in producing geopolymer)

and less iron than fly ash from bituminous coal. The physical and chemical

characteristics of the fly ash depend on the combustion methods, where it will come

from, and its particle shape. The chemical compositions of various fly ashes show a

wide range, indicating that there is a wide variations in the coal used in power plants

all over the world (Malhotra & Ramezanianpour 1994).

Aside from its chemical composition, other characteristics are taken into

consideration namely loss on ignition (LOI), fineness, and uniformity. LOI is a

method for estimating the unburned carbon content of fly ash. Fineness of fly ash

mostly depends on the operating conditions of coal crushers and the grinding process

of the coal itself. Finer gradation generally results in a more reactive ash and contains

less carbon. These properties are important because its spherical shape often helps to

the workability of concrete which serves as a filler of voids thus producing a dense

and durable concrete.

2.4 Coconut Husk

The Philippines is the world’s second largest producer of coconut that plays an

important role in the economy that comprises approximately one quarter of farm land
 13

in the country (Burton, 2018). However at the same time coconut husk wastes are

also produced such as coconut shell, coconut husk and coconut coir dust that majorly

contributed to the agricultural wastes of the country. That is the reason there is a need

for a study to recycle this wastes or may develop a technology to transform these into

a more advantageous product. Coconut shell is the most utilized agricultural by-

product to be used as an alternative aggregate (coarse aggregate) in concrete but the

reported utilization rate is very low (Sharma, Gupta, 2013).

The coconut husk is rich in silica and has a great potential to be an alternative

silica source which is a notable consideration because it will be a good reaction in

terms of same structural element present in the geopolymerization. Using XRD (X-

ray Diffraction) to determine the chemical composition of a coconut husk ash its silica

content significantly increased with the inclusion of alkaline treatment versus without

treatment. The reason for this is because SiO2 itself is a weak acidic element and only

reacts with strong bases like KOH and NaOH (Anuar, Khaidir, 2018). Therefore it is

proven that coconut husk ash would be a promising alternative source of silica to

reduce cost of production as it shows high purity of silica for use in other fields such

as ceramics and chromatography but more importantly a possible alternative to fly ash

based geopolymer concrete.

2.5 Alkaline Liquids

Alkaline activated solution plays a significant role in the geopolymer synthesis

for the dissolution of silica and alumina as well as for the catalysis of poly-

condensation reaction (Kumar, 2016). The most common of these is the combination

of sodium hydroxide (NaOH) or potassium hydroxide (KOH) and sodium silicate

(Na2SiO3) or potassium silicate (K2SiO3). Therefore a combination of sodium

hydroxide and sodium silicate is recommended because recent studies suggested that

such solution produces higher compressive strength at 28 days curing compared to

ordinary Portland concrete (Rangan, 2008). Higher concentration of sodium

hydroxide solution (in terms of molarity) plays a vital role in producing higher

compressive strength of geopolymer concrete. The alkaline activation of materials

can be defined as a chemical process that provides a rapid change of some specific

structures, partially or totally amorphous, into compact cemented frameworks. Alkali

activation specifically for fly ash is a process that differs widely from Portland cement

hydration and is very similar to the chemistry involved in the synthesis of large

groups of zeolites (Bakri, 2012).

2.6 ASTM Regulation

Since there is still no specific outline or procedures for producing geopolymer

concrete as the researchers are conducting the study, it has decided and done by recent

studies to comply with the guidelines and specifications of ASTM. Since the testing

will be done in a laboratory, ASTM C192 “Standard Practice for Making and Curing

Concrete Test Specimens in the Laboratory” is to be followed for this provides

standardized requirements for preparation of materials, mixing concrete, making, and

curing test specimens under laboratory conditions. Other specifications include

ASTM C33 “Standard Specification for Concrete Aggregates” for the aggregates with

its effects of its properties and grading will not be investigated in this study. Together

with the sieve analysis stated in ASTM C136 “Standard Test Methods for Sieve

Analysis of Fine and Coarse Aggregates”.

2.7 Optimization

The concept of optimization is discovering an option from which will give the

most efficient achievable performance including constraints that will be encountered,

by increasing the desired ones and reducing the undesired ones. In engineering

discipline, the optimization stage of the engineering design process is a systematic

process using design constraints and criteria to allow the designer to locate the

optimal solution. In addition, optimization can be a powerful tool from which a

designer will be able to use for its simplicity even in the complex of experimentation

or a problem (Shonaike & Advani 2003).

One study conducted was to optimize the alkali activated fly ash and blast

furnace slag concrete mixture for its application in a reinforced concrete cantilever

bench (Aldin 2017). The challenge of this study was to provide longer final setting

time for the reference mixture and to achieve required workability for casting in the

bench formwork. So the researcher divided the optimized study into four phases, first

is for setting time and workability using different admixtures, second was setting time

and compressive strength of geopolymer paste then testing of setting time and

different paste mixtures on concrete level and finally the optimized mixture from the

three phases is now tested on workability, setting time, compressive strength, flexural

strength, drying shrinkage, and elastic modulus.

Another study was to optimize the fiber-reinforced geopolymer concrete using

Principal Component Analysis (PCA) which means to transform the correlated

concrete properties to correspond to multi-response cases (Elaty, Ghazy, & Hameed

2017). Four responses were conducted namely: splitting tensile strength, critical

stress intensity factor, fracture energy, and degree of brittleness were conducted.
 16

Whereas each response was performed using Taguchi method to obtain the optimal

level/factor combination of the process. Later in the study it was concluded that the

PCA-Taguchi method is an effective and suitable one for the parametric optimization

of the fiber-reinforced geopolymer concrete process especially when using multi-

performance characteristics.

2.7.1 Sigma XL

Sigma XL is an add-in tool for Microsoft Excel program and is a common

statistical software use for optimization and graphical data analysis. This software was

also used in medical and scientific researches. Its function includes graphical analysis

such as Statistical Process Control Charts, Pareto Charts, Pivot Charts, Histograms,

Dotplots, Boxplots, Normal Probability Plots, Run Charts, Multi-Vari Charts, Scatter

Plots and also Analysis of Means or the ANOM Charts. There are also different

statistical tools included in these add-in software such as Descriptive Statistics,

Equivalence Tests, One and Two Sample T-Test, Paired T-Test, One way and Two

way Analysis of Variance (ANOVA), Equal Variance Test, Correlation Matrix,

Multiple Linear Regression, Logistic Regression, Chi-square and Fisher’s Exact Test,

Nonparametric and Nonparametric Exact Tests, Minimum Sample Size for Robust T-

Test and ANOVA, Power and Sample Size Calculators and Tolerance Interval

Calculator (Wikipedia, 2018).

This add-in is very useful specifically for optimization purposes since there

are different factors that must be considered and from these are the ones to be used to

find the optimized design. The design method will change depending to how many

number of factors that will be used. Afterwards, the range of highest and lowest value

of mixture will be inserted which will be based from the gathered data then each
 17

parameter will be labelled and the response is for will now be implemented for the

experimentation purposes. Such case is a researcher used a 3 parameter for his

experiment and from that he wanted to determine the most optimized compressive

strength of concrete. By running the software, clicking the result will quickly appear

on the screen. The result shows the number of samples to be needed to determine the

most optimized mixture of the concrete. Different types of combination will be

needed to determine the most optimize mixture, thus different types of combination

will depend on the range of the lowest and highest parameter inserted, and finally

these will be the guide for optimizing a said mixture. The result of the sample to the

response must be near to each other because the design method does not choose the

combination as a random number.

2.7.2 Response Surface Methodology (RSM)

Response surface methodology (RSM) is a compilation of mathematical and

statistical techniques that are useful for developing, improving, and optimizing

processes and generally includes mathematical and statistical tools for both the design

and analysis of response surfaces. The most extensive applications of RSM are in the

particular situations where several input variables potentially influence some

performance measure or quality characteristic of the process. Thus performance

measure or quality characteristic is called the response. The input variables are

sometimes called independent variables, and they are subject to the control of the

engineer. In the design of experiments, the objective is to optimize a response (output

variable) which is influenced by several independent variables (input variables).

First-order model is the approximated function of a response defined by a linear

function of independent variables. However, if there is a curvature in the response

surface, then a higher degree polynomial should be used then its approximating
 18

function with 2 variables is now called a second-order model. In order to get the most

efficient result in the approximation of polynomials the proper experimental design

must be used to collect data. Once the data are collected, the Method of Least Square

is used to estimate the parameters in the polynomials (Bradley, 2007). Since RSM

has an extensive application in the real-world, it is important to know how and where

Response Surface Methodology started in the history. Box and Wilson suggested to

use a first-degree polynomial model to approximate the response variable. They

acknowledged that this model is only an approximation, not accurate, but such a

model is easy to estimate and apply, even when little is known about the process

(Wikipedia 2006). The first goal for RSM is to find the optimum response and if

there is more than one response then it is important to find the compromise optimum

that does not optimize only one response (Oehlert, 2000). The second goal is to

understand how the response changes in a given direction by adjusting the design

variables or parameters. One example is the growth of a plant is affected by a certain

amount of water (x1) and sunshine (x2). The plant can grow under any combination of

treatment x1 and x2 so therefore, water and sunshine can vary continuously. In this

case, the plant growth y is the response variable, and it is a function of water and

sunshine. It can be expressed as y = f (x1, x2) + e where the variables x1 and x2 are

independent variables and response y depends on them. The error term e represents

any measurement error on the response, as well as other type of variations not counted

in f (Bradley, 2007). The response can be represented graphically, either in the three-

dimensional space or as contour plots that help visualize the shape of the response

surface. Three-dimensional graph shows the response surface from the side because

sometimes it is less complicated to view the response surface in two-dimensional

graphs. However, when there are more than two independent variables, graphs are
 19

difficult or almost impossible to use to illustrate the response surface, since it is

beyond 3-dimension.

A specific study was modelled using RSM to determine the optimal mix

proportions of a standard ready mixed concrete. These variables include aggregate

mixture ratio, percentage of super plasticizer content, and the water-to-cement ratio.

Three of these variables were formulated using regression analyses and at the same

time were simultaneously optimized by using RSM-based desirability function

method (Simsek et.al, 2016). It was then later concluded in the study that this

proposed method illustrates efficiency and effectiveness. The results belonging to

factors and the effect of the interaction on responses are quite promising.

2.8 Characterization of Materials

Characterization for the material is important because it indicates if a certain

chemical that is to be needed in a certain research is present in that specific material.

Therefore the certain chemical is magnified in the material if it is indeed present. A

specific study was conducted to synthesize the structural properties of coconut husk as

a potential silica source (Anuar, 2018). Coconut husk were burned at controlled

temperatures then its ash were later treated with chemicals to extract the highest

percentage of silica it can get.

2.8.1 Scanning Electron Microscopy with Energy Dispersive Spectroscopy

(SEM-EDS)

Using Scanning Electron Spectroscopy with Energy Dispersive Spectroscopy

(SEM-EDS) the coconut husk ash was observed to be rod-like in structure and

irregular in size. Sharp edges are clearly observed on the structure thus indicates that
 20

it has good crystallinity. SEM presents a higher and more detailed complexity level

compared to an optical microscope. It forms a highly energetic and focused electron

beam and then scans the specimen in a raster scan pattern or a bitmap image. Then,

different effects can result from the interaction between the electron beam and the

electrons in the specimen. Part of the electron beam will be dispersed, though most of

the electron beam interacts with the specimen and undergoes inelastic and elastic

scattering (Girao, Caputo & Ferro 2017).

X-rays are highly energetic photons resulting from electronic transitions in the

atoms of a targeted solid by an incident accelerated electron beam. If an electron

from another shell fills in that vacancy (electron transitions), then X-rays are emitted.

Electronic transitions to the K-shell (n=1) are named KX-rays, those to the L-shell (n=2)

are LX-rays and to the M-shell (n=3) are the MX-rays. These transitions are characteristic

of each chemical element and this is the main reason that led to the development of

Energy Dispersive Spectroscopy (EDS) detection systems in electron microscopy and

consequently widening its use in materials microstructural characterization (Girao

et.al 2017).

The preparation of specimens for examination in the SEM-EDS is the most

important step for an effective imaging acquisition, accurate analysis, and careful

determination of the depth of the X-rays generation and image. SEM-EDS is a highly

specialized technique largely used in the characterization of micro and nanomaterials.

The rising relevance of such advanced technique has been clearly increasing in use for

future studies regarding characterization of microplastics (Girao et.al, 2017).

2.8.2 X-ray Diffraction (XRD)

XRD is a rapid analytical technique primarily used for phase identification of

a crystalline material and can provide information on unit cell dimensions. The

analyzed material is finely ground, homogenized, and average bulk composition is

determined (Bunaciu, 2015). It is widely used for the identification of unknown

crystalline materials (e.g., minerals, inorganic compounds) that is very beneficial

especially in crystallography. It also characterizes single crystal, poly, and

amorphous materials that are important in the geopolymerization process where the

form must be amorphous for the alkaline liquid to successfully bind with the solid

aluminosilicate material. From the previous study mentioned above, using X-ray

powder diffraction (XRD) spectrum the silica was observed to be crystalline in form

after acid treatment but was amorphous in form after the alkali treatment.
 22

2.9 Conceptual Framework

Coconut Husk
Ash

Fly Ash
Fly Ash and Coconut
Alkaline Husk Ash based
Activator Geopolymer Concrete

Water

Fine
Aggregates

Coarse
Aggregates

Compressive
Strength Test
END
PASSED
Flexural Strength
Test

Compressive
Strength Test

Flexural Strength FAILED

Seek another
design mixture
for the Fly Ash
and Coconut
Husk Ash
Geopolymer
Concrete

Figure 2.1. Conceptual Framework for Optimization of Design mixture for Fly Ash and
Coconut Husk Ash based Geopolymer Concrete
 23

The basic concept of a flow chart is the process of inflow-outflow process of

an experiment. In the presented research the researchers will follow the standard

outlined procedures and testing but the design mixture proportions will be based on

how a geopolymer concrete is produced done by recent studies. A geopolymer

concrete is also the same as ordinary Portland concrete in terms of its structural use,

but the difference is geopolymer concrete uses an alkali-activating solution to bind the

solid constituents including fly ash, coconut husk ash, and aggregates to the liquid

constituents specifically water and sodium based solutions (which will serve as the

activator). Unlike in ordinary concrete, use of Portland cement is necessary to bind

the constituents needed in producing concrete.

There will be one set of inputs in the flow chart as shown in the figure. The

input requires a mixing and testing method for geopolymer concrete based on

standards. The concrete specimen will undergo two tests namely: compressive

strength and flexural strength. When the modified mixture surpasses the compressive

and flexural strength of the DPWH requirement then it will be considered as a passing

result. However if it doesn’t surpass the strength of the DPWH requirement, another

design mix proportion must be done.