SYNTHESIS AND CHARACTERISATION OF NANOPARTICLES FROM SELECTED

PLANTS AS CORROSION INHIBITOR FOR CARBON STEEL IN AN ACIDIC

MEDIUM

BY

OLATUJA SEGUN VICTOR

MME/14/8165

A PROJECT SUBMITTED TO

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING,

THE FEDERAL UNIVERSITY OF TECHNOLOGY, AKURE,

ONDO STATE, NIGERIA.

IN PARTIAL FULFILMENT FOR THE REQUIREMENT FOR THE AWARD OF

BACHELOR DEGREE OF ENGINEERING

(IN METALLURGICAL AND MATERIALS ENGINEERING)

SUPERVISED BY

DR. (MRS) O. A. OLASEINDE

November, 2019
 CERTIFICATION

This project report titled “SYNTHESIS AND CHARACTERISATION OF NANOPARTICLES

FROM SELECTED PLANTS AS CORROSION INHIBITOR FOR CARBON STEEL IN AN

ACIDIC MEDIUM” was prepared by OLATUJA SEGUN VICTOR with matriculation number

MME/14/8165 of the Department of Metallurgical and Materials Engineering, Federal

University of Technology, Akure, Nigeria in partial fulfilment of the requirement for the award

of Bachelors in Engineering (B.Engr.) in Metallurgical and Materials Engineering.

I certified that this report has not been tendered for award of any other degree or purpose.

Student’s Signature: ------------------------ ---------------------

Student’s Name: OLATUJA SEGUN VICTOR DATE

Supervisor’s Signature: ----------------------- ----------------------

Supervisor’s Name: DR. (MRS) O. A. OLASEINDE DATE

Head of Department’s Signature: ------------------- ----------------------

Head of Department’s Name: PROF. O. A. OYETUNJI DATE

1
 DEDICATION

This work is dedicated to the Godhead, the Alpha and Omega and my mum, Prophetess V. I.

OLATUJA.

2
 ACKNOWLEDGEMENT

Firstly, I would love to express my deepest sense of gratitude to God Almighty for His unfailing

love. I appreciate all my lecturers at the Metallurgical and Materials Engineering Department,

FUTA, who have in one way or the other assisted me in this project. Also, my project supervisor,

Dr. (Mrs.) O. A. Olaseinde, for her advice, direction, supervision and assistance all through the

period of this project. Again, I love to acknowledge the laboratory attendants of Mineral

Processing Laboratory and Corrosion laboratory, Metallurgical and Materials Engineering

Department, FUTA for their patience, assistance and attention throughout my practical work in

their laboratory. Furthermore, I love to acknowledge my loving friends: MME Class ’19,

RCFFUTA Redeemed of the Lord family and prayer unit, Joseph, Emmanuel, Yinka Makinde,

Set-Apart, ESF-FUTA, for their care and support. My Appreciation goes to Mr. and Mrs. Olusa

Adeola, Mr. and Mrs. Olusa Olorunfemi, all my cousins and all my siblings who have always

been supportive spiritually, materially and financially; My final acknowledgment goes to my

mum for her love and care, I say may my Heavenly Father reward you all bountifully.

3
 ABSTRACT

Nanotechnology has become a hot topic among scientists in recent years. Nanoparticles are

widely employed because of their small size, orientation, and physical qualities, which have been

demonstrated to alter the performance of any other substance that comes into touch with these

tiny particles. Different chemical, physical, and biological processes can all be used to make

these particles. However, the biological approach is the most popular method of preparation

because it is simpler than the others, more environmentally friendly, and takes less time. The

green synthesis was carried out with the help of an aqueous solution of ALOE VERA leaf extract

and AgNO3. Due to its evocative physical and chemical qualities, silver was of special interest

for this research. The color shift was noticed after a set ratio of plant extract to metal ion was

created, demonstrating the creation of nanoparticles. SEM was used to examine the

nanoparticles. Based on the SEM examination, the nanoparticles were found to be between 160

and 180 nm in size.

4
 TABLE OF CONTENT

TITLES PAGES

CERTIFICATION 1

DEDICATION 2

ACKNOWLEDGEMENT 3

ABSTRACT 4

TABLE OF CONTENT 5

LIST OF FIGURES 8

LIST OF PLATES 9

CHAPTER ONE

1.0 INTRODUCTION 10

1.1 BACKGROUND OF THE RESEARCH 11

1.2 STATEMENT OF THE PROBLEM 14

1.3 AIM OF RESEARCH 14

1.4 OBJECTIVES OF THE RESEARCH 14

1.5 JUSTIFICATION OF THE RESEARCH 15

1.6 SCOPE OF THE RESEARCH 15

1.7 EXPECTED CONTRIBUTION TO KNOWLEDGE 15

CHAPTER TWO

5
2.0 LITERATURE REVIEW 17

2.1 INTRODUCTION TO NANOTECHNOLOGY 18

2.2 ENVIROMENTAL ENGINEERING 20

2.3 ENGINEERING MATERIALS 26

2.3.1 CARBON STEEL 26

2.3.1.1 Properties of Carbon Steel

2.3.1.2 Application of Carbon Steel

2.4 CORROSION INHIBITION 30

2.4.1 Type of Corrosion inhibitor

CHAPTER THREE

3. MATERIALS AND METHODS 41

3.1 MATERIALS 41

3.2 EQUIPMENT USED 42

3.3 METHOD 42

3.3.1 Extraction from the selected plant

3.3.2 Synthesis of the Nanoparticles

3.3.3 Characterisation of the Nano-silver

3.3.4 Preparation of the corrosion sample

3.3.5 Testing for the corrosion inhibitive properties of the Nano-silver

6
CHAPTER FOUR

4. 0 RESULTS AND DISCUSSION 48

4.1 RESULTS

4.1.1 Compositional Characterization of Material Used

4.1.2 Scanning Electron Microscope of the Nano-silver

4.1.3 Corrosion inhibition properties of Nano-silver

4.2 DISCUSSION

4.2.1 Compositional Characterization

4.2.2 Scanning Electron Microscope (SEM)

CHAPTER FIVE

5.0 CONCLUSION ANE RECOMMENDATION 53

5.1 CONCLUSION 53

5.2 RECOMMENDATION 53

REFERENCES 54

LIST OF FIGURES

7
FIGURE 2. 1................................................................................................................................. 26

FIGURE 3.8……………………………………………………………………………………………… 44

FIGURE 3.9……………………………………………………………………………………………… 45

FIGURE 4.1……………………………………………………………………………………………….46

FIGURE 4.2……………………………………………………………………………………………… 47

FIGURE 4.2.1……………………………………………………………………………………………..48

FIGURE 4.2.2……………………………………………………………………………………………..49

FIGURE 4.2.3……………………………………………………………………………………………. 50

LIST OF PLATES

8
Plate 2. 1 Silver nitrate (AgNO3) .............................................................................................................. 31

Plate 2. 2 Aloe Vera Plant ......................................................................................................................... 32

Plate 3. 1 Finely cut Aloe Vera plant ........................................................................................................ 40

Plate 3. 2 Extract of Aloe Vera ................................................................................................................ 40

Plate 3. 3 The mixture of the Aloe Vera extract and silver nitrate .......................................................... 41

Plate 3. 4 (b) Dried Silver Nanoparticles ................................................................................................. 41

Plate 3. 5 Aqueous Silver Nanoparticle ................................................................................................... 41

PLATE 3. 6 Mounted mild steel specimen ............................................................................................... 43

9
 CHAPTER ONE

1.0 INTRODUCTION

Corrosion is the breakdown of metal due to chemical attack or interaction with its environment.

It's a never-ending problem that's difficult to entirely eradicate. It would be impractical and

difficult to eradicate the disease completely. Following the disruption of the protective barrier,

corrosion occurs quickly and is accompanied by a number of reactions that alter the composition

and properties of both the metal surface and the surrounding environment, such as the formation

of oxides, local pH changes, electrochemical potential, and metal cation diffusion into the

coating matrix. Carbon steel and iron corrosion is a topic of significant theoretical and practical

importance, and it has gotten a lot of attention as a result. Corrosion inhibitors must be added to

acid solutions used in industrial acid cleaning, acid descaling, acid pickling, and oil well

acidizing to prevent metal corrosion.

Corrosion is one of the most important problems confronting the metallurgical industry.

Corrosion is the degradation of a material's properties due to interactions with its environment.

(Omotayo Adewuyi, 2018) Efforts have been made to limit the impacts of corrosion to a bare

minimum, one of which involves the use of nanoparticles (Nanotechnology). Nanotechnology is

essentially engineering on a smaller scale. Nanoparticles are minuscule objects that, in terms of

mobility and properties, behave as a single unit. The impacts of nanoparticles on the corrosion

behavior of carbon steel in an acidic solution are the subject of this investigation. The chosen

plant for this research is Aloe Vera leaves, and the nanoparticle is Silver Nanoparticle.

Silver nanoparticles (AgNPs) are a type of substance with a size range of 1 to 100 nanometers.

Because of their unique and appealing physical, chemical, and biological features, there has

recently been a surge in interest in studying AgNPs and their diverse behaviors. Toxicity, surface

10
plasmon resonance, and electrical resistance are all recognized to be distinctive features of

AgNPs. On the basis of these findings, extensive research has been carried out to determine their

qualities and possible applications for a variety of reasons, including antimicrobial agents in

wound dressings, anticancer agents, electronic devices, and water treatment. Despite the fact that

AgNPs have toxic qualities that restrict bacterial growth, are harmful to zebra fish and the human

reproductive system, and are lethal to cell-based in vitro systems, they are nonetheless widely

used in commercial items like contraceptives and feminine hygiene products. As a result of these

health concerns, a number of studies recently conducted measurements and reported that various

consumer products emitted high levels of AgNPs into the environment (Elumala Ek, 2010).

AgNPs were discovered to be released into the environment at an average concentration of

11μg/L by washing machines. AgNPs were observed to be released into the environment from

exterior facades during early runoff episodes, with a maximum concentration of 145μg/L,

according to another study. Because the toxicity danger of AgNPs might be noticed near the

vicinity of consumers, particularly in the freshwater ecosystem, the aforementioned events raise

potential environmental and health alarms. Several review papers have been published to

examine the toxicological properties of AgNPs during their use as antimicrobial agents for

textiles, dental biomaterials, and biodetectors, as well as during their synthesis. For example, the

toxicity properties of capped and uncapped AgNPs, such as cytotoxicity and genotoxicity, have

been thoroughly examined. The mechanisms of toxicity upon oral exposure were also thoroughly

examined. Furthermore, a recent evaluation of AgNPs for antibacterial applications focused on

their production utilizing plant extracts. The majority of the aforementioned reviews concentrate

on the synthesis of AgNPs on a small scale. The difficulties that arise during the scaling up of

AgNP synthesis are largely lacking from these articles, despite the fact that this information is

extremely useful for industrial production. As a result, the purpose of this study is to fill that

11
vacuum, starting with their global usage and research trends and on to future challenges such as

environmental issues and scaled-up synthesis procedures. In addition, there is a case study on the

use of AgNPs in Malaysia that has never been published before. (Achmad Syafiuddin, April 20,

2017)

1.1 Background to the Study

Using the potentiodynamic polarization method, Oluwatoyin A. Olaseinde, Olajesu F.

Olarenwaju, and Silifa T. Mohammed et al studied the effect of silver nanoparticles on the

corrosion behavior of Mild steel and 316Austenitic stainless steel in 0.5M H2SO4. The

nanoparticles were made with Silver Nitrate (AgNO3) from sweet potato (Ipomoea batatas) plant

extracts and studied using Atomic Adsorption Spectroscopy, Fourier Transform Infrared

Spectroscopy, and Ultraviolet Visible Spectroscopy. The AAS findings revealed that the plant

extract is environmentally friendly because it is free of heavy metals. Alcohol O-H, Nitrile CN,

Alkyne CC, AlkeneC=C, and Benzene Ring C=C were the distinct functional groups found in

the extracts taken from different regions of the plant, according to the FTIR data. The UV-Vis

results revealed the presence of phenolic compounds, which helped to restrict the growth of the

bacteria. The potentiodynamic polarization results revealed that the nanoparticle derived from

the leaf has the highest corrosion inhibition effectiveness, and that the corrosion inhibition

efficiency improves as the inhibitor concentration increases. (Olaseinde, olarenwaju, &

Mohammed, 4, April 2019 )

Because of their strong ability to create self-assembled films on metal surfaces, nanometer sized

materials have sparked a lot of attention as corrosion protective films. The increased reactivity of

silver nanoparticles in aqueous acidic solution is widely recognized. The goal of this research is

to create coated silver nanoparticles that will protect carbon steel alloys from corrosive aqueous

12
acidic conditions. In this case, Ag nanoparticles colloid solutions were made by reducing

AgNO3 in an aqueous solution independently with trisodium citrate or in the presence of

stabilizers such poly(ethylene glycol)thiol and poly(vinyl pyrrolidone). TEM and DLS were used

to examine the morphology of the modified silver nanoparticles. The effect of HCl on the

stability of disseminated silver nanoparticles was investigated using the UV-Vis absorption

spectrum. Using the polarization method and electrochemical impedance spectroscopy, the

corrosion inhibition efficiency of the poly (ethylene glycol) thiol, the self-assembled monolayer

of Ag nanoparticles, was evaluated (EIS). The coated silver poly (ethylene glycol) thiol worked

as a mixed type inhibitor, according to polarization curves. The inhibitory efficiencies reported

through polarization measurements correlate well with those obtained through electrochemical

impedance studies. The rising popularity of AgNP research in recent decades is clear, as seen by

the number of linked publications that utilize the term "silver nanoparticle" as a keyword. It is

obvious evidence that studies on AgNPs are interesting and are still being studied today. In the

first two decades of the twentieth century, research on AgNPs was primarily focused on

chemical methods for producing and characterizing them. Physical and biological treatments

were also suggested because they are both safe and environmentally friendly. Many recent

studies have focused on biological techniques and applications for a variety of goals. The

primary topic area of AgNPs is materials science. Furthermore, the Journal of Nanoparticle

Research has published more articles about AgNPs than any other publication.

Iron is widely utilized in industrial production and many other fields due to its unique features

(high thermal and electrical conductivity, malleability, ductility, and so on), making study into

corrosion and protection of iron and its alloys critical. Self-assembled materials are superior

anticorrosion materials for iron (SAMs). The stable SAMs that develop can prevent corrosive

ions from reaching the metal surface and effectively shield it from corrosion. SAMs are made

13
from a variety of compounds that act as corrosion inhibitors on copper and iron. Shimura and

Aramaki were successful in protecting iron from corrosion by using ultrathin films to cover it.

Feng and his colleagues looked at using a self-assembly process to improve the iron's resistance

to corrosion in the environment. Because of their unique chemical and physical features,

significant efforts have been concentrated on the manufacture of Ag nanoparticles in recent

years. For the synthesis of metal nanoparticles, a variety of processes are currently available,

including gas reduction, precursor pyrolysis, microwave plasma synthesis, hydrodynamic

cavitations and liquid chemical reduction, and laser ablation. However, it was challenging to

synthesize well-dispersed and active Ag nanoparticles, partly because surfactant molecules were

ineffectively adsorbed on the surface of nanoparticles, resulting in agglomeration and oxidation

tendency. The dispersion of Ag nanoparticles can be regulated in the presence of modified

organic compounds based on polymer and thiol derivatives, according to earlier research.

Organic molecules containing heteroatoms (e.g., N, O, and S atoms) could, on the other hand, be

utilized as a stabilizer for Ag nanoparticles. In this regard, the goal of this research is to produce

well distributed and stable Ag nanoparticles in both aqueous and acidic conditions. In the

presence of silver nanoparticles modified with poly (ethylene thiol) aqueous acidic solutions, the

corrosion inhibition effciency of iron was determined using polarization.

Statement of Problem

Corrosion poses lots of threats, majorly which are;

 Reduction in properties of metals

 Devaluation of metals

 Negative impact on growth of metallurgical industry

14
  Threat against technological advancement

 High cost of maintenance. NACE study estimates global cost of corrosion at $2.5 trillion

annually (NACE, 2016).

1.2 AIMS AND OBJECTIVES

The aim of this project is to study and understand the effects of silver nanoparticles at various

loading weight when used as a corrosion inhibitor on the corrosion behaviour of carbon steel in

1M of HCL.

Objectives of the research include;

i. Production of plant extract and biosynthesis of silver nanoparticles.

ii. Investigate the corrosion behavior of the steel samples in varying concentration of

selected nanoparticles (silver nanoparticles) in 1M of HCL.

1.4 Research Justification

There are organic and inorganic compounds which can inhibit corrosion. Though many synthetic

compounds show good anti-corrosive activity but they are highly toxic to human beings and the

environment. This has resulted in the development of other efficient and environmentally

acceptable inhibitors. And nanoparticles are eco-friendly and nontoxic to living things in our

environment.

1.5 SCOPE OF STUDY

This study is limited to the effects of selected nanoparticles (silver nanoparticles) at varying

concentrations in 1M of HCL on carbon steel using the polarization method. The surface

examination and investigations of the mild steels are carried out using scanning electron

15
microscopy (SEM) and the crystal phase analysis of the nanoparticles are conducted using XRD

(X-ray Diffraction).

1.6 EXPECTED CONTRIBUTION TO KNOWLEDGE

The project work

i. Prove the effects of selected nanoparticles (silver nanoparticles) as organic inhibitors in

simulated environments and to the surface of steel samples in acidic environment as good

corrosion inhibitor. It also promote the use of nanoparticles, thereby enlighten the

populace about nanotechnology.

16
 CHAPTER TWO

2.0 LITERATURE REVIEW

Our environment is undergoing massive destruction as a result of rapid industrialization and

urbanization, with a large amount of hazardous and unnecessary chemical, gases, or substances

released. As a result, we now have a need to learn about the secrets that are present in Nature and

its products, which leads to the growth of advancements in the synthesis of nanoparticles. The

biological molecules are assembled in a highly regulated manner to make them ideal for the

production of metal nanoparticles, which has been found to be both reliable and environmentally

acceptable. Due to its potential uses in the creation of breakthrough technologies, the synthesis of

metal and semiconductor nanoparticles is a broad area of research. Nanoparticles have

completely new or better properties, such as particle size, dispersion, and shape, among others.

(PANIGRAHI, 2013)

Silver nanoparticles (AgNPs) are a type of substance with a size range of 1 to 100 nanometers.

Because of their unique and appealing physical, chemical, and biological features, there has

recently been a surge in interest in studying AgNPs and their diverse behaviors. Toxicity, surface

Plasmon resonance, and electrical resistance are all recognized to be distinctive features of

AgNPs. On the basis of these findings, extensive research has been carried out to determine their

qualities and possible applications for a variety of reasons, including antimicrobial agents in

wound dressings, anticancer agents, electronic devices, and water treatment. Despite the fact that

AgNPs have toxic qualities that suppress bacterial growth, are harmful to zebra fish and the

human reproductive system, and are fatal to cell-based in vitro systems, they are nonetheless

widely used in commercial items like contraceptives and feminine hygiene products. As a result

of these health concerns, a number of studies recently conducted measurements and reported that

17
various consumer products emitted high levels of AgNPs into the environment. AgNPs were

discovered to be released into the environment at an average concentration of 11g/L by washing

machines. AgNPs were observed to be released into the environment from exterior facades

during early runoff episodes, with a maximum concentration of 145g/L, according to another

study. Because the toxicity danger of AgNPs might be noticed near the vicinity of consumers,

particularly in the freshwater ecosystem, the aforementioned events raise potential environmental

and health alarms. Several review papers have been published to examine the toxicological

properties of AgNPs during their use as antimicrobial agents for textiles, dental biomaterials, and

bio-detectors, as well as during their synthesis. For example, the toxicity properties of capped

and uncapped AgNPs, such as cytotoxicity and geno-toxicity, have been thoroughly examined.

The mechanisms of toxicity upon oral exposure were also thoroughly examined. Furthermore, a

recent evaluation of AgNPs for antibacterial applications focused on their production utilizing

plant extracts. The majority of the aforementioned reviews concentrate on the synthesis of

AgNPs on a small scale. (Achmad Syafiuddin, April 20, 2017). Mild steel is utilized as a

structural material for vessels, reactors, pipes, and tanks, among other things, because it is known

to corrode when exposed to various solvents. From the standpoint of the nation's economy and

the financial consequences of corrosion, it is vital to implement appropriate means and methods

to prevent corrosion-related losses. Corrosion and prevention in acidic/alkaline aqueous

environments have been thoroughly investigated, however there are few data available for non-

aqueous solvents. (Sutiana Junaedi, Abdul Amir H. Kadhum, Ahmed A. Al-Amiery, Abu Bakar

Mohamad, Mohd Sobri Takriff, 1 April 2012).

2.1 INTRODUCTION TO NANOTECHNOLOGY

Nanotechnology is a new scientific subject. While there are no commonly accepted definitions,

nano is defined as having a dimension of 10-9 and nanotechnology is the technology linked with

18
it. Nanotechnology is defined as the near-atomic manipulation of matter to create new structures,

materials, systems, catalysts, and devices that display novel phenomena and features.

Nanotechnology is one of the most rapidly developing research topics. Nanotechnology is one of

the most rapidly developing branches of science. It will affect every aspect of life, including

medical, construction, and electronics, to name a few. It allows for the introduction of more

efficient and environmentally friendly technology. Nanotechnology is also used in the field of

electrical power engineering. Although the combination of nanotechnology and power

engineering may appear to be incompatible, it will improve the electrical, mechanical, thermal,

and chemical qualities of electric equipment. There are also a number of potential uses in high-

voltage electrical engineering.

Nanotechnology is defined as the ‘‘creation, processing, characterization, and use of materials,

devices, and systems with dimensions on the order of 0.1–100 nm, exhibiting novel and

significantly enhanced physical, chemical, and biological properties, functions, phenomena, and

processes due to their Nano-scale size" (American Ceramic society 2004). The most important

aspect of nanotechnology is the wide spectrum of new and better features that can only be

discovered and accessed through the ability to examine, regulate, and manipulate size.

Nanotechnology's essence is derived from the application of these new and better features in

economically and technologically viable ways. Nano-biotechnology, Nano-systems, Nano-

electronics, and Nano-structured materials are all hot topics in nanotechnology right now, and

nanocomposites are a big part of it. Nano-structured materials are expected to be developed

utilizing a bottom-up strategy using nanotechnology. The successful implementation of the

‘‘bottom-up" method in composites processing is exemplified by the integrated approach utilized

in composites processing. (Erik et al.,2004).

19
2.1.1 NANOPARTICLES:

A particle with a size in the range of 1nm - 100nm in at least one of the three dimensions is

referred to as a "nanoparticle." The physical, chemical, and biological properties of nanoparticles

in this size range differ significantly from the properties of individual atoms/molecules and bulk

materials. Nanoparticles can be created from a variety of chemical components, the most

frequent of which include metals, metal oxides, silicates, non-oxide ceramics, polymers,

organics, carbon, and biomolecules. Nanoparticles come in a variety of shapes and sizes,

including spheres, cylinders, platelets, tubes, and more. In general, nanoparticles are developed

with surface alterations that are customized to the needs of the individual applications for which

they will be utilized. The enormous variety of nanoparticles resulting from their wide chemical

nature, shape and morphologies, the medium in which the particles are present, the state of

dispersion of the particles, and, most importantly, the numerous possible surface modifications to

which nanoparticles can be subjected make this an active field of science.

2.1.2 TYPES OF NANOPARTICLES:

Nanoparticle is grouped into two,

1. Organic nanoparticles

2. Inorganic nanoparticles

Organic nanoparticles, such as carbon nanoparticles (fullerenes), and inorganic nanoparticles,

such as magnetic nanoparticles, noble metal nanoparticles (such as gold and silver), and

semiconductor nanoparticles, are two types of nanoparticles that can be generally classified (like

titanium oxide and zinc oxide). Inorganic nanoparticles, such as noble metal nanoparticles (gold

and silver), are gaining popularity because they have better material qualities and can be used in

a variety of applications. Inorganic particles have been investigated as prospective tools for

medical imaging as well as disease treatment due to their size properties and benefits over

20
available chemical imaging pharmacological agents and medications. Because of their various

qualities such as wide availability, rich functionality, high compatibility, and the capacity of

targeted drug delivery and controlled drug release, inorganic non-materials have been widely

used for cellular delivery.

2.1.3 SILVER NANOPARTICLES:

Silver nanoparticles are appealing due to their unique properties (e.g., size and shape-dependent

optical, electrical, and magnetic properties) that can be used in antimicrobial applications,

biosensor materials, composite fibers, cryogenic superconducting materials, cosmetics, and

electronic components. Synthesizing and stabilizing silver nanoparticles has been accomplished

using a variety of physical and chemical processes. For the manufacture of silver nanoparticles,

the most common chemical methods include chemical reduction utilizing a variety of organic

and inorganic reducing agents, electrochemical procedures, physicochemical reduction, and

radiolysis. Nanoparticle synthesis has recently emerged as one of the most fascinating scientific

fields, with an increasing focus on producing nanoparticles using environmentally benign

methods (green chemistry). Mixed-valence polyoxometalates, polysaccharides, Tollens,

biological, and irradiation processes are examples of green synthesis approaches that have

advantages over traditional methods that use chemical agents that are detrimental to the

environment. This chapter provides an overview of silver nanoparticle manufacturing methods,

including physical, chemical, and green synthesis. The purpose of this chapter is to reflect on the

existing condition and future prospects of the above-mentioned methodologies for industries,

particularly their potentials and limitations. Furthermore, we cover the uses of silver

nanoparticles and their incorporation into other materials, as well as the molecular elements of

silver nanoparticle antibacterial properties.

21
2.1.4 METHODS FOR NANOPARTICLE SYNTHESIS:

Physical approaches: Evaporation-condensation and laser ablation are two of the most

important physical techniques. The evaporation-condensation process has previously been used

to produce metal nanoparticles such as silver, gold, lead sulfide, cadmium sulfide, and fullerene.

Physical techniques provide several advantages over chemical processes, including the absence

of solvent contamination in the created thin films and the homogeneity of nanoparticle

dispersion. Silver nanoparticles might be manufactured using a small ceramic heater with a local

heating source, according to the researchers. Because the temperature gradient in the region of

the heater surface is extremely steep in compared to that of a tube furnace, the evaporated vapor

can cool at a suitable rapid rate. Small nanoparticles can be formed at high concentrations as a

result of this. This physical approach can be used as a nanoparticle generator for long-term

inhalation toxicity investigations and as a calibration device for nanoparticle measurement

equipment. Laser ablation of metallic bulk materials in solution could be used to make silver

nanoparticles. Many factors influence the ablation efficiency and characteristics of produced

nano-silver particles, including the wavelength of the laser impinging on the metallic target, the

duration of laser pulses (in the femto, Pico, and nanosecond regimes), the laser fluence, the

ablation time duration, and the effective liquid medium, with or without tweezers. The absence

of chemical reagents in solutions is a significant benefit of laser ablation approach compared to

other ways for producing metal colloids. As a result, this process can be used to create pure and

uncontaminated metal colloids for future uses.

Chemical approaches: Chemical reduction with organic and inorganic reducing agents is the

most frequent method for producing silver nanoparticles. For the reduction of silver ions (Ag+)

in aqueous or non-aqueous solutions, several reducing agents such as sodium citrate, ascorbate,

sodium borohydride (NaBH4), elemental hydrogen, polyol process, Tollens reagent, N, N-

22
dimethylformamide (DMF), and poly (ethylene glycol)block copolymers are utilized. The

reducing agents indicated above decrease silver ions (Ag+), resulting in the creation of metallic

silver (Ag0), which is then agglomerated into oligomeric clusters. The production of metallic

colloidal silver particles occurs as a result of these clusters. During the preparation of metal

nanoparticles, it is critical to utilize protective agents to stabilize dispersive nanoparticles and

safeguard nanoparticles that can absorb on or adhere to nanoparticle surfaces, preventing

agglomeration. Surfactants having functionalities (e.g., thiols, amines, acids, and alcohols) for

interactions with particle surfaces can help to stabilize particle development and prevent

sedimentation, agglomeration, and loss of surface characteristics. The Tollens method, a simple

one-step process, has recently been used to synthesize silver nanoparticles with a regulated size.

Silver ions are reduced by saccharides in the presence of ammonia in the modified Tollens

technique, giving silver nanoparticle films (50-200 nm), silver hydrosols (20-50 nm), and silver

nanoparticles of various shapes.

Biological approaches: The development of effective green chemistry methods that use natural

reducing, capping, and stabilizing chemicals to make silver nanoparticles with desired

morphology and size has become a key focus of researchers in recent years. Without the use of

harsh, poisonous, and expensive chemical chemicals, biological approaches can be employed to

produce silver nanoparticles. Environmentally benign, although chemically complex, bio-

reduction of metal ions by combinations of biomolecules found in extracts of certain animals

(e.g., enzymes/proteins, amino acids, polysaccharides, and vitamins). Many studies have shown

that organisms can successfully synthesize silver nanoparticles (microorganisms and biological

systems).

Synthesis of silver nanoparticles by plants: The main benefit of employing plant extracts

for silver nanoparticle production is that they are readily available, harmless, and nontoxic in

23
most situations, contain a wide range of metabolites that can aid in the reduction of silver ions,

and are faster in the synthesis than microorganisms. Plant-assisted reduction owing to

phytochemicals is the key mechanism suggested for the procedure. Terpenoids, flavones,

ketones, aldehydes, amides, and carboxylic acids are the primary phytochemicals involved.

Water-soluble phytochemicals such as flavones, organic acids, and quinones are responsible for

the rapid decrease of ions. Xerophytes contain emodin0, an anthraquinone that tautomerizes to

generate silver nanoparticles, according to research. Cyperoquinone, dietchequinone, and remirin

were discovered to be present in mesophytes. It's been proposed that phytochemicals are directly

engaged in ion reduction and silver nanoparticle production.

NEED FOR GREEN SYNTHESIS: Biosynthesis of nanoparticles is a type of bottom-up

technique in which reduction/oxidation is the primary process. The necessity for biosynthesis of

nanoparticles grew as physical and chemical methods became more expensive. Chemical

synthesis methods frequently result in the presence of harmful chemicals absorbed on the

surface, which might have negative consequences in medical applications. When it comes to

biosynthesized nanoparticles made by the green synthesis process, this is not a concern. In order

to find less expensive ways to make nanoparticles, scientists turned to microbial enzymes and

plant extracts (phytochemicals). They are usually responsible for the reduction of metal

compounds into their respective nanoparticles due to their antioxidant or reducing capabilities.

Green synthesis has advantages over chemical and physical synthesis in that it is less expensive,

more environmentally friendly, and easier to scale up for large-scale synthesis because it does

not require the use of high pressure, energy, temperature, or harmful chemicals.

SILVER NANOPARTICLES: Because of their unique properties and vast variety of uses,

silver nanoparticles (AgNPs) have been widely studied for many years. Catalysis, bio-sensing,

and imaging antimicrobial activity are all examples of this. (Patcharaporn Tippayawat,

24
Nutthakritta Phromviyo, Parichart Boueroy and Apiwat Chompoosor, 29 October 2016, p. 12)

and corrosion inhibition.

WHY SILVER?

Silver is one of the most fundamental elements that make up our world. It is a rare but naturally

occurring element with a hardness of somewhat less than gold and a ductile and malleable

nature. All metals have the maximum electrical and thermal conductivity, while pure silver has

the lowest contact resistance. Ag0, Ag2+, and Ag3+ are the four oxidation states in which silver

can exist. The former two are the most common, whereas the latter is insecure in the watery

environment. Metallic silver is insoluble in water, however metallic compounds like AgNO3 and

Silver chloride are soluble. Metallic silver is utilized in surgical prostheses and splints, as well as

in fungicides and coinage. Mental illness, epilepsy, nicotine addiction, gastroenteritis, and

infectious disorders like as syphilis and gonorrhea have all been treated with soluble silver

compounds like silver slats. Although the availability of free silver ions determines the acute

toxicity of silver in the environment, investigations have revealed that these concentrations of

Ag+ ions are too low to cause toxicity. Metallic silver appears to offer little damage to health,

whereas soluble silver compounds are more easily absorbed and can cause harm. Because of the

wide range of applications for silver, it can be ingested via a multitude of methods. Silver

compounds and colloidal silver proteins are mostly absorbed through the gastrointestinal tract.

Silver intake is predicted to be 7090μg per day in the diet. Silver is relatively non-toxic since it is

not thought to be hazardous to the immune, cardiovascular, neurological, or reproductive

systems, and it is not expected to be carcinogenic. Silver demand is expected to rise as the metal

finds new applications, particularly in the textile, plastics, and medical industries, resulting in a

shift in silver emission patterns as these technologies and products spread throughout the global

economy.

25
2.3 ENGINEERING MATERIAL

According to William D. Callister, Jr. materials used in field of engineering are divided majorly

to into three which are: (William D. Callister, 2007)

FIGURE 2.1

Plastics: These include the familiar plastics and rubber materials. Many of them are organic

compounds that are chemically based on carbon, hydrogen, and other non-metallic element.

They have large molecular structures, often chain like in nature that have a backbone of carbon

atoms. Common examples are polyethylene, polystyrene, nylon, polyvinyl chloride, poly

carbonate, silicone rubber.

Characteristics of polymer

i.) Low stiffness and strength

ii.) Low density

iii.) High ductility

iv.) Bad conductor of heat and electricity

v.) High formability

vi.) Low melting point

vii.) Good insulators

26
Ceramics: These are compounds between metallic and non-metallic elements. They are most

frequently oxides, nitrides, and carbides. Examples, alumina, silica, silicon carbides, silicon

nitrides, and other traditional ceramics such as clay, cement and glass.

Characteristics of ceramics

i.) Very hard

ii.) High susceptibility to fracture

iii.) Extremely brittle

iv.) Relative high stiffness and strength compare to metals

v.) Good Insulator

vi.) Low thermal and electrical conductivity

vii.) High refractoriness.

Metals: These are materials that are composed of one or more metallic elements (such as iron,

aluminum, copper, titanium, gold, and nickel) and often nonmetallic elements (for example

carbon, nitrogen and oxygen.) in relatively small contents. Atoms in metals are arrange in very

orderly manner and relatively dense in comparing with ceramics and polymer. Metals are

applicable in most materials both industrial and domestic uses, and the properties of metals are

enhance and increased by alloying the metals with other materials, taking iron (Fe) which have

the highest usage as at now.

Iron: Iron occur in nature as hematite and magnetite and major impurities are sulphur,

phosphorous and silicon with other metal in little percentage, in the process of extraction of iron,

calcium carbonate is use as the reducing compound by providing carbon monoxide. In most case

iron of found to contain little percentage of carbon. And the alloy is name steel because of the

presence of carbon in the iron.

Carbon Steel

27
Steel is considered to be a carbon steel when the minimum content of the alloying metals

(chromium, cobalt, molybdenum, nickel, niobium, titanium, tungsten, vanadium or zirconium, or

any other element to be added to obtain a desired alloying effect) are not specified or required.

Effect of carbon on the steel

1. The higher the carbon content the stronger and harder the steel becomes

2. Increase in carbon content lead to decrease in ductility of the steel

3. Increase in the carbon content leads to reduction in weldability of the steel

4. The carbon content also lead lowering of the melting point

Properties of carbon steel

a) Increased hardness

b) High strength

c) Lower ductility

d) Lower melting point

e) Reduces weldability

Application of carbon steel

1. Structural construction such as, bridges, buildings and monumental

2. Piping in oil and gas industry

3. Domestic utensils

4. Fabrication of trusses

2.4 CORROSION INHIBITORS

For millennia, the approach of metal corrosion prevention based on the employment of corrosion

inhibitors, i.e. chemical substances that, when present in a system at suitable concentrations,

reduce the rate of corrosion, has been known (ISO, 1989). However, it wasn't until the middle of

28
the twentieth century that a scientific understanding of inhibition was formed, as well as the first

accomplishments in the direct synthesis of inhibitors (Kuznetsov, 2004). Corrosion inhibitors are

utilized in a variety of systems, including water supply systems, microelectronics protection, and

modern military equipment. Given that metal corrosion losses in industrial countries surpass 5%

of GDP, the use of inhibitors, which is one of the most common techniques of corrosion

protection, should be considered a scientific and engineering task of current importance

(Kuznetsov, 2004).

2.4.1 CLASSES OF INHIBITORS

Chemicals can be used as corrosion inhibitors. Synthetic or natural, and thus classed as follows:

 Chemical nature as organic or inorganic

 Mechanism of action as anodic, cathodic, or an anodic-cathodic mix, and by adsorption

action

 As oxidants or not oxidants (C., F, & Alexandre, 2014)

2.4.2 MECHANISM OF INHIBITION

It is vital to understand the inhibition mechanism when creating an organic inhibitor system.

Organic molecules are thought to inhibit corrosion at the metal/solution interface by adsorption,

with the amount of adsorption varying depending on the chemical structure of molecules, the

chemical composition of solutions, the nature of the metal surface, the temperature, and the

electrochemical potential at the metal/solution interface. Many organic and inorganic inhibitors

have become effective by interaction with many corrosion products to generate a new protective

phase rather than absorption on the metal surface, according to evidence provided in recent

years. Inhibitors protect cells from acid damage by forming one or more molecular barriers. This

protective effect is frequently linked to chemical and/or physical adsorption, which involves a

29
charge variation in the adsorbed substance and charge transfer from one phase to the other. The

chemical structure and physicochemical properties of an organic inhibitor, such as functional

groups, electron density at the donor atom, p-orbital character, and the electronic structure of the

molecule, are related to the performance of an organic inhibitor, according to Amitha and

Bharathi (2012).

Corrosion inhibition usually results from one or more of three general mechanisms:

1. The inhibitor molecule is adsorbed on the metal surface by the process of chemisorption,

forming a thin protective film either by itself or in conjunction with metallic ions.

2. The inhibitor causes a metal to form its own protective film of metal oxides, thereby

increasing its resistance.

3. The inhibitor reacts with a potentially corrosive substance in the water.

In summary, Adsorption can be:

1. Physisorption due to electrostatic attractive force between the inhibiting ions or dipoles

and the electrically charged metal surface.

2. Chemisorption caused by the interaction between unshared electron pairs or electrons

with metals to form a coordinate type of bond. Chemisorption takes place when there are

heteroatom such as P, Se, S, N and O present with lone pair electrons and/or aromatic

rings in the adsorbed molecules.

3. A combination of the above factors.

This is without prejudice to a publication by Kirk (1989) which classified adsorption into

electrostatic, chemisorption, and ᴫ-bond (delocalized electron) types.

When choosing the corrosion inhibitor for your application, several things need to be considered,

as follows:
30
 1. Materials to be protected

2. Method of application (dip, spray, brush, etc.)

3. Type of protection required (in process, storage or shipping)

4. Type and thickness of coating residue desired

5. Storage, packaging and/or shipping conditions (temperature, humidity seasonal

conditions)

6. Interaction with subsequent processes, if not removed

7. Environmental, health and safety requirements

8. Type of product (oil/solvent or water-based.

2.4.3 BACKGROUND INFORMATION ON INHIBITOR SUSBTANCE

2.4.3.1 Silver Nitrate (AgNO3)

Silver nitrate is an inorganic compound with chemical formula AgNO3. This compound is a

versatile precursor to many other silver compounds, such as those used in photography. It is far

less sensitive to light than the halides. It was also known as the stone of hell because it is very

corrosive. Silver nitrate has a molecular weight of 169.872 g/mol. The structure for silver nitrate

is:

Plate 2. 1 Silver nitrate (AgNO3)

31
2.4.3.2 ALOE VERA

Aloe vera is a natural product that is now widely used in the cosmetics industry. There are a

variety of indications for its use. For generations, the Aloe vera plant has been known and used

for its health, cosmetic, medical, and skin care benefits. The name Aloe Vera comes from the

Arabic word "Alloeh," which means "shining bitter substance," and "Vera," which means "truth"

in Latin. Aloe vera was regarded as the universal panacea by Greek scientists 2000 years ago.

Vitamins, enzymes, minerals, carbohydrates, lignin, saponins, salicylic acid, and amino acids

were revealed as potentially active ingredients as a result of these findings.

Plate 2. 2 Aloe Vera Plant

Within the Aloe Vera there are:

1. Vitamins: It contains vitamins A (beta-carotene),C and E, which are antioxidants. It also

contain vitamin B12, folic acid, and choline. Antioxidant neutralizes free radicals.

2. Enzymes: It contains 8 enzymes: aliiase, alkaline phosphatase, amylase, bradykinase,

carboxypeptidase, catalase, cellulase, lipase, and peroxidase.

3. Minerals: It provides calcium, chromium, copper, selenium, magnesium, manganese,

potassium, sodium and zinc.

32
 4. Sugars: It provides monosaccharides (glucose and fructose) and polysaccharides:

(glucomannans/polymannose).These are derived from the mucilage layer of the plant and

are known as mucopolysaccharides.

5. Anthraquinones: It provides 12 anthraquinones, which are phenolic compounds

traditionally known as laxatives. Aloin and emodin act as analgesics,

antibacterial and antivirals.

6. Fatty acids: It provides 4 plant steroids; Cholesterol, campesterol, β­sisosterol and lupeol.

7. Hormones: Auxins and gibberellins that help in wound healing and have anti-inflammato

ry action.

8. Others: It provides 20 of the 22 human required amino acids and 7 of the 8 essential amin

o acids. Though Aloe Vera has wide spectrum of properties and uses. (Surjushe et al.,

2007)

Gel is found in Aloe Vera leaves, and this gel has inhibitory characteristics. Weight loss, EIS,

and Tafel polarization were used to investigate the influence of Aloe Vera gel on mild steel

corrosion in 1M HCl media. Atomic force microscopy (AFM) and scanning electron microscopy

(SEM) were used to supplement the findings (SEM). Both physisorption and chemisorption

adsorbed the inhibitor, according to the activation conditions. At an optimum dosage of 200ppm,

the inhibitor showed >90% inhibition efficiency and the lowest corrosion rate (Singh and Pani

2016).

2.4.4 CORROSION MEASUREMENT TECHNIQUES

The application of various methodologies to determine the corrosiveness of the environment and

the rate of metal loss is known as corrosion measurement. Corrosion measurement is a way of

evaluating the performance and effectiveness of corrosion control and preventive strategies that

is usually quantitative. Following the completion of the evaluation, the feedback gained is used

33
to develop and enhance the techniques. Corrosion is measured using a variety of methods,

including polarization curves, linear polarization resistance, open circuit potential decay, ac

impedance measurement, electrochemical noise measurement, and weight loss measurement, all

of which aid in the analysis and determination of corrosion rates. Electrochemical techniques are

appropriate for studying corrosion processes because corrosion is caused by electrochemical

reactions. (2018, Gamry).

2.4.5 LINEAR POLARIZATION RESISTANCE

Linear polarization resistance (LPR) is a rapid, non-destructive testing method for obtaining

corrosion rate data in material corrosion research. The material is polarized in this manner, often

on the order of 10mV, in relation to its Open Circuit (OC) potential, which is the potential

measured when no [net] current is flowing. When the material's potential (working electrode) is

adjusted, a current is produced to flow between the working and counter electrodes, and the

slope of the potential versus current curve can be used to determine the material's resistance to

polarization. The Stern-Geary equation can then be used to calculate the corrosion rate of the

material using this resistance. Theory behind the Linear Polarization is as follow:

The most common polarization resistance mode is three electrodes. A working electrode (your

material sample), a CE (graphite and platinum are common), and an independent reference

electrode (Saturated Calomel Electrodes (SCE) and Silver/Silver Chloride (Ag/AgCl) are the

most frequent) are used in this configuration. LPR works best in aqueous solutions and has

proven to be a quick response method. This monitoring of the actual corrosion rate provides

operators with near-instant feedback. The main benefit of LPR monitoring is the speed with

which it can deliver a corrosion rate measurement. LPR monitoring can also reveal metal

34
behavior, such as when an alloy transitions from a passive to an active state, resulting in

increased corrosion susceptibility (Robert et al., 2003).

For electrochemical experiments, a potentiostat is commonly employed. It is usually attached to

three electrodes before being connected to a computer that contains the necessary software.

When started automatically, the Potentiostat changes the potential at a constant pace between

two preset potentials, causing current to flow through the cell. The provided current passes

through the counter electrode and into the working electrode. The working electrode's potential

is thus measured in relation to the reference electrode. The computer is in charge of logging the

potential and current data.

2.4.6 ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY

Electrochemical Impedance Spectroscopy (EIS) is a frequency domain measurement that is

performed by perturbing a system with a sinusoidal disturbance, usually a voltage. Processes

happening on timelines of the inverse frequency (e.g., f=10 Hz, t=0.1 s) are connected to

impedance at a certain frequency. Many other electrochemical tests, such as cyclic voltammetry

and chronoamperometry, focus on driving a system far from equilibrium with potential sweeps

or steps, whereas EIS uses minor perturbations. The frequency analysis is substantially

simplified because these minor deviations from equilibrium are believed to have a linear

response; however, linearization of physical models might lead to indistinguishable situations. In

practice, EIS is accomplished by sweeping through a wide frequency range with a single

perturbation amplitude. Instrumentation has developed over the previous several decades,

allowing researchers to analyze both fast kinetic and sluggish transport processes at frequencies

ranging from 10-4 to 108 Hz (Bard and Faulkner 2001).

35
Impedance is the resistance of an electrical system to the flow of electric current, and it is

measured in Ohms, Ω. It reduces to resistance under the following conditions:

1. There is no phase shift in current under an applied potential, and vice versa

2. All potentials and currents can be used (i.e. there is no saturation potential)

3. The impedance is not a function of frequency (Gamry 2017)

Under these conditions, the well-known Ohm’s Law applies:

V=IR or R = V/I ……………………………………………………………..(EQU 2.1)

Where V is the voltage in V, I is the current in A, and R is the resistance in Ω. However, in EIS

both V and I are time dependent, sinusoidal functions. A single frequency potential input with

amplitude, Vo, and radial frequency, ω, can be expressed as:

𝑉 (𝑡) = 𝑉𝑜cos (𝜔𝑡)………………………………………………………….(EQU 2.2)

Note that EIS data is usually discussed in terms of linear frequency, f, with units of Hz. The

conversion is ω=2πf. In a real system, the current output will have some phase shift, φ, and

anamplitude, Io, expressed as:

𝐼(𝑡) = 𝐼𝑜cos(𝜔𝑡 + 𝜑) …………………………………………………………..(EQU 2.3)

For a generalized expression of impedance, Z, the previously stated conditions for Ohm’s law are

relaxed, and the time-dependent expressions for V and I are substituted into Eq. 1:

Again, we see that if the system exhibits no phase shift (φ=0), Eq. 4 reduces to Ohm’s Law

(Orazem et al., 2008).

36
2.4.7 MATERIAL CHARACTERIZATION

The characterization techniques used in this work include UV Spectroscopy, X-Ray Diffraction

(XRD), Fourier Transform Infra-Red (FTIR), X-Ray Photoelectron Spectroscopy (XRPS),

Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM).

2.4.8 UV SPECTROSCOPY

UV/VIS spectroscopy (ultraviolet-visible spectroscopy) is a technique for determining how much

light is absorbed and scattered by a sample. The extinction is a parameter that is defined as the

sum of the absorbed and scattered light. A sample is positioned between a light source and a

photo-detector, and the intensity of a beam of light is measured before and after passing through

the sample in its most basic form. The wavelength dependent extinction spectrum of the sample

is quantified by comparing these observations at each wavelength. A Shimadzu uv-2203 double

beam spectrophotometer was used to detect UV/VIS absorption spectra. The test was carried out

in order to assess the nanoparticles' absorbance, which helps to identify the peaks where certain

compounds are present. UV Spectroscopy is effective for determining the fundamental

characteristics of produced nanoparticles as well as monitoring the synthesis and stability of

silver nanoparticles. Silver nanoparticles have special optical properties that make them highly

reactive to light of a specific wavelength.

2.4.9 X-RAY DIFFRACTION (XRD)

This is used for the analysis of both molecular and crystal structures, qualitative identification of

various compounds, quantitative resolution of chemical species, measuring the degree of

crystallinity.

2.4.10 FOURIER TRANSFORM INFRA-RED (FTIR)

37
The Fourier Transform Infrared Spectrophotometer (FTIR) is used to determine which active

chemical bonds (functional groups) are present in a molecule. The chemical bond, which is

displayed in a spectrum, determines the wavelength of light absorbed. The chemical bonds in a

molecule can be established by reading the infrared absorption spectrum. The active functional

groups present in the generated plant extracts were detected using FTIR analysis of various

portions of the plant extracts. The FTIR offers precision, repeatability, and a good signal-to-noise

ratio. FTIR allows for the detection of minor absorbance changes on the order of 10-3, which

aids in the performance of difference spectroscopy.

2.4.11 X-RAY PHOTOELECTRON SPECTROSCOPY

To estimate empirical formulae, quantitative spectroscopic surface chemical analysis is used.

2.4.12 SCANNING ELECTRON MICROSCOPY (SEM)/TRANSMISSION ELECTRON

MICROSCOPY (TEM)

SEM is utilized for surface imaging because of its capacity to resolve varied particle sizes,

whereas TEM is used to assess particle and/or grain size quantitatively.

38
 CHAPTER THREE

3.1 MATERIALS AND METHODS

3.1.1 MATERIALS

Materials used during the course of the project are;

1. Carbon Steel

2. Silver Nanoparticles

3. Bath, to contain the simulated environment and solutions of nanoparticles

4. HCL (Acidic) Solution

5. Saturated Calomel Electrode (SCE)

6. Platinum Grid (Counter Electrode)

7. Whatmann Filter Paper

8. Distil Water

9. Silver Nitrate

10. Silver-Silver chloride Electrode

11. Aloe Vera

3.1.2 EQUIPMENT USED

1. Potentiostat/Galvanostat

2. UV via Spectroscopy

3. X-Ray Diffractometer (XRD)

4. Fourier Transform Infra-Red Spectroscopy (FTIR)

5. X-Ray Photoelectron Spectroscopy (XPS)

6. Scan Electron Microscope (SEM)

7. Transmission Electron Microscope (TEM)

39
3.2 METHOD

3.2.1 COLLECTION OF ALOE VERA PLANT

The Aloe Vera plant will be collected from the surrounding preferably a cultivated garden,

washed to remove dust that might be presentand later sun dried to remove residual moisture.

3.2.2 PREPARATION OF ALOE VERA EXTRACT

50g of Aloe Vera leaves that had been rinsed with deionized water are finely cut into small

pieces; the chopped leaves are then boiled in 50ML of deionized water for 20 minutes and then

allowed to cool. The cooled leaf broth is then filtered with Whatmann filter and stored in a

refrigerator at 4ºc; the resulting extract is used as the Aloe Vera extract solution.

Plate 3. 1 Finely cut Aloe Vera plant Plate 3. 2 Extract of Aloe Vera

3.2.3 PREPARATION OF SILVER NANOPARTICLES

0.2 Mol of AgNO3 is first dissolved in 50ml of the Aloe Vera extract solution under vigorous

stirring at room temperature for 30 minutes, the mixture is placed in Teflon lined vessel of 100ml

capacity which is then heated and maintained at various time and temperature conditions. The

mixture is then cooled to room temperature.

40
A grey precipitate is collected by filtration and washed with de-ionized water several times and

finally oven dry.

Plate 3. 3 The mixture of the Aloe Vera extract and silver nitrate and silver nanoparticles

precipitate

The above plate 3.3 is used is the images of the mixture of the aloe vera extract and silver

nanoparticles Precipitate in the Aloe Vera extract, the extract was mixed with the silver nitrate

and stirred then left for some hours to precipitate, it was then filtered and dried in the oven.

Plate 3. 4 (a) Aqueous Silver Nanoparticle Plate 3. 4 (b) Dried Silver Nanoparticles.

41
3.3 CHARACTERIZATION

The crystal phase analysis of the nanoparticles is conducted using the X-Ray Diffractometer is

used for the characterization of synthesized nanoparticles and to monitor the synthesis and

stability of the silver nanoparticles since they have unique optical property. Scanning Electron

Microscopy (SEM) is used to characterize the atoms or elements present in the extract.

3.4 PREPARATION OF SOLUTIONS FOR CORROSION TESTING

After the synthesis of the silver nanoparticles have been carried out from the Aloe Vera,

solutions of different concentrations of the extracts, varying amounts of silver nanoparticles and

fixed concentration of HCl at 1mol were prepared according to the permutations/combinations

shown in Table below:

3.5 PRE-CORROSION MATERIALS CHARACTERIZATION

X-Ray Fluorescence, Scanning Electron Microscopy, X-Ray Diffractometery and X-Ray

Photoelectron Spectroscopy were used to characterize the as-cast alloys before the corrosion

tests.

3.6 SAMPLE PREPARATIONFOR CORROSION TESTING

The working electrodes (the steel samples) were machined to cylindrical shape coupons of

dimensions 1.5cm x 1.0cm. A total of 100 coupons were used for all the tests carried out in this

work. The coupons were polished with silicon carbide (SiC) grit papers of various grades.The

selected steels were cold mounted using polyester resin, after which the samples were polished

with series of emery paper from 60-1,200 grade to remove any mill scale.

42
PLATE 3. 5 Mounted mild steel specimen

3.7 POLARIZATION MEASUREMENT

The Autolab Potentiostat with Nova 2.0 software and with a potential of -0.2mv to 1.2mv at a

scan rate of 0.1mv was used to determine the polarization of the test sample in the solutionusing

platinum counter electrode. The Autolab potentiostat after carrying a Linear Voltammetrysweep

test on the steel samples in different varying environments analyzed and recorded the corrosion

parameters, such as the Icorr in area per centimeter square, Ecorr, in voltage and the corrosion

rate in millimeter per year among other parameters.

3.8 Scanning Electron Microscope

The SEM was carried out, below is the image that shows how SEM works.

FIGURE 3.8 Operation of a Scanning Electron Microscope

43
Figure 3.8 shows the process of scanning a specimen having connected the microscope to

electric source. The electron from the electron gun is beam through a magnifying lens and focus

on the sample with is surrounded by the scanning coil to prevent loss of any particles.

3.9. The Biosynthesis Process

FIGURE 3.9 Showing the Biosynthesis Process of Silver Nanoparticles

Figure 3.9. Shows the biosynthesis process involved the extraction of silver nanoparticles in an

Aloe Vera Extract using hydrothermal method. The Crystalized AgNPs is collected after some

minutes in the stirred mixture of the extract.

44
 CHAPTER FOUR

RESULTS AND DISCUSSIONS

4.1 RESULT

4.1.1 POLARIZATION AND MEASUREMENT OF TEST RESULT

The graph of the applied voltage is being plotted against the Logarithm of the current density and

the potentiodynamic curve was obtained from the plot showing the corrosion behavior of the

steel in the different environment which is affected by the presence of inhibitors in the

environment. For, the experiment that involves inhibitors, the inhibitor efficiency in percentage

can be obtained from:

𝑬𝑖𝑛ℎ = 𝑪𝑹𝑂 − 𝑪𝑹1 ÷ 𝑪𝑹𝑂 ∗ 100 ……………………… (Equ. 4.1)

Where, Einh = efficiency of the corrosion inhibitor, CR0 = corrosion rate with 0% inhibitor

CR1= corrosion rate in the presence of an inhibitor

4.1.1 Compositional Characterization of Material Used

FIGURE 4. 1 MICROSTRUCTURE OF MILD STEEL

45
Table 4.1. Showing the concentration of each elements in the Low Carbon Steel

C Mn Si Cu P S Cr Mo Ni V N B Al

0.29 0.52 0.20 0.15 0.035 0.031 0.17 0.011 0.077 0.003 0.023 0.0002 0.007

Zn Pb Sb Ca Ti Fe Co As Sn

>0.027 0.007 0.018 0.003 0.002 98.3 0.007 0.006 0.026

Figure 4.1 above shows the micro structure of the mild steel before the extracted nanoparticle is

used as corrosion inhibitor on it, it was taken at 20 micrometer, and has a clean interface. The

microscopic feature of the mild steel is still very stable as the phases of the metals in the alloys

which are iron and carbon are formed into almost one phase which is austenitic phase, but as the

temperature and other physical environment are uttered the phases begin to change and the steel

begins to disintegrate which is called corrosion, the silver nanoparticle is to attack the corrosion

and reduce to minimal the corrosion rate of the carbon steel.

4.1.2 Scanning Electron Microscope

Plate 4. 2 Scanning Electron Microscope

46
Plate 4.2. Showing a typical plate of Scanning Electron Microscope (SEM), SEM is use in

capturing and magnifying particles and giving out the structure and phases in the particles.

4.2.2 Scanning Electron Microscope (SEM)

Below are the results for the SEM of the sliver nanoparticles at different Magnifications and

WD.

WD MAGNIFICATION WAVELENGTH PRESSURE VOLTAGE SIZE

1 11.0 6000 10 70 20 10

2 13.3 6000 11 70 20 10

3 9.0 5000 10 70 20 10

Figure 4. 2. 1 Scanning Electron Microscope for Silver Nanoparticles

47
Figure 4. 2. 2 Scanning Electron Microscope for Silver Nanoparticles.

Figure 4.2.1 and Figure 4.2.2 are the SEM result of the nanoparticles taking at different

magnification ranging from 5000 to 6000 and the image gotten shows a grey colour symbolising

the present of abundant of silver nanoparticles. SEM is a surface imaging tool that can resolve

diverse particle sizes, size distributions, nanomaterial forms, and surface morphology of

manufactured particles at the micro and nano scale. By manually measuring and counting the

particles or by utilizing appropriate software, we may investigate the morphology of particles

and build a histogram from the images using SEM. To evaluate silver powder morphology and

undertake chemical composition analysis, a combination of SEM and energy-dispersive X-ray

spectroscopy (EDX) can be utilized. SEM has the drawback of not being able to discern interior

structure, but it can provide useful information about particle cleanliness and degree of

aggregation. The morphology of nanoparticles less than 10 nm can be identified using a current

high-resolution SEM. (Xi-Feng Zhang, Zhi-Guo Liu, Wei Shen, and Sangiliyandi Gurunathan,,

2016)

48
4.2.3 Fourier Transformed Infrared

Figure 4. 2. 3 FTIR for Silver Nanoparticles.

Figure 4.2.3. Shows the corrosion inhibitive properties of the silver nanoparticles against a carbon steel in

acidic environment. FTIR has the ability to give accuracy, repeatability, and a good signal-to-noise

ratio. Small absorbance changes on the order of 103 can be detected using FTIR spectroscopy,

allowing difference spectroscopy to be performed, allowing the small absorption bands of

functionally active residues to be distinguished from the massive background absorption of the

entire protein. FTIR spectroscopy is extensively employed in academic and industrial research to

determine whether biomolecules are involved in the creation of nanoparticles. Furthermore,

FTIR has been applied to the investigation of nano-scaled materials, such as the confirmation of

functional molecules covalently grafted onto silver, carbon nanotubes, graphene, and gold

nanoparticles, or enzyme-substrate interactions during the catalytic process. In addition, it is a

49
non-invasive procedure. Finally, FTIR spectrometers have benefits over dispersive spectrometers

in terms of data collecting speed, signal strength, signal-to-noise ratio, and sample heat-up.

Attenuated total reflection (ATR)-FTIR spectroscopy, a type of FTIR spectroscopy, has recently

progressed. We can determine the chemical characteristics on the polymer surface using ATR-

FTIR, and sample preparation is simple compared to traditional FTIR. As a result, FTIR is a

suitable, beneficial, non-invasive, cost-effective, and straightforward tool for determining the

involvement of biological molecules in silver nitrate reduction to silver. (RagaaA. Hamouda1,2,

Mervat H. Hussein3, RashaA.Abo-elmagd3 & Salwa S. Bawazir1, 2019)

4.2 DISCUSSION

The method for synthesizing AgNPs described in this paper is both environmentally friendly and

simple. A hydrothermal condition was used to reduce silver nitrate in an aloe vera plant-extract

solution. As both a reducing and stabilizing agent, aloe vera plant extract solutions were used.

Nanoparticles with a fine spherical shape were made. By changing the hydrothermal

temperature, AgNP particle size can be adjusted. Attenuated total reflection (ATR)-FTIR

spectroscopy, a type of FTIR spectroscopy, has recently made significant progress. We can

determine the chemical properties of the polymer surface using ATR-FTIR, and sample

preparation is much easier than with traditional FTIR. As a result, FTIR is a suitable, beneficial,

non-invasive, cost-effective, and straightforward tool for determining the involvement of

biological molecules in silver nitrate reduction to silver.

Aloe vera leaf extract functions as a reducing and stabilizing agent in the green production of

silver nanoparticles. A color shift that may be measured spectrophotometrically indicates the

reduction of silver ions into silver nanoparticles after exposure to the leaf extract. Due to the

activation of surface plasma oscillations, silver nanoparticles in aqueous solution take on a

50
brown color. Within 24 hours of incubation, silver nanoparticles made from leaf extract and

silver nitrate solution show a high emission peak at 430nm. The SPR occurred at 430 nm at the

start of the reaction and remained stable at that wavelength even after the reaction was

completed. The maximum synthesis of silver nanoparticles was adjusted using various

concentrations of silver nitrate. A larger quantity of silver nitrate supported a bigger amount of

AgNPs synthesis. As a result of the adjusted medium, the maximal creation of silver

nanoparticles happened, and the reaction occurred extremely quickly. SEM was used to

determine the size and morphology of synthesized nanoparticles (made from 10mMAgNO3 and

a 3:2 dilution of Aloe vera leaf extract) (SEM). Synthesized AgNPs were spherical in form,

dispersed well, and aggregated less. AgNPs have a particle size of 10 to 11 nanometers. A rise in

the concentration of silver nitrate solution may result in the production of big particles.

51
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATION

5.1 SUMMARY

Nanoparticles is discovered to have inhibiting tendency, and the Aloe vera plants extracts used in

the synthesis show that nanoparticles can be extracted from any plants, the silver nanoparticles

can act as inhibitor against corrosion of carbon steel.

5.2 CONCLUSIONS

From the results of this investigation, the following conclusions were arrived at;

1. A silver nanoparticles with silver nitrate using Aleo Vera extract was prepared.

2. The microscopy of thr silver nanoparticles was examined with Scanning Electron

Microscope (SEM)

5.3 RECOMMENDATIONS

Based on the findings arrived at this work and the experimental results obtained, the following

recommendations are offered

1. Auxiliary research can be carried out by using other electrochemical test such as

Electrochemical Impedance Spectroscopy (EIS) with weight loss and EDS.

2. That other Characterization techniques such as x-ray, TEM, and Linear Polarization

Resistance Method should be explored.

52
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 APPENDIX

Table of the composition of elements in the Low carbon Steel as Received.

58