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Ships' Hull Corrosion Prevention Using ICCP System

Preprint · April 2021

DOI: 10.13140/RG.2.2.23815.52640

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 Ships' Hull Corrosion Prevention Using
ICCP System
Impressed Current Cathodic Protection Approach
(A Case Study of Sudan Navy Ships, Portsudan
2017/2019)

Authors
Engineer Surag Mohammed Saeed Ali
Major in Naval Forces, PortSudan, Sudan
Dr. Mohamed El Mubarak
Red Sea University, Faculty of Engineering, PortSudan,
Sudan
Dr. Osama Mohammed Elmardi Suleiman Khayal
Nile Valley University, Faculty of Engineering and
Technology, Atbara, Sudan

April 2019

i
 Dedication
In the name of Allah, the merciful, the compassionate

All praise is due to Allah and blessings and peace is upon his
messenger and servant, Mohammed, and upon his family and
companions and whoever follows his guidance until the day of
resurrection.

This research study is dedicated mainly to undergraduate

engineering students, especially mechanical, and production
engineering students where most of the applications presented are
focused on the necessity and importance of studying of corrosion.
This study aims to at increase ships' power and performance by protecting
its hull from corrosion and bio-fouling which cause reduction of the vessels
power.

This work is dedicated to the soul of my mother

To my father

To my brothers and colleagues

To my family and friends

To my beloved country Sudan

Hoping to contribute in its development and superiority

Last but not least, may Allah accepts this humble work and i hope
that it will be beneficial to its readers.

ii
 Acknowledgements
I thank Allah the Almighty who made it possible to me to achieve this work.
My thanks are extended to my supervisor Dr. Mohamed El Mubarak for his
patience and guidance throughout the period of conducting this dissertation.
His long experience and vast knowledge has a pivotal role to support me in
the area of the study. I benefited a lot from his recommendations,
suggestions and advice. I appreciate his modesty behavior and simplicity.
My deep thanks is also extended for all the faculties libraries staff for their
helps and kind treatment: To mention a few, Red Sea University Library,
The Sudan Library, The Library of Faculty of Engineering - University of
Khartoum, Library of the Faculty of Engineering - Sudan University of
Science and Technology, and Faculty of Engineering and Technology - Nile
Valley University Main Library. I also extend my thanks to my friends and
colleagues who encouraged and advised me.

iii
 Abstract

This study aimed at increasing ships' power and performance by protecting

its hull from corrosion and bio-fouling which cause reduction of the vessels
power. The study is based on four assumptions. First, the vessels hulls
should be protected from corrosion to increase their power and performance.
Second, vessels hulls corrosion can instantly be controlled using Impressed
Current Cathodic Protection 'ICCP'. Third, coating has a great effect on
protecting vessels hulls and increasing their performance. Finally, there are
many factors that contribute on ships' hull corrosion. The data were gathered
through experimental approach. The researcher used multi physic software
program (Comsol 5.3a) to build a model of 'ICCP'. The experiment included
two cases to protect ships' hulls from corrosion effectively and efficiently.
The first case is hull with coated propeller and the second one a non-coated
propeller. The researcher runs the corrosion model on 'Comsol 5.3a', the
results were set in the form of graph and chart that shows the value of the
current density for corrosion prevention for coated and non-coated case. The
results have shown a significant difference. For the coated propeller the
demanded current for protection is 4 A. In this case the potential distribution
across the ship hull surface is quite uniform (greenish color), except in the
region close to the anode surface and the propeller and shaft surfaces. For
the uncoated case, the value of the total current density over the shaft and
propeller surfaces is 9A. The potential distribution across the ship hull
surface is less uniform (reddish color) compared to the coated propeller
case. There is high ionic current flow from the anode surface to the shaft
and propeller surfaces which lead to oxidization of the anode more than the
coated case. The total current demand is found to be higher in case of the
iv
uncoated propeller compared to the coated propeller case which leads to the
higher consumption of the anode material than in the coated case. The study
concluded with some recommendations: Impressed Current Cathodic
Protection (ICCP) should be used in corrosion protection of the ship hull to
increase the ship performance and to prolong the vessel structure to its
maximum allocated lifetime. The anode material is consumed based on the
current density, i.e. the higher current the more consuming anodes.
Therefore, the research recommend for coated cases to reduce the amount
of the protection current, this leads to less consuming of anodes. It is
important to set a periodic time to check the serviceability of the anodes to
ensure the structure protection from corrosion. The protection current
density should be checked periodically to its limit to ensure vessels' hull
protection from corrosion.

v
 ‫مستخلص‬

‫ته د دده الد د د إاى ه ىيدد د د ا د د د ا د د د ااط قد د د اى ك د ددا ا ا تهد د د ابوىد د ددا ا ه اد د د ا ا تآهد د د ا د د د اى تد د د ا‬

‫لاا‪،‬ا‬
‫ى عوى د ددحاى ة و د د اى د ددناتك د د اى ةد ددها د د اط ق ه د د ‪.‬اتك د د لهاى ه ىيد د د ا د د اتي ع د د اى ى د د ‪.‬ات ا‬

‫اجد د د ا ه اد د د ا ا تد د د اى ك د ددا ا د د د اط ق هد د د ا ت ى هد د د ‪.‬اث ناد د د اا‪،‬ااهتد د د اى د د د ةت ا د ددنا د ددهتا ا تد د د ا‬

‫ى كد ددا ا وي د د اب ا د ددحاى اد د د ياى قك د د اا ةه ا د د ااى هات د د ا(‪(ICCP‬ا‪.‬اث ثاد د د ا‪،‬ا آاد ددب ات د د ث ا د د د ا‬

‫عآ د د ا ه ا د د ا ا ت د د اى كد ددا ا د د ات ى ه د د ‪.‬اتخ د د اىا‪،‬الل د د اى عهعد ددها د د اى عوى د د اى د ددناتك د د ل ا د ددنا‬

‫ت ت د د د ابد د دده اى كد د ددا ااك د د د وح اى د د د ةت ا ه د د د ‪.‬ات د د د احهد د ددناى ا ن د د د ا د د د اخد د ددب اى د د ددله اى ج د د ددن‪.‬اا‬

‫‪(Comsol‬ا لد د د انه د ددو اى اد د د ياى قكد د د اا‬ ‫اى ا د د د اى ه ع د دده ا)‪5.3a‬‬ ‫ىدد د د ه اى ب د ددااب ند د د‬

‫ا ةه ا د د د د اتحك د د د د اى كد د د ددا ا د د د د اى ت د د د د ا‬ ‫ةه ا د د د د ااى هات د د د د ا"‪."ICCP‬اشد د د ددهآةاى ج د د د د ا د د د د‬

‫دد د ا‬ ‫د د اى د دده نابا د ددب ااا ى ث نا د د اتع بد د د ياى ه‬ ‫د د ال د ددناتع بد د د يا‬ ‫باع ا د د ا اد د د ‪.‬اى ة د د د اى‬

‫‪."Comsol‬اتد د د ا‬ ‫ا" ‪5.3a‬‬ ‫د ددهتاعآد د د اب ند د د‬ ‫انه د ددو اى‬ ‫اط د ددب ‪.‬ااقد د د اى ب د ددااب د د د‬

‫د ددهتاا‬ ‫تو د دداتاى ل اج د د ا د ددناشد ددت اا ا د د اا يدد ددو ابا نا د د اتو د ددتا اه د د اا ث د د اى ب د د يا هلد ددناى‬

‫‪.‬ا‬ ‫اى ل د د د اىخ ب ا د د د ا ع د د د اىابد د د اى ةد د د‬ ‫ا يحد د د اى ةه اد د د ا و د ددة ابد د د وى ‪.‬اتظهد د د‬ ‫آةد د د‬

‫د ددهتالد ددوا‪4‬ات د د ‪.‬ا ا د ددنا‬ ‫د د اى هاآا د د ا‪،‬ااتد ددو اى ا د د ياى هاآد ددو ا آةه ا د د ا د د اى‬ ‫ب لكد ددب ا آه‬

‫لد د د إاى ة د د د اانج د ددهااتو د ددناى جه د ددهاع د د د اد د دداتا اتد د د اى ك د ددا ل ا ل اهد د د اته ا د د د ا(ى آ د ددو اىخ د د د )ا‬

‫دددد ا‬ ‫د د ددت اى ةه اد د د د اى ب د د د د ا لا د د ددناى هلاقد د د د اى ق بد د د د ا د د د د اد د د دداتاى ن د د ددو ا اد د د دداتاى ه‬

‫د د د اى د د د اا اآاد د د ا‪،‬ات آد د د ا‬ ‫ى عهد د د او ا ل د ددناىقد د د ا ه اد د د ا د د د اى هاتد د د ‪.‬اى د د د اب لك د ددب ا ة د د د اى ه‬

‫د د د ااا‪9‬ات د د د ا ل د ددناىعآد د د ابتث د د د ا د د د ا‬ ‫اهد د د ا ث د د د اى اد د د ياى سآاد د د اعآد د د اتد د دداتاى عه د ددو ا ى ه‬
‫‪vi‬‬
‫ى ة د د د اى كد د د بق ‪.‬ا د ددنالد د د إاى ة د د د انج د ددهاتو د ددناى جه د ددهاع د د د اد د دداتا اتد د د اى ك د ددا ل اتقد د د اىتكد د د اق ا‬

‫د د د د اى هاآا د د د د ا ى اى آد د د ددو ا‬ ‫ه د د د د ا ب د د د د ع ا د د د د ا ت د د د د ا خ د د د د )ا ق ين د د د د ابة د د د د اى ه‬ ‫(ى آد د د ددو اى‬

‫ىلخ د د د اى ه كد د دح‪.‬اعوح د ددهات د دده حاتع د ددونناليتاد د د داى اد د د يا د د د اد د دداتاى ن د ددو ا د د د اتد د دداتاى عه د ددو ا‬

‫د د ا ى د د اعد ددأل ا د د اتتكد دده اى ند ددو ‪.‬اىخ هد ددةاى ه ىيد د د ابد ددبعتاى و د ددا ا ىلق ى د د د ا‬ ‫ىه‬

‫د ددهتاا)‪(ICCP‬ا‬ ‫ه د ددها د د د اى ه ىيدد د د ‪.‬ااجد د د اىدد د د هى ان د د د اى اد د د ياى قكد د د ااا آةه اد د د ا د د د اى‬

‫ا هد د د ‪.‬اعد د د اىدد د د هب ا د د د اى ن د ددو ا‬ ‫دد د‬ ‫د ددناى ك د ددا ل ا د د د ات ى لد د د ا ط د د د اى عهد د د اى ال د ددناى ه‬

‫(‪(anode‬ابل د د د اعآ د د د ا ث د د د اتا د د د ياى ةه ا د د د اى قك د د د اا سآه د د د ا د د د اى ا د د د ياى قك د د د ااع د د د نا د د د ا‬

‫د د د اى هاآاد د د ا‬ ‫ىدد د د هب ااى ن د ددو ى ا(‪(anodes‬اىتثد د د ‪.‬ا د د د صا‪،‬اعو د ددناى بة د دداا د ددنا د د د اى ه‬

‫تقآ د د ا قد ددهىياى ا د د ياى قك د د اا آةه ا د د ا قآ د د اىد د د هب اىلند ددو ا تد ددو ا ه ا د د اىت د د ‪.‬اا د د اى هه د د ا‬

‫د د دده ا ه ا د د د ا ات د د د اى كد د ددا ا د د د د ا‬ ‫ت ااةد د دده ا ق ا د د د ا يا د د د ا آ ةقد د ددحا د د د ا د د ددب ا اى ند د ددو ى ا‬

‫ا د د دده ا ث د د د اتا د د د ياى ةه ا د د د اب د د ددوي ا يا د د د ا د د د اتح د د د اتد د ددو ا‬ ‫ى ت د د د ‪.‬ا ىا د د د ااج د د د ا ة د د د‬

‫‪.‬ا‬ ‫ى ةه ا اى ب‬

‫‪vii‬‬
 Table of Contents

Description Page

Dedication ii

Acknowledgements iii

Abstract iv

‫مستخلص‬ vi

Table of Contents viii

List of Abbreviations xvi

Definition of Terms xvii

List of Tables xviii

List of Figures xix

Chapter One: Introduction

1.1 An Overview 1

1.2 Statement of the Problem 2

1.3 Objectives of the Study 2

1.4 Questions of the Study 3

1.5 Research Hypotheses 3

1.6 Significance of the Study 3

viii
1.7 Methodology 4

1.8 Limits of the Study 4

Chapter Two: Literature Review

2.1 Introduction 5

2.2 Corrosion 5

2.3 Environmental Factors of Corrosion 6

2.3.1 Oxygen 7

2.3.2 Biological Activity 8

2.3.3 Temperature 8

2.3.4 Velocity 9

2.3.5 Salinity 9

2.3.6 pH 9

2.4 Corrodibility of Various Metals 10

2.5 Corrosion Mechanism 14

2.6 Types of Corrosion 16

2.6.1 Uniform Corrosion 16

2.6.2 Pitting (hole) Corrosion 16

2.6.3 Crevice (Crack) Corrosion 17

ix
2.6.4 Galvanic (and thermo galvanic) Corrosion 18

2.6.5 Selective Leaching (leak) 19

2.6.6 Erosion Corrosion 19

2.6.7 Stress Corrosion Cracking, Hydrogen Damage 19

and Corrosion Fatigue
2.6.8 Inter granular Corrosion 20

2.7 Corrosion Control Methods 21

2.7.1 Water-Resistant Coatings 22

2.7.2 Cathodic Protections 22

2.7.2.1 The principal of Cathodic Protection 25

2.7.2.2 Cathodic Protection by Sacrificial Anode 27

2.7.2.3 Cathodic Protection by Impressed Current 29

(ICCP)

2.7.2.4 Impressed Current Method Requirements 30

2.7.2.5 Anode Materials & Surrounding for Impressed 31

Current System

2.8 Bio fouling 34

2.9 Types of Bio-fouling 36

2.9.1 Plant Fouling 36

2.9.1.1 Bacteria and bacterial slimes 36

x
2.9.1.2 Diatoms 37

2.9.1.3 Seaweeds 37

2.9.2 Animal Fouling 39

2.9.2.1 Arthropods 39

2.9.2.2 Tubeworms (Annelids) 40

2.9.2.3 Mussels (pelecypods) 41

2.9.2.4 Bryozoa 41

2.9.2.5 Sea Squirts 41

2.9.2.6 Hydroids 42

2.9.2.7 Protozoa 42

2.10 Bio-fouling Mechanism 43

2.11 Stages of Bio-fouling 44

2.12 Antifouling coating formulation and methods 45

2.12.1 Coating System 45

2.12.1.1 Formulation of Anti Fouling Paints 45

2.13 Antifouling Methods 47

2.13.1 Traditional Antifouling Methods 48

2.13.1.1 Lead Sheathing 48

xi
2.13.1.2 Copper Sheathing 49

2.13.1.3 Other Sheathing Elements 50

2.13.2 Modern antifouling methods: protective paints 50

2.13.2.1 Antifouling paints 50

2.13.2.2 Environmentally friendly antifouling paints 55

2.14 Characteristics of Antifouling Paints 59

2.14.1 Anti-corrosiveness 59

2.14.2 Durability 60

2.14.3 Adhesion 60

2.14.4 Abrasion 60

2.14.5 Smoothness 61

2.14.6 Drag friction 61

2.14.7 Wettability 62

2.15 Environmental Risk Assessment 62

2.16 The Hull friction (Drag) and Roughness 63

2.16.1 Flow around a ship's hull 64

2.16.2 Sources of Hull Roughness 66

2.16.2.1 Structure of the paint 66

xii
2.16.2.2 Inadequate surface preparation 66

2.16.2.3 Poor Application Standards 67

2.16.2.4 Failure of the paint system 67

2.16.2.5 Mechanical damage 67

2.16.2.6 Fouling 67

2.17 Measurement of Hull Roughness 67

Chapter Three: Research Methodology

3.1 Introduction 70

3.2 A case Study 70

3.3 Methods 70

3.4 Program Parameters 71

3.5 Procedures 72

3.5.1 Create Corrosion Model Wizard on 'Comsol 72

5.3a' Program

3.5.1.1 Build Ship Hull Geometry 73

3.5.1.2 Global Definitions 73

3.5.1.3 Secondary Current Distribution (Cd) 76

3.5.1.4 Coated Propeller 84

3.5.1.5 Uncoated Propeller 84

xiii
 Chapter Four: Data Analysis and Discussions

4.1 Introduction 89

4.2 Result and Discussion 89

4.2.1 Ship Hull Atmosphere 89

4.2.2 Total 'ICCP' Current Demand 94

4.2.3 Analysis Hull Potential with Coated Propeller 97

4.2.4 Analysis of Current Density to the Shaft for 98

Coated Case
4.2.5 Analysis Hull Potential with Uncoated Propeller 98

4.2.6 Current Density to the Shaft Surface for 99

Uncoated Case

4.2.7 Electrode Phase ICCP Potential Plot 100

Chapter Five: Conclusions, Recommendations and Suggestions

for Further Studies

5.2 Conclusions 102

5.3 Recommendations 103

5.4 Suggestions for Further Studies 103

References 104

Appendices 106

xiv
 List of Abbreviations

No. Abbreviations Word/s

ICCP Impressed Current Cathodic

1
Protection

2 SCC Stress corrosion cracking

3 SACP Sacrificial Anode Cathodic Protection

4 IMO International Marine Organization

5 MIC Microbial Induced Corrosion

6 SRB Sulphur-reducing Bacteria

7 EPS Extracellular Polymeric Substances

8 HMS His Majesty's Ship

xv
 Definitions of Terms

Term Definition

The degradation of a material’s properties or

Corrosion
mass over time due to environmental effects.

Seawater A biologically active medium that contains a large

number microscopic and macroscopic organisms

The standard The tendency of each metal to be oxidized and

electrode potential is expressed in volts

An established corrosion control method for

Cathodic
protection of underground and undersea metallic
Protection
structures i.e. Ship Hull

A complex process involves the growth of a

Bio fouling community of organisms on a surface in contact
with an aqueous medium.

Coating System The use of an anticorrosive paint and an

antifouling paint.

xvi
 List of Tables

Tables No. Description Page

Table (2.1) The Value of pH and Corrosion Rate 10

Table (2.2) Electromotive Potential Series 11

Table (2.3) Galvanic Series 13

Table (2.4 ) Efficiencies of several common anode materials 29

Table (2.5 ) Anode materials for ICCP under different 32

environments
Table (2.6) Resistance of fouling organisms towards toxins 42

Table (3.1) ICCP Parameters 72

Table (4.1) Electrode Kinetics Parameters 92

xvii
 List of Figures

Figure No Description Page

Figure (2.1) Crevice Corrosion 18

Figure (2.2) Types of Corrosion 21

Figure (2.3) Cathodic Protection 23

Figure (2.4) pH Diagram 24

Figure (2.5) Potential / pH Diagram 25

Figure (2.6) Cathodic Protection Polarization 26

Diagram

Figure (2.7) Sacrificial Anode Cathodic Protection 28

Figure (2.8) Impressed Current Cathodic Protection 30

Figure (2.9) Ship's Hull with ICCP System 34

Figure (2.10) Fouling and Bio Corrosion on the Hull 35

of a Ship
Figure (2.11) Plant Fouling 36

Figure (2.12) Animal Fouling 39

Figure (3.1) ICCP System 71

Figure (4.1) The Geometry of the Ship Hull, which 90

is Exposed to the Sea Water

xviii
 The zoomed-in Model Geometry of the
Ship Hull Highlighting Anode, Shaft,
Figure (4.2) 90
Propeller Surfaces and Electrolyte
Domain.
Figure (4.3) The Mesh used in Model. 93

Figure (4.4) The mesh used in model, zoomed-in 94

around propeller.
Figure (4.5) Graphical User Interface of the Ship 96
Hull ICCP Simulator
Figure (4.6) A Surface Plot of the Hull Potential for 97
the Coated Propeller Case
Figure (4.7) A Surface Plot of the Total Current 98
Density for the Coated Propeller
Figure (4.8) A Surface Plot of the Hull Potential for 99
Uncoated Propeller.
Figure (4.9) A Surface Plot of the Total Current 100
Density Uncoated Propeller
The Electrode Potential Variation
Figure (4.10) along the Keel of the Ship for Both 101
Coated and Uncoated Propellers.

xix
 Chapter One
Introduction
1.1 An Overview

Nowadays, ships have been very significant worldwide as sea transportation

mean and it is considered safe, economic and cheap. However, there are
some challenges that face operation and maintenance of sea vessels.

Ships sail on different water surfaces such as oceans, seas, lakes and rivers.
Oceans, seas and lakes are considered as the most corrosive environment that
ships could encounter. Therefore, it important to find suitable maintenance
measures and protection system to resist tough atmosphere and to increase
the performance of sea vessels.

There are many factors in marine environment such as salinity, pH, and
temperature, velocity which cause corrosion and also, aquatic organism bio-
film which covers the vessels hull. This phenomenon is called fouling and it
results in increasing hydrodynamic drags, lower the maneuverability of the
vessels and increase the fuel consumption. All these factors lead to the
deficiency of ships performance. There are many methods that can be used to
prevent vessels from the results of fouling and corrosion, among these
methods coating i.e. Using a highly corrosion resistant material on the ship
hull and cathodic method i.e. using zinc for electro mechanic interaction
could be effective if implemented properly.

Ships maintenance has paramount role in ensuring ship's high performance

operation and makes it free from corrosion. However, lack of maintenance
principles may cause corrosion accumulation to the ship's hull and deficiency
of vessels performance. The researcher, therefore, is intended to find a
suitable way to increase ships performance by controlling the factors the

1
affects ship's hull to corrode using Impressed Current Cathodic Protection
System 'ICCPS' to instantly monitor these factors and react against; besides
setting an effective maintenance measures.

Maintenance does not only keep any mechanical equipment or machinery

going but also can help with prolonged life and a favorable outcome and
increase it is performance. For a ship, maintenance is the one thing that
keeps machinery in smooth running condition and it has a paramount feature
of the national economy. Each year, large amounts of money are located for
maintenance purpose. Poor or failed maintenance planning can result in
serious incidents and high penalty costs arising from operation downtime
(Dekker 1996).

1.2 Statement of the Problem

From his 8 years of experience in the field of marine, the researcher

observed that the ships aren't enrolled effectively in service due to many
circumstances. First, the regulations of ship maintenance are not followed
effectively. Second, the corrosive environment in seas and oceans extremely
damages the ship's hull. The researcher, therefore, is intended to conduct an
experiment to minimize or eliminate hulls' corrosion through continuous
observation of the factors that cause corrosion using 'ICCPS'. Besides,
setting suitable maintenance measures that serve in protection of vessels hull
from corrosion.

1.3 Objectives of the Study

The researcher intends to monitor vessels maintenance and hull protection
using 'ICCPS' to increase ships power and performance. The sub objectives
are to:

1. To maintain the vessel hull from corrosion so as to increase its power and
performance.
2
2. To detect the factors that affects the corrosion of ships' hull.

3. To instantly control the process of hull corrosion using 'ICCPS'.

4. To determine the effect of coating on vessel performances.

1.4 Questions of the Study

The researcher is going to answer the following research questions:

1. How can we maintain vessels' hull from corrosion to increase their power
and performance?

2. What are the factors that causes corrosion of ships' hull?

3. How does the corrosion of ship hull be controlled using 'ICCPS'?

4. How does coating affect vessel performance?

1.5 Research Hypotheses

In order to answer the research questions, the researcher set the following
hypotheses:

1. The vessels hulls should be protected from corrosion to increase their

power and performance.

2. There are many factors that contribute on ships' hull corrosion.

3. Vessels hulls corrosion can instantly be controlled using 'ICCPS'.

4. Coating has a great effect on protecting vessels hulls and increasing their
performances.

1.6 Significance of the Study

This study is hoped to develop the ship maintenance in Sudanese marine. It
increases ships' power and performance, and extends their lifetime by setting
standard maintenance measures. The study is also expected to reduce the
maintenance costs by good maintenance planning and scheduling. Moreover,
the study will decrease the risk and incident factors which is caused by poor
maintenance.
3
1.7 Methodology
The study is experimental through which an 'ICCPS' modeling simulation
will be carried out using 'software applications' i.e. "comsol 5.3a" to detect
the important parameters and produce a suitable 'impressed current' for
protection. In the experiment, ship's hull structure represent cathode, the sea
water represent the surrounding atmosphere, and anode boundaries i.e. a
metal which is higher in potential than the cathode (Hull) are used. The
second method is coating, the researcher has created the program to show the
effect of ICCP system for coated and non-coated structure.

1.8 Limits of the Study

This study is confined to Sudan Navy Ships-Zamzam and Almaz. It
investigates the hull protection from corrosive environment and ship
maintenance using coating system and Impressed Current Cathodic
Protection System. The use of ICCP needs high technology, therefore the
research will implement the ICCP system on modeling simulation software
program 'Comsol 5.3a'. The study will be conducted in Sudan, Port Sudan
during the period 2017/2019.

4
 Chapter Two

Literature Review
2.1 Introduction
The ship's hull protection to resist the rough surrounding environment
requires knowledge about the different factors that affect vessels frame and
how to protect it from the damage due to accumulation of corrosion and
fouling. The researcher, therefore should give an overview about the
phenomena of corrosion, bio-fouling, factors that affect hull structure and
various hull protection methods.

2.2 Corrosion

There are three main reasons concerning the study of corrosion. These
reasons are safety, economics, and conservation. Early failure of vessels hull
due to corrosion can result in human injury or even loss of life. Failure of
operating equipment can have the same disastrous results. Corrosion is
defined as the degradation of a material’s properties or mass over time due to
environmental effects. It is the normal inclination of a material’s
compositional elements to return to their most thermodynamically stable
state. For most metallic materials, this means the formation of oxides or
sulfides, or other basic metallic compounds generally considered to be ores.
Luckily, the accumulation rate of these processes is low enough to enable the
making of useful building materials. Only inert environments and vacuum
can be considered free of corrosion for most metallic materials. Under usual
circumstances, iron and steel corrode in the presence of both oxygen and
water. If either of these materials is not present, corrosion usually will not
take place. High corrosion rates may take place in water, in which the rate is
increased by the acidity or velocity of the water, due to the movement of the
metal, and the increase in the temperature or it may take place in aeration,
due to the presence of microorganisms, or takes place due to other less
5
common factors. On the other hand, corrosion is generally stopped by films
(or protective layers) consisting of corrosion products or adsorbed oxygen;
high alkalinity of the water also reduces the rate of corrosion on steel
surfaces. The amount of corrosion is controlled by either water or oxygen,
which are necessary for the process to take place. For example, steel will not
corrode in dry air and corrosion is insignificant when the relative humidity of
the air is below 30% at normal or reduced temperatures (Wells, 1948).
Protection from corrosion by dehumidification is based on this fact. All
structural metals corrode to some degree in natural environments. These
corrosion processes follow the basic laws of thermodynamics. Corrosion is
an electrochemical process and as such, under controlled conditions, it can
be measured, repeated, and predicted. Since it is governed by reactions on an
atomic level, corrosion processes can act on isolated regions, uniform
surface areas, or result in subsurface microscopic damage. These forms of
corrosion are complicated with further subdivisions. Just consider adding
basic environmental variables such as pH, temperature, and stress, and the
predictability of corrosion begins to be more difficult.

2.3 Environmental Factors of Corrosion

Seawater is a biologically active medium that contain a large number

microscopic and macroscopic organisms. Many of these organisms are
commonly observed in association with solid surface in seawater, where they
form bio-fouling films, these bio films play a vital role in aggravating
corrosion on vessels hull. Immersion of any solid surface in seawater
initiates a continuous and dynamic process, beginning with absorption of
nonliving, dissolved organic material and continuing through the formation
of bacterial and algae slime films and the settlement and growth of various
macroscopic plants and animals. This process by which the surface of all

6
structural materials immersed in seawater become colonialized, adds to the
variability of ocean environment in which corrosion occurs (Rodgers, 1968)

The amount of oxygen and other gases dissolved in seawater depends on the
temperature and salinity of the seawater and the depth of water. In some sea
water compositions, hydrogen sulfide is also present. Hydrogen sulfide is
formed in sea water by the action of sulfate–reducing bacteria (SRB), usually
under deposit where oxygen is depleted or when the sea water is stagnant or
polluted and becomes anaerobic, even in large volumes. Silt deposit in
estuarial waters are also contributory. Mineral and organic materials are also
carried in suspension by the sea water, particularly near the mouth of the
river (Craig &Anderson, 1995).

Since sea water is a complex environment, delicately balanced solutions of

many salts containing living matter, suspended silt, dissolved gases and
decaying organic materials, the individual effect of each of the factors
affecting the corrosion behavior is not readily separated. Because of the
interrelation between many of the variables in the sea water environment, an
alteration of one variable may affect the relative magnitude of the other
variables. In the following subsections, the roles of oxygen, biological
activity, temperature, velocity, salinity, and Ph are presented (Fink, 1993).

2.3.1 Oxygen

The dissolved oxygen content is a major factor affecting the corrosively

seawater. The oxygen level in seawater is of different range up to 12 ppm.
Photosynthesis of green plants, wave action etc., tends to increase the
oxygen level, whereas the biological oxygen demand of decomposing of
dead organisms will reduce it. For a given location, seasonal variation in
oxygen level will influence corrosion behavior. For metals like copper and
iron, complete elimination of oxygen will reduce the corrosion to negligible

7
amounts. However, metals that depend on formation of a passive film for
corrosion protection, i.e. stainless steel, often corrodes rapidly where the
oxygen supply to the metal surface is restricted.

2.3.2 Biological Activity

When a metal or other surface is first immersed in seawater, a biological

slime tends to develop in a matter of hours. During an active season, a great
variety of organisms are found in an immersed surface. From a corrosion
point of view, the sessile organisms are of most concern. They arrive at
slime-covered surface in minute emergent form and become firmly attached.
Once attached, they rapidly transform to the mature form and become
immobile. Organisms, which build hard shells, are: annelids, barnacles,
encrusting, bryozoans, mollusks, and corals. Organisms without hard shell
are: marine algae, filamentous bryozoans, coelenterates, or hydroids,
tunicates, calcareous, and siliceous sponges.

2.3.3 Temperature

An increase in temperature is normally expected to speed up a chemical

reaction according to thermodynamic considerations. This also would be the
case for the corrosion reaction in seawater where it is possible to hold all
other variables fixed. Since it is not normally possible to do this, the effect of
temperature has to be established indirectly. Oxygen solubility decreases
with increase in temperature, biological activity increases as the water
temperature increases, and the chemical equilibrium involved in the
precipitation (production) of calcium carbonate and magnesium hydroxide is
altered (replaced) so that calcareous scale is more likely to deposit on the
metal as the temperature is increased. For temperature variations of seasonal
(cyclic) nature, iron, copper, and many of their alloys show a high rate of
attack during the warm months.

8
2.3.4 Velocity

Many metals are sensitive to velocity effects in sea water. For metals like
iron or copper, there is a critical velocity beyond which corrosion becomes
excessive. Stainless steel and certain nickel-chrome-molybdenum alloys tend
to be more resistant in high-velocity seawater. Special forms of corrosion are
associated with seawater velocity, i.e. (erosion-corrosion caused by high-
velocity silt-bearing seawater, impingement attack, where air bubbles are
present, and cavitation, where collapsing vapor bubbles cause mechanical
damage and often corrosion damage as well.

2.3.5 Salinity

The major oceans of the world are completely connected and mixing is
continuous. The average salt content of the sea is 3.5 wt % with the
composition comprised mainly of the following irons: sodium, magnesium,
calcium, potassium, chloride, bromide, carbonate, and sulfate. In addition,
seawater contains measurable quantities of iodide, fluoride, phosphate, gold,
silver, arsenic, rubidium, copper, barium, manganese, lithium, lead, iron,
strontium, and zinc irons. Ammonia is also present, with free oxygen,
nitrogen, and other gases. Variations in salinity in open-ocean surface water
typically range from 3.25 – 3.75 wt %.

2.3.6 PH

PH is a number range from 0 to 14 which shows how strongly acid or

alkaline a substance is. The number below PH 6.5 is acid and above PH 7.5
is alkaline.

In a case of marine environment, the PH of seawater may vary slightly

depending on the photosynthetic activity. Plant matters consumes carbon
dioxide and affects the PH during the daylight hours. The carbon dioxide in
9
seawater, close to the surface is influenced by the exchange with carbon
dioxide in the atmosphere. The slight daily shift in PH has little direct effect
on the corrosion behavior, however it can be a factor in calcareous-scale
deposition, which affects the corrosivity. As pressure is increased, PH is
reduced according to thermodynamic considerations. Thus, at great depths,
there is some evidence of fewer tendencies for protective carbonate-type
scale formation. Table (2.1) below shows the value of PH and corrosion
rate.

Table (2.1) the Value of PH and Corrosion Rate

Acidity and Alkalinity of Surroundings PH values Corrosion Rate

Extremely acid Below 4.5 Highest corrosion
Very strongly acid 4.5-5.0
Strongly acid 5.1-5.5
Medium acid 5.6-6.0
Slightly acid 6.1-6.5
Neutral 6.6-7.3 Least corrosion
Mildly alkaline 7.4-7.8
Moderately alkaline 7.9-8.4
Strongly alkaline 8.5-9.0
Very strongly alkaline 9.1- higher Higher corrosion

2.4 Corrodibility of Various Metals

The luster, ability to conduct heat and electricity, malleability of some and
ductility of others are only some of the main characteristics, which define
metals. However, it is the varying ability of a metal to lose its electrons and
form a positive iron that is essential in understanding the range of metals
that are capable of corroding. It is this understanding which is used widely in
industry as the first measure for corrosion control (i.e. choosing a metal that

10
will not corrode easily by giving up its electrons). The electrochemical field
has developed a list, which details the range of most metals relative tendency
to be oxidized, called an electromotive series. The list provide nearly all the
information required to determine which metals are most subjective to
corrosion. The series tells us which species behaves best as the anode
undergoing oxidation and the cathode undergoing reduction. The list begins
with metals most easily oxidized, end with the metals least capable of
oxidation, or with the greatest capability of reduction. In other words, the list
begins with metals, which are most easily corrode (i.e. behave as anode in
the corrosion reaction), and ends with metal, which can best behave as
cathode in the corrosion reaction. The tendency of each metal to be oxidized
is given in terms of 'the standard electrode potential' or 'oxidization potential'
and is expressed in volts, which is measured relative to the standard
oxidization of hydrogen gas, which is assigned as an arbitrary potential of (0
volts). Table (2.2) below provides an electromotive series as a list of major
industrial metals. As you can see from the list, metals such as magnesium,
zinc and iron will oxidize easier and therefore corrode easier than platinum
or gold. This list should provide the sufficient background needed to predict
which metal during the experiment should corrode more easily. Furthermore,
the electromotive series has a large influence on a particular type of
corrosion, known as galvanic corrosion. Table (2.2) below shows
electromotive potential series.

Table (2.2) Electromotive Potential Series

Element Reaction Electrode Potential

Gold Au+ + e- = Au 1.692

Platinum Pt2+ + e- = Pt 1.18

Silver Ag+ + e- = Ag 0.7996

11
 Copper Cu+ + e- = Cu 0.521

Copper Cu2+ + 2e-= Cu 0.3419

Hydrogen (Acid) 2H+ + 2e- = H2 0

Iron Fe3+ + 3e- = Fe - 0.037

Lead Pb2+ + 2e- = Pb - 0.1262

Tin Sn2+ + 2e- = Sn - 0.1375

Iron Fe2+ + 2e- = Fe - 0.447

Chromium Cr2+ + 2e- = Cr -0.913

Titanium Ti2+ + 2e-= Ti -1.63

Aluminum Al3 + 3e- = Al -1.662

Magnesium Mg+ + e- = Mg -2.7

Sodium Na+ + e- = Na -2.71

Calcium Ca2+ + 2e- = Ca -2.868

Potassium K+ + e- = K -2.931

Lithium Li3+ + e- = Li -3.0401

Calcium Ca+ + e- = Ca -3.8

The electromotive series serve as a corrosion map for metals in particular

concentrations of their own salts. It fails in describing the behavior of such
metals in various corrosive environment based on varying temperature,
humidity, salinity, etc. Therefore, a more general table developed by
electrochemists, called galvanic series is used in practical application, (Efrid
& Lee, 1997). The following Table (2.3) shows galvanic series scale.

12
Table (2.3) Galvanic Series

13
2.5 Corrosion Mechanism

Common structural metals are obtained from their ores or naturally-

occurring compounds by the expenditure of large amounts of energy. These
metals can therefore be regarded as being in a metastable state and will tend
to lose their energy by reverting to compounds more or less similar to their
original states. Since most metallic compounds, and especially corrosion
products, have little mechanical strength a severely corroded piece of metal
is quite useless for its original purpose.

Virtually all corrosion reactions are electrochemical in nature. At anodic

sites on the surface the iron goes into solution as ferrous ions, this
constituting the anodic reaction. As iron atoms undergo oxidation to ions
they release electrons whose negative charge would quickly build up in the
metal and prevent further anodic reaction, or corrosion. Thus this dissolution
will only continue if the electrons released can pass to a site on the metal
surface where a cathodic reaction is possible. At a cathodic site the electrons
react with some reducible component of the electrolyte and are themselves
removed from the metal. The rates of the anodic and cathodic reactions must
be equivalent according to Faraday’s Laws, being determined by the total
flow of electrons from anodes to cathodes which is called the “corrosion
current”. Since the corrosion current must also flow through the electrolyte
by ionic conduction, the conductivity of the electrolyte will influence the
way in which corrosion cells operate. The corroding piece of metal is
described as a “mixed electrode” since simultaneous anodic and cathodic
reactions are proceeding on its surface. The mixed electrode is a complete
electrochemical cell on one metal surface.

The most common and important electrochemical reactions in the corrosion

of iron are as follows:

14
 Anodic reaction (corrosion)

(1) Fe → Fe2+ + 2 e

Cathodic reactions (Simplified)

(2 a) 2H+ + 2e → H2

Or
1
(2b) H2O + O2 +- 2e → 2O H−
2

Reaction in (2a) is most common in acids and in the pH range 6.5 – 8.5. The
most important reaction is oxygen reduction in (2b). In this latter case
corrosion is usually accompanied by the formation of solid corrosion debris
from the reaction between the anodic and cathodic products.

Fe2+ + 2O H− → Fe (OH) 2, iron (II) (hydroxide)

Pure iron (II) hydroxide is white but the material initially produced by
corrosion is normally a greenish color due to partial oxidation in air.

1
2Fe (OH) 2 + H2O + O2 → 2Fe (OH) 3 hydrated iron (III) oxide
2

Further hydration and oxidation reactions can occur and the reddish rust that
eventually forms is a complex mixture whose exact constitution will depend
on other trace elements which are present. Because the rust is precipitated as
a result of secondary reactions it is porous and absorbent and tends to act as a
sort of harmful poultice which encourages further corrosion. For other metals
or different environments different types of anodic and cathodic reactions
may occur. If solid corrosion products are produced directly on the surface as
the first result of anodic oxidation these may provide a highly protective
surface film which retards further corrosion, the surface is then said to be
“passive”. An example of such a process would be the production of an
oxide film on iron in water, a reaction which is encouraged by oxidizing
conditions or elevated temperatures.
15
 2 Fe + 3H2O → Fe2O3 + 6H+ + 6e

2.6 Types of Corrosion

There are several forms of corrosion that can occur. Each form of oxidization
has specific arrangement of anodes and cathodes and the corrosion which
occurs has specific location and pattern. Each form of corrosion can be
effectively controlled during design if it is anticipated. By understanding the
various forms of corrosion, the conditions under which they occur, and how
they are quantified, then they can be addressed and controlled. The most
common types of corrosion are: (Khayal, O.M.E.S., 1993).

2.6.1 Uniform Corrosion

Uniform corrosion results from the sites, is not necessarily fixed in location,
and is distributed over a metal surface where the anode and cathode reactions
happen. Uniform corrosion damage, something called wastage (wear), is
usually manifested in the progressive thinning of a metal part until it
virtually dissolves away (melts). (Khayal, O.M.E.S., 1993).

2.6.2 Pitting (hole) Corrosion

The initiation of a pit (hole/cavity) occurs when electrochemical or chemical

breakdown exposes a small local site or a metal surface to damaging species
such as chloride irons. The sites where pits (dents) initiates are not
completely understood, but possibly could be found at scratches, surface
composing heterogeneous inclusions, or place where environmental
variations exists. The pit grows if the high current density and the area of
breakdown initiation are exceedingly small. If the rate of repassivation in not
sufficient to choke off (block) the pit growth, two new conditions develop.
First, the metal iron produced by the breakdown process are precipitated as
solid corrosion products (such as Fe (OH) 2) which usually cover the mouth

16
of the pit. This covering traps the solution in the pit and allows the building
of positive hydrogen irons through a hydrolysis reaction. Then, chloride or
another damaging negative iron diffuses into the pit to maintain charge
neutrality. Consequently, the repassivation becomes considerably difficult
because the solution in the pit is highly acidic, contains a large concentration
of damaging irons and metallic irons, and contains a low oxygen
concentration. Thereby, the rate of pit growth accelerates.

The pit is the anode of an electrochemical corrosion cell, and the cathode of
the cell is the none-pitted surface. Since the surface area of the pit is a very
small fraction of the cathodic surface area, all of the anode corrosion current
flows to the extremely small surface area of the breakdown initiation site.
Thus, the anodic current density becomes very high and pitting can be rapid.
(Khayal, O.M.E.S.).

2.6.3 Crevice (Crack) Corrosion

Crevice corrosion results when a portion of a metal surface is shielded in

such a way that the shielded portion has limited access to the surrounding
environment. Such surrounding environments contain damaging corrosion
species, usually chloride irons. A typical example of crevice corrosion is the
crevice formed at the area between two metal surface in close contact with a
gasket and another metal surface. The environment that eventually forms in
the crevice are similar to that formed under the precipitated corrosion
product that covers a pit. Similarly, an electrochemical corrosion cell is
formed from the couple between the unshielded surface and the crevice
interior exposed to an environment with a lower oxygen concentration
compared with the surrounding medium. The combination of being the
anode of corrosion cell and existing in an acidic, high chloride environment
where repassivation is difficult to make the crevice interior to corrosive
attack. Figure (2.1) shows the chemical mechanism of crevice corrosion.
17
 Figure (2.1) Crevice Corrosion

2.6.4 Galvanic (and thermo galvanic) Corrosion

Two metals having different potentials in a conducting electrolyte result in

the more anodic metal usually being attacked by galvanic corrosion. Because
of electrical contact between the two different metals, galvanic corrosion
differs from the other forms of corrosion described previously in that anode
and cathode sites of the corrosion cell reside (stay) separately on the two
coupled different metals comprising the corrosive cell, while for the other

18
forms of corrosion, the cathodes and anodes exist on the surface of the same
metal.

The value for the difference in potential between two dissimilar metals is
usually obtained from a listing of the standard equilibrium potentials for the
various metals.

Another factor besides the coupling of two different metals that can lead to
galvanic corrosion is a different in temperature at separate sites on the same
metal surface. Such a situation leads to thermo galvanic corrosion. This type
of corrosion can be found in heat exchanger systems where temperature
differences are common. (Khayal, O.M.E.S., 2018).

2.6.5 Selective Leaching (leak)

This kind of corrosion occurs when the components of an alloy is removed

selectively by corrosion because of differences in potential between different
constituents of an alloy i.e. a situation analogous to that of the galvanic
corrosion of couple dissimilar metals. This results in an increase in the
concentration of the remaining components and selective leaching occurs.
This type of corrosion is also called parting. The most common example is
selective leaching out of 'zinc' from 'brass' (dezincification).

2.6.6 Erosion Corrosion

Erosion corrosion is caused by the disruption of protective passive films by

erosive (wearing) or abrasive (scratch) processes. Once the protective or
passive film is removed in an aqueous electrolyte, the electrochemical
processes for the types of corrosion described above take place.

2.6.7 Stress Corrosion Cracking, Hydrogen Damage and

Corrosion Fatigue
19
Stress corrosion cracking (SCC) is a form of localized corrosion, which
produces cracks in metals by the simultaneous action of a corroding and
tensile stress. The electrochemical cell between the exterior and the interior
environment of a crack is similar to that described above in section (2.6.3)
for a crevice. Because of the necessity for the application of the stress, the
breakdown of the passive layer on a metal service surface in SCC is
generally attributed to mechanical causes but many suggest that
electrochemistry is significant factor because it controls the rate of repair of
the passive layer cracked by mechanical stress.

Corrosive fatigue has a somewhat similar mode of failure to SCC. It mainly

differs from SCC in that it involves situation where the stress is applied
cyclically rather than as a static sustained tensile stress. With both corrosion
fatigue and SCC, the issues of film mechanical breakdown, repassivation,
and adsorption of damaging species, hydrogen embrittlement and
electrochemical dissolution are to greater or lesser extents involved in
determining weakness. (Khayal, O.M.E.S., 1993).

2.6.8 Inter - granular Corrosion

Figure (2.2) below shows the different types of corrosion that is found in
metallic structures.

With the exception of metallic glasses, the metals used in practical devices
are made up of small crystals (grains) whose surface join the surfaces of
other grains to form grains boundaries. Such boundaries or the small regions
neighboring to these boundaries can under certain conditions be considerably
more reactive (by being more anodic) than the interior of the grains. The
resulting corrosion is called inter - granular corrosion. It can result in a loss
of strength of metal part or the production of debris (grains that have fallen
out). (Khayal, O.M.E.S., 1993).

20
 Figure (2.2) Types of Corrosion
2.7 Corrosion Control Methods

In marine technology, the application of organic coating is an old method

used to stop corrosion but this method has a limited time then the hull starts
to corrode again. However, by selecting a suitable coating the ship hull could
be protected for the lifetime span of the ship. Barrier (coating), cathodic
(electrochemical) and inhibitive (oxygen deprivation) are the main three
methods of controlling the corrosion. (Khayal, O.M.E.S., 1993).
21
2.7.1 Water-Resistant Coatings

The most commonly used method of preventing corrosion is to place a water

resistant barrier between the sheet metal and the electrolyte (sea water). The
type of anti-corrosive coating required is dependent on two main factors: the
type of antifouling to be used and the location of application on the ship.
Obviously the antifouling and the anti-corrosive must be compatible, there
must be good adhesion between them and also no reaction to impair the
properties of either coating. Different areas of the ship require specific anti-
corrosives; for example, around the steering gear, the hull and the splash
zone where the environmental situations are very different.

Although it is not ideal, in practice only one anticorrosive coating is used

and this is based either on a chlorinated rubber resin or a pitch base, the
system being chosen to be compatible with the antifouling to be used.

Inevitably the coatings will not be continuous and pinhole free, and in
service are likely to be damaged. There are also areas of the ship, such as
steering gear, propulsion units and anchorage points which cannot be
permanently coated, consequently other techniques to combat corrosion have
been developed.

2.7.2 Cathodic Protections

Cathodic protection is an established corrosion control method for protection

of underground and undersea metallic structures, such as ships' hull, oil and
gas pipelines, cables, utility lines and structural foundations. Cathodic
protection is generally useful in the protection of ships' hull platforms,
dockyards, jetties, submarines, condenser tubes in heat exchangers, bridges
and decks, civil and military aircraft and ground transportation systems. The
designing of cathodic protection systems is rather complex. However, it is
based on simple electrochemical principles. Corrosion current flows between
22
anodes and cathodes due to the existence of a potential difference between
the two elements. (Khayal, O.M.E.S., 2018).

As can be seen in Figure (2.3) below which shows cathodic protection,

electrons released in an anodic reaction are consumed in the cathodic
reaction. If we supply additional electrons to a metallic structure, more
electrons would be available for a cathodic reaction which would cause the
rate of cathodic reaction to increase and that of anodic reaction to decrease.
This action would finally minimize or eliminate corrosion. This is basically
the purpose of cathodic protection. The additional electrons are supplied by
direct electric current. If enough direct current is applied, the potential
difference between the anode and cathode is eliminated and corrosion would
finally stop.

Figure (2.3) Cathodic Protection

23
Figure (2.4) and Figure (2.5) below demonstrate how cathodic protection
works in terms of E-pH diagram. Cathodic protection brings down the
potential of a metal that has a free corrosion potential at the active potential
and pH to a lower potential that is defined as an “immune” area. Figure (2.5)
below demonstrates

Figure (2.4) pH Diagram

24
 Figure (2.5) Potential / pH Diagram

2.7.2.1 The Principles of Cathodic Protection

25
The main principle of cathodic protection is reducing the potential of the
metal surface to a protective potential E where E<Ecorr. In elaborating
cathodic protection in terms of polarization diagram, the figure below could
be used. Figure (2.6) below attempts to explain cathodic protection by
schematic polarization diagram showing corrosion point ‘C’ and protective
point ‘P’ for iron (assuming that oxygen reduction occurs and no other
oxidizing agents are present).

Figure (2.6) Cathodic Protection Polarization Diagram

From Figure (2.6) above, if the applied potential E, and the applied current I

are more than Ea and Ia respectively, metal dissolution is possible along the

curve Ea - C. External supply of electron must be provided to the system to

reduce metal dissolution if the applied potential and current are between E a
and Ecorr and Ia and Icorr respectively. Ideal cathodic protection is achieved if

applied potential is the open circuit potential of the metal (E ≤ E a) and the

applied current is purely cathodic (I ≤ I p). If applied potential is less than Ea

26
the metal is also protected at a higher current, but hydrogen evolution is
possible leading to coating defects or hydrogen embrittlement. The principle
above is applied in the real world mainly by two methods. One method
involves current supplied to protected metal using a sacrificial metal that is
galvanically more active than the protected metal which is termed
“sacrificial anode”. The other method involves supply from an external DC
current source termed “impressed current” method (Perez. N. (2004).

2.7.2.2 Cathodic Protection by Sacrificial Anode

In cathodic protection, the structure to be protected must be given a cathodic

current flow so that it operates as a cathode. The requirement for an external
DC current to achieve this can be eliminated by using an anode constructed
of a metal that is more active in the galvanic series than the metal to be
protected called a sacrificial anode. A galvanic cell is established with the
current direction as required.

One example of sacrificial anode material is magnesium or magnesium-

based alloys. Magnesium is more active than steel, has a greater tendency to
ionize. The open-circuit potential difference between magnesium and steel is
about 1 volt. This means that one anode can protect only a limited length of
pipeline or over a defined surface area. This low voltage can have an
advantage over higher impressed voltages in that the danger of
overprotection to some portions of the structure is less and because the total
current per anode is limited; the danger of stray-current damage to adjoining
metal structures is reduced. Magnesium rods have also been used in steel hot
water tanks to increase their service life. The greatest degree of protection is
in more conductive electrolyte such as hard waters, compared to soft waters
which have lower conductivity. Figure (2.7) shows sacrificial anode cathodic
protection (SACP).

27
 Figure (2.7) Sacrificial Anode Cathodic Protection (SACP)

Zinc and Aluminium have been used extensively in seawater applications.

Sacrificial anodes for offshore structures in seawater are commonly made of
special Aluminium alloys because these anodes are low in cost and provide
the highest current output per anode weight. Zinc anodes are used on coated
and buried pipelines offshore, where the risk for passivation of Aluminium
anodes is higher due to a lower current density requirement. Zinc and
Aluminium sacrificial anodes used on ship hulls are usually combined with a
paint system. The anodes are placed close to each other on the area around
the propeller because the current could leak to the propeller, and the current
demand is high due to turbulence around this area. Ballast tanks on tankers
and bulk carriers also use Zinc and Aluminium anodes (Bardal, 2004). The
energy content and efficiency of these metals are shown in Table (2.4)
below. Table (2.4) shows the efficiencies of several common anode
materials.

28
 Table (2.4) Efficiencies of Several Common Anode Materials

Each of the anodes have their own limitations. Zinc is more economical to
use than magnesium, but because of the relatively small cell voltage it
produces, it is primarily useful to protect ships in seawater or to prevent
corrosion in systems that require only small currents. Although magnesium
is more expensive and consumed faster than zinc or Aluminium, it provides
the largest potential and current. Aluminium cannot be used in environments
with pH more than 8, since alkaline conditions will make Aluminium self-
corrodes rapidly.

2.7.2.3 Cathodic Protection by Impressed Current (ICCP)

This system uses external source of electricity. High voltage from the
external source is converted to low voltage DC current by means of a
transformer-rectifier. This direct current is impressed between buried anodes
and the structure to be protected. Use of inert anode is preferred, as this will
last for the longest possible time. Typical anodes used are graphite, titanium,
silicon and niobium plated with platinum. The applied current is limited by
electrolyte resistivity and by the anodic and cathodic polarization. Impressed
current system makes it possible to apply the potential level that is necessary
to obtain the current density required by means of the rectifier, whatever the
value of the potential is. Electric current flows in the soil from the buried
anode to the underground structure to be protected. Therefore, the anode is
connected to the positive terminal of the rectifier and the protected structure

29
to the negative terminal. All cables from the rectifier to the anode and to the
structure are electrically insulated. If not insulated, wires from the rectifier to
the anode can act as an anode and deteriorate rapidly, while cables from the
rectifier to the structure may pick up some of the electric current, which
would then be lost for protection (Durham & Durham, 2005). Figure (2.8)
shows impressed current cathodic protection.

Figure (2.8) Impressed Current Cathodic Protection

2.7.2.4 Impressed Current Method Requirements

Metal to be protected and the environment it is exposed to determine the
current density required for complete protection. The applied current density
must always be larger than the current density equivalent to the measured
corrosion rate under the same conditions. Therefore, as the corrosion rate
increases, the impressed current density must be increased to provide
protection. Three factors affect current requirements:

1. The nature of the electrolyte

30
2. Resistivity of the electrolyte.

3. The degree of aeration.

The current requirement increases with increasing acidity of the electrolyte.

For example, surroundings with high resistance have a lower cathodic
current needed to provide protection. The required current to provide

cathodic protection can vary from 5 to 220 mA/m2 of bare surface.

Application of impressed current technique in the real world requires field
testing to determine the necessary current density to provide cathodic
protection in a specific area. The testing techniques are only some way to
obtain approximations. After installation of the system, it is necessary to
conduct a potential survey and make the necessary adjustments to provide
the desired degree of protection (Zakoski, K and Darowicki, 2004).

2.7.2.5 Anode Materials & Surrounding for Impressed Current

System
The determination of anode materials and the surrounding (atmosphere)
material used in impressed current systems in different environments and
applications play a major role, because these anodes are the mean through
which the protective current is delivered to the protected structure or metal.
The type of anode is vital in influencing the reactions on the anode surface.
For consumable metals such as scrap steel or cast iron, the main reaction is
the anodic metal dissolution. Metal dissolution is negligible if the anode has
passive surfaces and the main reactions are gas evolutions. For example,
oxygen is evolved in the presence of water, and chlorine gas is evolved if the
electrolyte contains chloride ions. The gas evolution reactions also happen
on non-metallic conducting anodes surfaces such as graphite. On partially
passive surfaces, both the metal dissolution and gas evolution reactions could
happen. Corrosion product buildup is associated with the metal dissolution
reaction.
31
A wide range of materials can be used for impressed current anodes. The
balance between anode performance and costs play a big role in determining
the right anode material to be used. The following Table (2.5) shows selected
anode materials in general which are used under different environmental
conditions (Shrier .L.L & Hayfield, 1986).

Table (2.5) Anode Materials for ICCP under Different Environments

Atmosphere (Surrounding)

Marine Concrete Potable water soil Pure

liquids
Platinized Platinized High-Si iron Graphite Platinized

surfaces surfaces Iron and steel High-Si cast surfaces

Iron and steel Mixed- Graphite iron //

metal
Anode Materials

Mixed-metal oxides Aluminum High-Si iron //

oxides Polymerized // Mixed metal //

Graphite // // oxides //

Zinc // // Platinized //

High-Si Cr // // surfaces //
cast

iron // // Polymeric, //
iron

32
 // // // steel //

The properties of atmosphere that hold the impressed current anodes are also
important. To increase the effective anode size and lower the resistance of
soil, carbonaceous material such as coke breeze and graphite are used. This
type of atmosphere also reduces consumption of the anode material because
the anodic reaction is transferred from the anode to the holder atmosphere.
Three factors are considered to ensure low resistivity of the surroundings
material

1. Composition.

2. Particle size.

3. Degree of compaction.

The particle size and degree of compaction also influence how anode-
generated gases escape. Since it is quite problematic to properly establish the
above surrounding properties properly in the ground, ready-made anodes and
atmosphere inside metal containers that are factory-prepared according to the
best of the above factors are used. These metal containers will be eventually
consumed under operational conditions. A set of parallel cylindrical anode
rods placed vertically deep underground are commonly used in the industry
(termed vertical deep anode). These provide minimized anode bed resistance
and induced stray currents, smaller right-of-way surface area, and improved
current distribution. However, vertical deep anodes also incur higher capital
expenditure per unit of current output, are difficult to repair in case of any
anode damage, and may block gas generated at the anode from escaping
(PETRONAS, 1987).

33
 Figure (2.9) Ship's Hull with ICCP System

2.8 Bio Fouling

Bio fouling is a complex process which involves the attachment and growth
of a community of organisms on a surface in contact with an aqueous
medium. For the shipping industry in particular, bio-fouling is a critical
problem, leading to the reduction of the maximum speed and upraise of the
fuel and maintenance costs. Consequently, as known, higher fuel
consumption also translates into higher emission of greenhouse gases such as
NOx and SOx. Also, an increase of at least 50% of CO 2 emissions until
2030, under extreme scenarios, was estimated by the International Maritime
Organization (IMO). The settlement and accumulation of marine organisms
also leads to the increase of the drag created between the ships’ hull surface
and the sea water. Drag friction increases up to 40% could be reached.
Figure (2.10) below shows fouling and bio corrosion on the hull of a ship.

34
 Figure (2.10) Fouling and Bio Corrosion on the Hull of a Ship

Bio-fouling is also associated to bio-corrosion of surfaces, reducing the

lifetime of the structures under a marine environment, which is also
promoted by the corrosive effect of sea water itself. Microbiological fouling
should be strictly controlled since it can create Microbial Induced Corrosion
(MIC). For example, Sulphur-reducing Bacteria (SRB) come from the
marine sediment and gain energy using electrons from the steel structures,
chemically reducing the sulphates from the sea water to sulphates, causing
the pitting corrosion of steel surfaces.

Additionally, bio-fouling also contributes to the emigration of certain marine

species to other areas, as occurred in Ponta Delgada, Island, and Portugal,
where alien species of fouling organisms such as barnacles were found.
Amphibalanus Amphitrite was one of the species of barnacles detected and it
is assumed that it is originated from the Indo-Pacific Ocean. Therefore, it is
presumed that due to the fouling propensity of the reported species and given

35
their origin, this reallocation was caused by the increasing boat traffic in the
last years.

2.9 Types of Bio-Fouling

The bio-fouling organisms are classified into two different groups. The
groups are 'Plant Bio-fouling' and 'Animal Bio-fouling'. The following
section elaborates the species of bio-fouling.

2.9.1 Plant Fouling

There are three types of plant fouling species as discussed in the following
subsections: Figure (2.11) below shows plant fouling.

Figure (2.11) Plant Fouling

2.9.1.1 Bacteria and Bacterial Slimes

The bacteria which cause bacterial slimes are present in the sea water all the
year round; they present a major fouling problem as settlement occurs within
minutes of immersion. The slime is generated after the settlement of the
bacteria by secretion of mucus, the species of bacteria being classified by
36
this mucus. Once attached, these bacteria begin to reproduce by cell
division, the daughters not normally being released into the sea water but
being held in the parents' mucilage thus very quickly the slime thickness and
the fouled area increases. The slime thickness can vary from a few microns
to several millimeters depending on the conditions, and this thickness
directly affects the hull surface roughness and reduce the ship power due to
the drag caused by these bacterial slimes. However, these bacterial slimes are
important because they can influence the rate at which toxins are released
from an antifouling coating by forming a diffusion barrier on the surface. But
the slime can also trap spores and larvae of other fouling organisms thus
promoting macro fouling and worsen the roughness of hull surfaces.

2.9.1.2 Diatoms

Diatoms are microscopic plants with a characteristic brown color, they are
similar to bacteria in size and again secrete mucus through their external
siliceous shell although this is less slippery than that produced by the
bacteria to those listed above, and it also affects the hull surface and causes
drag that reduce ship performance.

2.9.1.3 Seaweeds
Diatoms cause similar problems .These are algae and three main classes are
found; namely, green, brown, and red seaweeds .

The commonest species of green seaweed is enteromorpha (seagrass) and

this is found near the waterline forming a carpet up to 10 centimeters thick
and extending to a depth of several meters on the hull. Its success as a
fouling organism stems from its ability to tolerate a wide spectrum of toxins
and also its worldwide distribution. This marine algae exists as long 'grass
like' filaments which contain up to five million cells in an average frond 7-8
centimeters long, each cell being capable of producing eight zoospores
37
(reproductive spores). These spores leave the parent cell as free swimming
zoospores directed by four flagellae, they settle preferentially in surface
irregularities. When the zoospore makes contact with the surface the
flagellae act as brushes and clean the point of settlement, a cement is
released and within seconds the organism is firmly bound to the surface. It is
at this stage that it is most vulnerable to toxins as it is surrounded by only a
thin membrane, but within four hours a protective wall is formed and the
zoospores begin to develop into the mature algae, after a few days it is
already a few millimeters long and a centimeter or more within two weeks.

The most common brown seaweed is ectocarpus which reproduces in a

similar fashion to enteromorpha and again has worldwide distribution. The
plant is composed of two parts, the rhizoidal, a root-like part and an upright
part supporting the spore bearing structure, this being branched and limp.
Each plant is capable of producing 40 x 10 spores and each of these spores
have two flagellae. They swim in the sea until a suitable settlement site is
found (usually in surface defects) where they attach themselves and begin
to develop a protective wall, this occurring at a slower rate than with
enteromorpha; usually taking 24 hours, after which time growth of the new
plant will have started. These seaweeds are found lower down on the hull
than enteromorpha.

The commonest red seaweeds found are ceromium and polysuphonia, their
reproduction and settlement behavior is similar to that described above but
these seaweeds are highly branched and much larger than either of the other
two species; they are found much lower down on the hull where the light
intensity is very low. It has been shown that these fouling organisms, like
the other seaweeds are most vulnerable to toxins during their settlement
period; the resistance of the mature seaweeds to toxins is considerably higher
than that of animal fouling organisms.

38
2.9.2 Animal Fouling
The second type of bio-fouling is 'Animal Fouling' which is sorted into seven
groups: Figure (2.12) below shows animal fouling.

Figure (2.12) Animal Fouling

2.9.2.1 Arthropods

This is a class of the animal kingdom which includes all organisms with
chitinous external skeleton and joined appendages, many of these have a
skeleton which is hardened by calcareous deposits .

The barnacle (cirripedia), of which there are many different types, is the
most common arthropod to be found on a ship's hull. It is a hermaphrodite,
but sexual reproduction is preferred, a sexual reproduction occurring only
under adverse conditions. The eggs are produced in the parent shell, when
the conditions are correct the nauplii )free swimming) larvae are liberated,
and depending on the species they metamorphosize up to eight times, the
39
final transformation producing the cypris (settling) larvae. The cypris
larvae either swim or crawl around until they find a suitable area in which to
settle, this is often a site which has previously been inhabited by a barnacle
community. A protein, arthropodine, is secreted by mature barnacles and it is
this which acts as a reference for renewed settlement.

The settling stage is the most vulnerable period for the young barnacles, the
toxins in conventional anti-fouling coatings effectively kill the majority at
this stage, and hence on recently painted ships there is no serious fouling
problem due to barnacles. If they do survive and grow to their adult form
not only do they cause increased surface resistance but also their shells tend
to cut through the underlying coatings causing a corrosion problem.

A particularly difficult type of barnacle fouling is that produced by the goose

barnacle: its settlement and growth occurring rapidly and vigorously even in
the open sea.

There are many other arthropods found in the sea, these include isopods,
amphipods, crabs, shrimps and insects, but these only foul static structures
and therefore do not present a fouling problem on seagoing vessels.

2.9.2.2 Tubeworms (Annelids)

The coral effect on fouled underwater surfaces results from the activity of
tubeworms. Reproduction can be either sexual which results in free
swimming larvae and thus a new area of infestation, or asexual when the
parent acts as host to the new larvae which eventually bore holes through
the calcareous shell of the parent and grow as new entities although still
attached to the parent. This process produces a random frosted effect on the
surface. As the creature grows the shell is extended; this continues until the
death of the animal, by which time there may be a large hard calcareous
growth which remains attached to the surface and this can only be removed
40
by abrasive treatments such as grit blasting. The presence of tube worms can
be used as a good indication of the state of exhaustion of the matrix toxins in
antifouling paints as they are normally vulnerable to toxins.

2.9.2.3 Mussels (Pelecypods)

The mussel is one of the few shellfish which foul vessels since generally
shellfish are very susceptible to toxins not only during settling but also in the
adult organism. This is due to their method of feeding and also the
susceptibility of the settling larvae to toxins. Many mussels reproduce
sexually although some species are reproduced asexually, the resulting
fertilized eggs being either held within the parent which releases free
swimming larvae or the eggs are liberated into the water and hatch to
produce the free swimming larvae. These larvae initially settle by means of
a foot followed by the formation of a byssus (a web like system of roots)
which firmly secures the adult. Again the shell remains attached to the
surface after the death of the organism and is difficult to remove.

2.9.2.4 Bryozoa

These may be divided into three main groups depending on their pattern of
growth. Encrusting Bryozoa grow over the substrate to produce a network of
shell growth similar to tube worms. Erect Bryozoa grow outwards from the
substrate, and Stolonate Bryozoa have an intermediate pattern of growth.
Reproduction is again sexual or asexual, the fertilized eggs either being
retained by the parent or existing in the sea. Settlement occurs several hours
after hatching, then the adult develops. The most susceptible time for
poisoning Bryozoa is during the settling period, after which time it is
difficult to kill this species of fouling .

2.9.2.5 Sea Squirts

41
These produce free swimming larvae which become attached to a surface before
metamorphosis can occur. The parent is a very lowly form of vertebrate existing as a
sack through which water is filtered. They are not a common fouling organism on
ships as, like mussels, they feed via filtration of water and so are very susceptible to
toxins.

2.9.2.6 Hydroids

The free swimming hydroid larvae, produced either sexually or asexually, cements
itself to a hard surface and grows into the adult. The adult is very firmly attached to
the surface and resembles seaweed; it is quite resistant to toxins unlike the young free
swimming hydroid which is easily poisoned.

2.9.2.7 Protozoa

These are single cell animals which range in size from 0.002 mm to several
centimeters. Their small size and their inability to form large colonies render
them unimportant as fouling organisms. They do however provide, like the
micro fouling organisms in the plant kingdom, sites for settlement of other
fouling organisms.

Generally plants are more resistant to toxins than animals because their
method of feeding involves the absorption of nutrients by osinosis which
prevents the ingestion of the toxin whereas animals take in food and toxins
directly and are therefore more easily killed. The resistance of fouling
organisms to commonly used toxins is shown in Table (2.6) below.

Table (2.6) Resistance of Fouling Organisms towards Toxins

No Resistance Organism

1 Very High Bacteria and Diatoms

42
 Ectocarpus, Enteromorpha, Hydroids, Barnacles and
2 Very High
Polyzoans

3 Moderate and Barnacles Tubeworms, Hydroid

Weeds (Green & Red), Sea Squirts, Mussels and
4 Low
Oysters Sea Squirts and

2.10 Bio-Fouling Mechanism

There are some factors affecting the settlement of fouling organisms; the
more important factors being the geographical location, the season, the
movement of the water relative to the surface, the texture of the surface, the
intensity of illumination and the presence of slime films.

The geographical and seasonal influence are of major importance as the

reproduction of the fouling organism is governed by the water temperature
consequently, in some areas of the world's oceans no fouling may occur
during the winter. The longer the summer season the greater the fouling as
the reproduction of fouling organisms is far more prolific during the warmer
season. Wherever there is a warm water current, excessive fouling can be
expected, as is found in the Gulf Stream. One of the implications of the
geographical and seasonal factors is that it may be necessary to have several
different types of anti-fouling paint that are suitable for the different areas in
which ships operate.

The first step in fouling is settlement and this cannot occur when the ship is
moving above 13 km, thus a stationary ship is an ideal site for fouling. The
majority of fouling occurs when the ship is in harbor, as there is a higher
water temperature, consequently a larger fouling population and the flow of
water past the hull is usually very slow. Ships which spend a very short time
in harbor are found to be relatively free from animal fouling although they

43
have a large amount of plant fouling, this being due to the ease and rapidity
of settlement of the latter.

The surface texture of the coating is important because imperfections in the

surface provide sheltered environments where the fouling organisms can
settle and be protected from the flow of water past the hull. The settlement of
fouling on a moving ship is thought to be due to a combination of static flow
patterns created on certain areas of the ship and also micro fouling
organism's entrapping the settling larvae of macro fouling organisms in their
mucilage, thus enabling the larvae to grow into the adult form.

The light intensity plays an important role in plant fouling as this can only
exist where there is sufficient light to allow photosynthesis to occur.
Consequently the seaweeds requiring most light (green) are found near the
water line, whereas those requiring less light (brown and red) are found
lower down on the hull. Animal fouling is independent of the light intensity
although some animal fouling organisms settle preferentially near the water
line.

2.11 Stages of Bio-Fouling

Bio-fouling is characterized by four main stages throughout the time. The

first stage initiates after the earliest minutes of immersion, where the
physical adhesion of organic molecules of proteins, polysaccharides,
glycoproteins and others, occur. In this stage, Van der Waal’s forces and
electrostatic interactions promote this adsorption phenomenon. The
movement of water leads to the contact and colonization between the
microorganism and the surface. This attachment leads to the second phase,
after 24 hours of immersion, where the reversible adsorption of bacteria and
unicellular algae occurs. Bacteria and other colonizing microorganisms
secrete Extracellular Polymeric Substances (EPS) to enclose and hold

44
the substrate, forming a microbial film. Consequently, the local surface
chemistry is altered, being propitious to stimulate further growth and
settlement of macro-organisms.

This microbial film feeds spores of microalgae, allowing their attachment,

which will constitute a bio-film (1 week, third stage). The bio-film
generated is a mass of microorganisms and the EPS secreted creates a
gel matrix providing enzymatic interaction and high resistance to biocides.
Also, the arrangement of the microorganisms in the biofilm protects
them from the predators and from environmental variations, facilitating
the obtainment of the nutrients necessary for the settlement of other
microorganisms. This bio-film is capable of attracting more particles and
organisms as larvae of marine macro-organisms, characterizing the fourth
stage, after 2 or 3 weeks of immersion. The roughness of the surface
created by the irregular microbial communities will also help the
accommodation of the new attracted organisms. All of these conditions will
contribute to the adhesion and attachment of macro algae and marine
invertebrates.

2.12 Antifouling Coating Formulation and Methods

2.12.1 Coating System

The coating system on a ship is required to prevent corrosion and fouling,

this being achieved by using an anticorrosive paint and an antifouling paint.

2.12.1.1 Formulation of Anti Fouling Paints

There are two sets of criteria which must be applied when formulating
antifouling paints, one set applying to the toxin and the other to the paint
film. With current conventional antifouling coatings toxins are the most
important ingredients, since they are the components which prevent fouling.
They function by controlled release of toxin from the paint matrix into the
45
laminar sub layer thus in theory killing the fouling organism before
settlement. The important characteristics of the toxins are:

A. They should have a low solubility in sea water but, not of course be
totally insoluble,

B. They should have a wide spectrum of toxicity to marine fouling

organisms,

C. They should not create an ecological problem,

D. They should be compatible with the paint medium in which they are
placed and stable,

E. They should be of reasonably low price, and

F. They should not present an application problem .

Many toxins are patented each year most of which are of little use to the
antifouling chemist as the above criteria are not satisfied. The main biocides
which are used in commercially available anti-fouling today are: copper I
oxide, copper I thiocyanate, zinc oxide, and tripheny l tin fluoride, often a
combination of these being used to broaden the range of toxicity of the
coating.

The role of the paint film is that it must be able to release the toxin at a rate
which allows the prevention of fouling, while retaining its structural
integrity so that its ability to adhere to the hull and withstand mechanical
stresses is not reduced .

The paint formulation is dependent on the toxin and also the mode of release
of the toxin. The compounds used in a successful paint formulation have
generally been selected on the basis of a trial and error approach as there is at

46
present no satisfactory method by which the antifouling nature of the paint
can be predicted .

The ultimate test for an antifouling is to paint a ship's hull but prior to this
cheaper and less expensive tests are conducted. Test panels coated with the
new antifouling are immersed in sea water, usually under a raft in an estuary,
the flow of water past these panels simulating the ship's passage through
water. This tests the ability of the coating system to prevent fouling and also
gives a guide to its active life and to the integrity of the film after prolonged
exposure. If a new coating system appears to be promising, the next stage in
testing is to attach coated bilge keel panels to a ship in service, the last stage
before full scale ship trials are test patches (50-100m) painted on various
ships. The expense involved in each of the test methods increases.
Therefore, it is essential that only antifouling which are virtually certain to
prove adequate are applied as test patches. The development of a new
antifouling can take up to six or seven years due to the lengthy testing
periods required.

The leaching of toxins from an antifouling coating can be determined very

easily in the laboratory as can the lethal dose to the fouling organism,
although it is impossible to apply this data to the real situation; generally a
much higher leaching rate is required in practice than would be predicted
on the basis of laboratory estimates. This illustrates that the factors which
influence leaching rates form a complex matrix of interacting physical and
chemical parameters impossible to quantify.

2.13 Antifouling Methods

The advice to protect the ship hulls from marine bio-fouling, to avoid
material damages and excessive fuel consumption, has led to an intensive
research for economical and environmentally friendly solutions. Therefore, a

47
"traditional" and "modern" antifouling methods are elaborated in the
following subsections.

2.13.1 Traditional Antifouling Methods

Marine bio-fouling has been an annoyance for more than 2000 years. At that
time due to the lack of advanced technology and in order to overcome this
problem, natural products were used to resist corrosion and biofouling.

For example, Phoenicians and Carthaginians were said to have used pitch
and possibly copper sheathing on ship hulls, whereas other ancient cultures
used wax, tar and asphalt. The use of coatings made with arsenic and sulphur
mixed with oil were also used to resist shipworms, in the past.

A brief description of the ancient (old) antifouling methods is presented

below:

2.13.1.1 Lead Sheathing

As mentioned above, pitch, copper sheathing, wax, tar, asphalt or a mixture

of arsenic and sulphur with oil, were applied to protect ship hulls.
Alternatively, lead sheathing was also used for this purpose.

Lead sheathing consisted of covering the ship hulls with lead patches in
order to protect them from biofouling and corrosion. Ancient cultures such
as Phoenicians employed this prevention method in 700 B.C., while the
Greeks were reported to use lead sheathing and tar and wax, in the 3 rd (third)
century B.C. Greeks and Romans also used copper nails to secure the
sheathing.

In the period between 45 and 125 A.D., Plutarch mentioned the method of
scraping the ship’s sides to remove weeds, slime and filth, in order to
facilitate the motion of the ship on the water.
48
Later, in 10 A.D, Vikings occasionally used seal tar. From the 13th to 15th
century, the use of pitch was abundant, being sometimes mixed with oil,
resin or tallow.

In the 16th century, lead sheathing was largely adopted, being employed by
Spain, France and England, although wood sheathing was more usual.

However, the British Admiralty discarded the use of lead sheathing, in 1682,
due to the corrosion caused on the iron components of the ships.
Subsequently, lead sheathing was then alternated with wood sheathing. After
applying the latter, it was painted with several mixtures such as tar, grease,
pitch and brimstone and then nailed with large headed copper or iron nails
very adjacently, in order to form a metallic sheathing.

2.13.1.2 Copper Sheathing

The first reference regarding to the underwater use of copper was in 1618,
during the reign of the Danish King Christian IV, who used a coppered keel.

However, the first reference regarding the use of copper as an antifouling

agent was patented by William Beale, who used a mixture of cement,
powdered iron and a copper compound (copper sulphates or copper arsenic
ore).

The use of copper sheathing was firstly reported in 1758 on 'His Majesty's
Ship' (HMS) Alarm frigate, whose success motivated other ships to use
copper, mostly the British Navy, around 1780. The application of copper on
wooden ships was so successful that England prohibited the exportation of
this metal.

Only in the 19th century, Humphrey Davy showed that the fouling
prevention was attained due to the dissolution of copper in the sea water.

49
Anyhow, the use of copper sheathing on iron ships (introduced late in the
18th century) was discontinued, due to the uncertainty of its antifouling
action and corrosion effects on iron.

2.13.1.3 Other Sheathing Elements

Due to the introduction of iron ships and the abandonment of copper

sheathings on this type of boats, more alternatives were tried, to obtain
protection against bio-fouling.

Sheathings of zinc, lead, nickel, arsenic, galvanized iron and alloys of

antimony, zinc and tin and coppered wooden sheathings were the alternatives
tested. Non-metallic alternatives such as soaking felt in tar or using cork,
rubber and plain brown paper were often applied to separate the copper
sheathing from the iron hull. Wooden sheathings were also tested on these
ships, although without success, due to its high cost.

2.13.2. Modern Antifouling Methods: Protective Paints

Novel antifouling systems were developed to overcome the limitations of the

ancient methods. These systems consisted of paints such as enamels,
varnishes, primers, sealers and many others. The majority of antifouling
coatings is mainly composed by a primer (anticorrosive) and a topcoat. The
latter incorporates anti-foulants to protect the hull from bio-fouling.

2.13.2.1 Antifouling Paints

In the mid of 1800, different paints were created, by dispersing a toxicant in

a polymeric base. These toxicants consisted of copper oxide, arsenic and
mercury oxide, whereas the solvents used were turpentine oil, naphtha and
benzene. Linseed oil, shellac varnish, tar and diverse types of resin were
employed as binders.

50
Nevertheless, these paints required the application of a primer in order to
protect the steel hull from the pigments used, since its direct utilization on
the hull caused corrosion.

In the meantime, more paints were launched, such as “hot plastic paints”
consisting of copper sulphates in a metallic soap composition, shellac based
paints (rust preventive) and “cold plastic paints” which used diverse
synthetic resins or natural products either solely or in mixtures. The latter
effectively decreased fouling and were easily applicable due to “airless”
spraying, enabling dry docking periods of up to 18 months.

However, the antifouling industry changed after the Second World War,
leading to the appearance of new synthetic petroleum based resins with
improved mechanical characteristics. Also during this period, organometallic
paints were introduced and contained tin, arsenic, mercury and many others,
which after several developments, led to tributyltin (TBT) based paints. The
TBT based paints revealed to be remarkably efficient against bio-fouling.

Additionally, more paints’ technologies were developed to overcome the

environmental issues of organometallic based paints, and classified
according to the chemical properties of the binder and by their water
solubility: soluble matrix and insoluble matrix paints.

a) Soluble Matrix Antifouling Paints

Soluble matrix antifouling paints contain rosins and their derivatives as

binders and toxic pigments (copper, iron, zinc oxides, arsenic and mercury).
The toxic compounds can dissolve in sea water, forming a thin leached layer
which easily releases the toxic material as the sea water penetrates. The
thickness of the leached layer decreases when the ship speed increases,
which consequently leads to an exponential increase of the release rate. On
the other hand, at static conditions, the settlement of organisms is
51
accentuated and the insoluble salts can block the coating’s pores, which
consequently decreases the release rate of the biocides. In addition, these
paints are less mechanically resistant than the insoluble paints due to the
brittleness of the resin and its instability to oxidation and as consequence, the
life span of these paints is short (12 to 15 months). Nonetheless, they present
the advantage of being easily applied on smooth bituminous-based primers.

b) Insoluble Matrix Antifouling Paints

Insoluble matrix antifouling paints have a polymeric matrix such as acrylic,

vinyl or chlorinated rubber, which are insoluble in sea water. When the
coating is immersed in sea water, the soluble toxic materials dissolve and
consequently leave a multiporous layer known as leached layer, which
enables the further penetration of the water and the release of more
poisonous compounds. The advantage of this type of paint is the high
mechanical resistance and stability to oxidation and photo degradation.
Although the coatings are thick to increase the content of toxic material, at
some stage, the efficiency will decrease due to the gradual release of the
toxic compounds. Consequently, the empty space left by the dissolved
biocides will modify the roughness of the surface and capture pollutants
from the sea water, which will restrain the water penetration and as a result
decrease the release rate, leading to the reduction of the life span of this type
of paint to 12 to 24 months.

c) Tributyltin Self-Polishing Copolymer Coatings

Since the insoluble and soluble matrix paints have some drawbacks,
alternative coatings have been developed in order to improve these paints.

The first tributyltin self-polishing copolymer (TBT-SPC) technology was

patented by Milne and Hails, in 1974, revolutionizing the entire shipping
industry. Organic tin and its derivatives have been generally used as
52
antifoulants due to their broad-spectrum characteristic. Tributyltin oxide
(TBTO) and tributyltin fluoride (TBTF) were the organotin compounds used,
also known as powerful fungicides, completely capable of inhibiting the
growth of most fouling organisms at a very low concentration.

As known, every paint contains pigments to confer the desired color.

Usually, metallic copper, copper thiocyanate and cuprous oxide are the
dominant copper pigments used in antifouling paints. However, the copper
ions as Cu2+ have a major role in antifouling, yet they can only target
specific fouling organisms.

TBT-SPC paints were based on acrylic polymer (usually methyl

methacrylate) with TBT groups tethered to the polymer backbone by an
ester. When immersed in water, the soluble pigment particles such as zinc
oxide (ZnO) or copper oxide (CuO) would begin to dissolve.

The water penetration was prevented by the hydrophobic nature of the

polymer of TBT methacrylate and methyl methacrylate. Thus, the water
could only fill in the pores created by the dissolution of the soluble pigment
particles. Furthermore, the carboxyl-TBT bond is easily hydrolyzed in
slightly alkaline environments as sea water (pH of 7.5 to 8.5), which slit the
TBT portion from the copolymer and then released the biocides into the
water. As the TBT portions were split, the partially reacted brittle polymer
backbone became prone to be washed off by the moving sea water, exposing
a fresh coating surface. The hydrolysis process provided a low hull
roughness (about 100 μ m), which did not influence significantly the drag
friction of the ship’s hull.

One of the advantages of this kind of coating was the control of the polishing
rate by the manipulation of the polymer chemistry, being possible to balance
the high effectiveness and a long life span in function of the ships’ operating

53
conditions and sailing speed. Studies have proven that the release rate of
TBT in the sea water is almost constant with the sailing speed, which confers
a high antifouling performance even at static or low speed. Additionally,
TBT-SPC paints had high mechanical resistance, high stability to oxidation
and short drying times.

This type of paint was widely applied in the shipping industry due to its high
efficiency and versatility.

Consequently, the extensive use of TBT introduced high levels of

contamination in the environment and thus negatively affected the marine
communities. TBT is extremely toxic to non-target organisms ranging from
bacteria to fish and mammals, affecting their growth, development,
reproduction and survival. For example, before the 1980’s, populations of
gastropods were ceased due to the presence of TBT compounds in the sea
water. This disappearance is explained by the fact that TBT causes a
hormonal imbalance, which leads to the development of male sex organs on
female gastropods, which hinders the breeding of gastropods.

In 2001, IMO (International Maritime Organization) (IMO) banned the use

of TBT in the manufacturing of paints from 1st January 2003 and the
presence of these paints on ship hulls from 1 st January 2008. However, this
ban did not apply to copper, since it is an essential element needed for the
growth of all plants and animals, besides being naturally present in the sea
water. It is also lipophilic and thus less bio accumulative. Nevertheless, it is
possible that copper based paints may end up facing the similar regulations
as TBT. For instance, Sweden, Denmark and USA are planning to strengthen
the legislations regarding the use of copper-based antifouling paints, since
the excessive boat traffic can lead to the contamination of the marine
environment.

54
2.13.2.2 Environmentally Friendly Antifouling Paints

Due to the ban of the most efficient and versatile TBT-SPC paints, the paint
producers felt the urge to develop new and less environmentally harmful
paints. Therefore, Tin-free SPC technology was developed and commercially
introduced.

The tin-free coatings can be divided into three categories: tin-free controlled
depletion paints (tin-free CDPs), tin-free self-polishing copolymers (tin-free
SPCs) and hybrid paints (conjugation between the CDPs and SPCs).

Despite the fact that these paints are free of TBT, their mechanism consists
of biocide release, whose action has not always been fully explained.
Considering this, the development of fully biocide-free antifouling paints is
still in course.

a) Tin-Free Controlled Depletion Paints (Tin-Free CDPs)

The tin-free CDPs are an improved version of the traditional soluble matrix
paints, where organically synthetized resins reinforce the binder, although
presenting the same antifouling mechanism as the conventional rosin matrix
paints. The synthetized resins are more resistant than rosins and control the
dissolution of the soluble binder.

These paints are also known as ablative/erodible paints, containing

polymeric compounds capable of controlling the relative rate of
dissolution/erosion. They also contain a large proportion of a non-toxic
binder, which is soluble in sea water. The biocide content is high and
dissolves in the sea water, in conjunction with the soluble binder. The rate of
erosion becomes constant after short time of immersion.

55
However, these paints transform into an empty matrix, due to the dissolution
of the soluble compounds incorporated in the paint into the sea water,
affecting their behavior. Consequently, a high amount of copper and co-
biocide is needed, which rises the concern towards the environment. Also, as
the compounds dissolve, the roughness of the coating increases, thus
promoting biofouling formation. The leached layer formed may be removed
prior to recoating.

Regarding to the lifespan of these paints, these confer a protection a bit

longer than 3 years. They do not require a tie coat when repainted and are
less expensive than TBT-based self-polishing paints.

Usually, leisure boats and small ships with short service time apply these
paints.

b) Tin-Free Self-Polishing Copolymer Paints (Tin-Free SPCs)

The tin-free SPCs contain an acrylic copolymer matrix combined with

booster biocides, where different pendant groups are linked to the polymeric
backbone and released after the contact with sea water. This process
resembles the hydrolysis of TBT-SPC paints.

In this type of paint, the antifouling activity is induced as the chemical reaction through
hydrolysis of copper, zinc or silyl acrylates occurs, forming an acidic polymer, which
is soluble in sea water and can be washed from the surface.

The hydrolysis process is followed by the loss of the dissolved layer of polymer,
smoothening the surface.

These paints present a life span 3 to 5 years, due to their high polishing rate. Anyhow,
they are not as efficient as TBT-based-self-polishing paints.

56
For instance, when insoluble Zn acrylate is used, it hydrolyzes to soluble acidic
polymer and the following reaction is assumed:

-
Polymer−COO−Zn (solid)–X + Na+→Polymer−COO−Na (solid) +X + Zn2+

The Zn2+ is released into the sea water for antifouling properties and the soluble acidic
polymers can be washed from the surface. Currently, metallic copper, copper
thiocyanate and cuprous oxide are the dominant compounds used in antifouling paints.

In comparison with the TBT antifouling paints and as mentioned before,

copper-containing coatings can only target specific fouling organisms. To
improve the antifouling properties and thereby the selectivity to macro algae,
barnacles and bryozoans, booster biocides such as Irgarol 1051, Diuron,
copper pyrithione, zinc pyrithione, isothiazolone, Zineb, Econea and many
others are added, as an alternative to TBT derivatives. Although the toxicity
of the majority of the biocides aforementioned has not been fully assessed,
zinc pyrithione and Zineb seem to be the least toxic, whereas Irgarol and
Diuron are reported to be more poisonous.

a) Hybrid Paints

The antifouling mechanism of hybrid paints is a conjunction of the

mechanisms of both CDPs and TF-SPCs. The leached layer, cost and the
performance of these paints is intermediate.

An example of these hybrid paints are the microfibers incorporated in paints,

by Hempel.

b) Biocide-Free Coatings

Due to the toxicity of the biocides used in the antifouling paints, novel
biocide-free technologies have been investigated to replace the biocide based
coatings.
57
Non-stick “fouling-release” coatings, containing fluoro polymers and
silicone, have been tested regarding to the release of macro fouling
organisms, using robust hydrodynamic conditions. Apparently, fluoro
polymers and silicone appear to possess the desired properties to promote
antifouling by release. Some low surface energy coatings have also been
prepared with modified acrylic resin and nano-SiO2. Moreover, accumulated
fouling organisms are not easily released, being difficult to develop an
environmentally friendly and simultaneously effective coating.

Additionally, these methods have some drawbacks such as high cost, poor
mechanical properties and the difficulty of recoating.

Recently, researchers have been focusing in combining “fouling-release”

coatings with hydrogel technology. For example, Hempel has been investing
in this technology by modifying the surface of commercial PDMS
(polydimethylsiloxane) coatings in order to generate a hydrogel in contact
with water, with weak adhesion properties. This layer promotes its
detachment from the former paint layer together with any attached bio-
fouling (e.g. slime or algae) on the coating. Experiments were also
performed on ships, showing that this new coating is able to keep the surface
clean even at low speeds.

In summary, despite the fact that hydrogel based “fouling-release” coatings

are showing positive results on the bio-fouling prevention, their durability
and effect on the environment are still unknown, which should motivate a
deep research in this field in order to develop an effective, durable and non-
toxic coating.

For this purpose, advanced characterization techniques should be performed

to evaluate the mechanical characteristics and the environmental

58
compatibility, to proceed to further improvements and finally introduce new
potential benign products in the market.

2.14 Characteristics of Antifouling Paints

After developing the desired polymeric matrix of the coating, it is

necessary to proceed to characterization tests in order to check if the
coating is in accordance with the standards.

Generally, the requirements for an optimal antifouling coating consist of

being anticorrosive, environmentally acceptable, economically viable,
durable, smooth, compatible with the underlying system, resistant to
abrasion, biodegradation and erosion.

2.14.1 Anti-Corrosiveness

If the substrate (ship's hull) is steel, the paint should protect it from corrosion
caused by the exposure to the marine environment.

To prevent this problem, at least one coating of primer or anticorrosive paint

is applied before the layer of antifouling paint. The latter may contribute
materially to the protection of the hull from corrosion, depending
primarily on the thickness of the antifouling coating and its resistance
to the ingress of sea water. Thus, thick paints impede corrosion and provide
the necessary toxic storage for extended fouling prevention. The adequate
thickness is generally specified by the paint providers in the technical data
sheet of the product. For instance, Jotun’s antifouling paints’ thickness
ranges from 75 to 150 μ m, whereas the primers’ thickness ranges from 40 to
250 μ m.
Also, the chemical compounds added into de coating should be taken into
account, since they might tend to quicken the corrosion effect. For instance,
common toxic pigments such as metallic copper and salts of copper and

59
mercury have the tendency to intensify corrosion if they are applied directly
on the hull.

2.14.2 Durability

The durability of a coating is dependent on its resistance to

mechanical damage, on the erosion caused by the water motion and
on the components present in the paint formulation. If it contains any
biocide, the coating disintegration must be also taken into account, since it
degrades as the sea water penetrates and releases the toxic biocide.
Therefore, a balance between toxicity and durability should be established.
The resistance to the erosive effect of the water motion is a notable problem
in high speed vessels, such as motor torpedo boats and hydroplanes.
Considering this, it is necessary to develop suitable paints, which can confer
a hard and thus resistant surface to overcome this drawback.
The loss of durability is more accentuated near the waterline, due to the
mechanical dam age caused by the floating debris and the alternation
between the wet and dry conditions and also due to the exposure to the sun.
These factors intensify the coatings’ cracking, being necessary to develop a
paint which can resist all of this harm.

2.14.3 Adhesion
The adhesion is an important property, since the paint should adhere
adequately to the substrate where it is applied, regardless of the natural
conditions existing during this procedure. This means that the paint should
adhere suitably either when it is applied during winter (high moisture and
low temperature) or summer (low moisture and high temperature).
Low adherence may lead to the disintegration of the coating and therefore
exposes the hull to the marine environment, leaving it unprotected.

2.14.4 Abrasion
60
The assessment of the abrasion resistance of antifouling paints is a relevant
factor, since it can indicate the paints’ resistance to friction caused by
moving particles transported by the wind or water. These particles can erode
the paint, when the ship is in motion or in the port, compromising the
durability of the coating.

2.14.5 Smoothness

The paint must be applied uniformly to confer a smooth surface, which,

therefore, will create less frictional drag and bio-fouling attachment.
Additionally, it is also desirable that paints with a high viscosity (needed to
form thick coatings( have sufficient elasticity to fill up the minor
irregularities present on the ship’s surface.

2.14.6 Drag Friction

As known, a ship must be designed to move efficiently through the water
with a minimum of external force. However, when it is propelled through the
water, it has drag associated with it, which must be overcome by thrust to
move forward.
Drag is defined as the force that opposes forward motion through the fluid
and is parallel to the direction of the free-stream velocity of the fluid flow.
When moving on the water, the drag of a ship presents two major
components: wave-making drag and skin frictional drag. The frictional
drag typically accounts 60-90% of the total resistance and can be
reduced by applying an appropriate surface coating, which softens the
surface. The roughness of the surface and, thereby, the frictional resistance
is influenced by different factors such as the age or condition of the ship hull,
the surface preparation, the paint application, the paint system and marine
fouling.
The skin frictional drag is increased when microbial communities, present in
the sea, attach to the surface of the coating, leading to extreme fuel and
61
maintenance costs of the ships and CO2 emission. Several papers have
studied the effect of marine fouling on the hydrodynamic performance of a
surface. For example, Bohlander (1991) performed full scale power
trials on a frigate and concluded that microfilms of bio-fouling increased
the drag friction by 8 to 18%.
For this purpose, it is of utmost importance to assess the coating regarding
the drag friction effect, to avoid excessive fuel consumption and subsequent
penalties .
Several experiments have been applied to measure the drag friction of the
coatings, including a rough plate or a rotating disc or cylinders.
It is important to mention that the selection of the coating type does
influence the drag friction effect. Several studies have been carried out to
compare the drag resistance of silicone based “foul release” coatings with
tin-free self-polishing coatings. The former has shown positive results in
comparison with the latter, mainly due to its surface texture (less rough).

2.14.7 Wettability

The wettability of a solid by a liquid can be determined by measuring the

contact angle (or wetting angle), ϴ. The contact angle is described as the
angle between the surface of the liquid and the outline of the contact surface,
when an interface between a liquid and a solid exists.

2.15 Environmental Risk Assessment

Since the main mechanism of action of the majority of antifouling paints

consists of releasing biocide into the sea water, a severe environmentally
compatibility assessment should be carried out before the introduction of
these paints in the market.
After the ban of TBT based paints, alternative biocides have been used in
conjunction with copper, which can be less or equally harmful .

62
For instance, the leaching of copper from the antifouling paints on Swedish
boats tends to be harmful to the Baltic Sea’s key-species bladder wrack
and Fucus vesiculosus, leading the Swedish Chemicals Agency to restrain
the use of paints leaching excessive copper and prohibit copper based paints
on leisure boats (length < 12 m).
Another example is regarding a study carried out in Hong Kong, which
consisted of testing the toxicity of five commonly used booster biocides
(Irgarol, Diuron, Zinc pyrithione, Copper pyrithione and Chlorothalonil) on
the growth or survival of 12 marine species, concluding that Irgarol is even
more toxic than TBT and copper pyrithione is as toxic as TBT.
Considering this, it is important to perform an accurate evaluation of the
environmental risks that these paints can pose to the marine species, by
carrying out biodegradability tests or mechanical tests that enable the
collection of leachates for toxicity analysis.

2.16 The Hull Friction (Drag) and Roughness

The frictional resistance to a ship's movement through water (Drag). The

total resistance to a ship's movement through water is normally defined as
the force required to tow a ship at a given speed in calm waters. The total
resistance is the sum of the frictional resistance and the residual resistance,
the latter being a feature of the ship's design whereas the former is due to the
tangential shear forces caused by the movement of water parallel to the ship's
hull. It can be seen that only the frictional resistance can be influenced by the
surface coatings or surface treatment.

In 1874 Froude showed experimentally that the frictional resistance for

towed planks could be expressed by the equation:

Rf = f.s.vn

63
Where R f = frictional resistance, f = frictional coefficient, s = the wetted
surface area, v = the velocity, and n = a number nearly equal to 2.

From the results Froude obtained that it was obvious that the frictional
resistance depends on the nature of the surface, the values of n being very
nearly equal to two whereas the values of ' f ' varied greatly depending on the
smoothness of the surface; these observations were not utilized until well
into the twentieth century.

2.16.1 Flow around a Ship's Hull

The resistance caused by the flow of water around a ship's hull, the residual
resistance, is governed by the hull geometry and operational speeds, this can
be approximated to the flow around a plane plate for which the formulation
below is applicable:

V1
Re =
Ó

Where v = the velocity of the flow past the hull, 1 = the distance from the
bow of the ship and Ó = the kinematic viscosity which is the ratio of the
viscosity to density, the units being Stokes and the dimensions being 1 2t -1.

"Re" is called the Reynolds Number a dimensionless parameter, which

provides a useful indicator of the type of flow around the hull: when its value
7
is below 5 x 105 laminar flow is observed, whereas at a value ≥ 10 the flow

is turbulent, 5 x 105 and 107 are critical values of "Re" between which the
flow changes from laminar to turbulent.

It has been shown by Izubuchi from tests on the Japanese destroyer 'Yudachi'
that at normal operating speeds the residual resistance forms a relatively
small proportion of the 0 total resistance. These results were in agreement
64
with those obtained by the U.S. Navy using the U.S. Destroyer 'Hamilton' as
the test craft. More recent work has demonstrated that the relative
contribution of each of these resistance components to the total resistance
depends on both the size and the speed of the vessel.

The reduction of frictional resistance is of major importance for efficient

operation, the residual resistance only becomes important at relatively high
operating speeds and is affected by the design and building of the vessel;
most commercial vessels operate in the 10-20 KN range. A vast amount of
research has been and continues to be conducted on design whereas, the
frictional resistance can be very significantly lowered, with consequent
economic benefit, by the application of a high performance antifouling.

The water around the hull of a ship moving at low speed can be divided into
two parts; a laminar sub layer which is a continuous layer of water adjacent
and parallel to the ship's hull and moving with the ship, the thickness of this
layer being dependent on the speed of the ship; at greater distance from the
hull flow becomes turbulent due to the shear forces created by the passage of
water around the hull; the faster the ship moves the thinner the laminar sub
layer. At a low Reynolds Number for a given ship operating under standard
conditions a relatively thick laminar sub layer is present, with increasing
speed (and therefore increasing Reynolds Number) the thickness of the
laminar sub layer decreases and between certain Reynolds Numbers the
laminar sub layer becomes discontinuous.

The smoother the hull, the lower the kinematic viscosity and so the greater
the Reynolds Number. The increase in resistance created by turbulent flow
(i.e. the energy required to produce turbulence) is thus related to the surface
roughness and is directly proportional to the Reynolds Number.

65
A surface is considered to be rough if the peaks of roughness protrude
through the thickness of the laminar sub layer, if the peaks are smaller and
remain within the laminar sub layer the surface is considered to be hydro
dynamically smooth.

The thickness of the laminar sub layer is dependent on the velocity of the
hull and it has been determined that for a ship operating at V knots a hydro
dynamically smooth hull occurs when the surface roughness is less than or
230
equal to µ. This criterion is very rarely satisfied even for a freshly
V
painted hull.

2.16.2 Sources of Hull Roughness

Hull roughness is directly related to the frictional resistance and may be

affected by numerous factors, these being described in the following
sections.

2.16.2.1 Structure of the Paint

As a consequence of the cost of dry docking and repainting, ship owners

have sought shorter dry-docking times.

This has led paint manufacturers to compromise between adhesive paints

that spray smoothly, but sag easily when sprayed thickly, and thixotropic
paints which tend to ripple on the surface but can be applied in thicker coats
without sagging. Both of these paint systems cause hull roughness, the
former being less than the later.

2.16.2.2 Inadequate Surface Preparation

The removal of fouling organisms and the repair of surface defects to

provide a smooth finish to which the new antifouling is to be applied is of

66
major importance in producing a smoothly painted hull. This, however, is
not always realized because of the cost of preparation, consequently in many
instances surface roughness is built in this way, the roughness increasing
with each repainting.

2.16.2.3 Poor Application Standards

The application of any coating system is really a skilled job but due to
working conditions and pay, the average worker is either unskilled or
untrained and consequently the manufacturer ~ spraying instructions are
often not followed closely. The environment also plays an important role; for
example, variations in humidity and wind speed can result in poor
application.

2.16.2.4 Failure of the Paint System

This occurs when the ship is in service and the main problems are: blistering,
detachment and corrosion.

2.16.2.5 Mechanical Damage

This includes berthing and grounding damage as well as that incurred from
cable chafing.

2.16.2.6 Fouling

This is the major cause of hull roughness, it is caused by an ineffective or

exhausted antifouling coating, thus the roughness caused by fouling
increases with time.

2.17 Measurement of Hull Roughness

67
Surface roughness of a ship's hull is expressed as the maximum peak height
to minimum valley depth over a distance of 50 rom, this is more commonly
known as the mean apparent amplitude or MAA per 50 mm. This method of
measurement gives reasonable correlation between hull roughness and ship's
resistance.

Many instruments are available to measure surface roughness in the

laboratory, Talysurf, Surfometer, Electron Microscope, etc. but it is only
recently that the British Ship Research Association (BSRA} have developed
an instrument which can measure the surface roughness of a ship's hull in dry
dock. The instrument (B.S.R.A. Roughness Gauge) consists of three wheels
supporting a carriage through which protrudes a stylus. When the apparatus
is pushed across the hull the stylus records the surface profile. The gauge's
sample length is 50 mm and it measures the maximum peak to minimum
trough distance.

This apparatus gives reasonable correlation with the standard laboratory

instruments but it does not account for waves with a large wavelength as the
sampling distance per measurement is too short and there is no fixed
reference.

The results obtained by measuring a ship's roughness have to be corrected

for defects which cause residual resistance, i.e. plate curvature, welds, etc.
and then the surface roughness of the hull may be calculated, this being
displayed usually as a histogram.

To measure the ship's roughness in practice the hull is divided up into

sections and each section is measured using the B.S.R.A. gauge before
painting, the same procedure is followed after painting, sufficient
measurements being taken to ensure a random sampling. The data may then

68
be correlated to the ship's performance before and after painting to provide
evidence for the increased fuel consumption due to surface roughness.

Scott has shown that the cost of surface roughness for a typical ship results
in a one per cent increase in power to maintain the ship at a constant speed
for every 10µ of roughness above 100µ. The surface roughness of a new ship
is generally about 130µ, this figure increasing with service time for a ship
painted with a conventional anti-fouling preparation as was shown by the
Norwegian Ship Research Institute.

69
 Chapter Three

Research Methodology

3.1 Introduction

This chapter deals with methods of data collection on the phenomenon of

vessels hull protection. It gives an overview about the case study to show
how ship's hull corroded in Sudan Navy, Red Sea State (Port Sudan). Then,
it shows the suggested method of corrosion protection using Impressed
Current Cathodic Protection (ICCP). Finally, the chapter shows the
procedures of designing ICCP system using multi physics software program
(Comsol 5.3a).

3.2 A Case Study

This study is intended to investigate the problems of corrosion on vessels

hull. A case study is taken from Sudanese's Navy. The ship type called
Zamzam which is considered as an arbitrary model affected by corrosion.
The ship's hull is made of naval iron. The length of the ship is 42 meters
and the width is 4 meters. Also, the ship type called Almaz is taken as a case
study due to its massive affection by corrosion. They are three in number
constructed of naval iron. The length of the ship is 41 meters and the width
is 4.8 meters.

3.3 Methods

The research use two different methods to conduct the study. The first
method used in this study is Impressed Current Protection modeling
simulation using (Comsol 5.3a) program. Impressed Current Cathodic
Protection (ICCP) is a commonly employed strategy to mitigate ship hull
corrosion, by which an external current is applied to the hull surface,
70
polarizing it to a lower potential. Although there are various parameters such
as salinity, temperature, hull surface coating that contribute to the demand
for current, the area of bare metal (mainly propeller) is the most governing
parameter. In this model, ship's hull structure represent (Cathode), the sea
water represent the surrounding atmosphere, and anode boundaries i.e. a
metal which is higher in potential than the Cathode (Hull) are used. The
second method is coating. The researcher created the program to show the
effect of ICCP system for coated and non-coated structure. Figure (3.1)
below shows ICCP system.

Figure (3.1) ICCP System

3.4 Program Parameters

The researcher used the following parameters to design the ICCP model to protect the
ship's hull efficiently and effectively. Table (3.1) below shows ICCP Parameters.
71
 Table (3.1) ICCP Parameters

Name Expression Value Description

Ship hull potential vs reference,
Evsref -0.85[V] −0.85 V
imposed by ICCP system
sigma 4[S/m] 4 S/m Sea water conductivity
Equilibrium potential of propeller
Eeq_prop -0.31[V] −0.31 V
vs. Ag/AgCl
1.5E- Exchange current density of
i0_prop 0.15 A/m²
02[mA/cm^2] propeller
Anodic transfer coefficient of
alphaa_prop 0.78 0.78
propeller
Cathodic transfer coefficient of
alphac_prop 0.45 0.45
propeller
Equilibrium potential of shaft vs.
Eeq_shaft -0.18[V] −0.18 V
Ag/AgCl
1.3E-
i0_shaft 0.0013 A/m² Exchange current density of shaft
04[mA/cm^2]
alphaa_shaft 0.44 0.44 Anodic transfer coefficient of shaft
alphac_shaft 0.57 0.57 Cathodic transfer coefficient of shaft
ilim 5[A/m^2] 5 A/m² Limiting current density at cathodes

3.5 Procedures
The research creates the Impressed Current Cathodic Protection simulation
through metaphysics software program (comsol 5.3a). The procedures are as
follows:

3.5.1 Create Corrosion Model Wizard

In the New window Comsol 5.3a program, click Model Wizard to build the
Corrosion Model: 1. In the Model Wizard window, click 3D. 2. In the Select
Physics tree, select Electrochemistry> Primary and Secondary Current
Distribution>Secondary Current Distribution (cd). 3. Click Add. 4. Click
Study. 5. In the Select Study tree, select Preset Studies>Stationary. 6. Click
Done.

72
3.5.1.1 Build Ship Hull Geometry
To build the geometry of the ship hull from a geometry file:

a. Import 1 (imp1) geometry file

1. On the Home toolbar, click Import. 2. In the Settings window for Import,
locate the Import section. 3. Click Browse. 4. Browse to the model’s
Application Libraries folder and double-click the file
ship_hull_geometry.mphbin. 5. Click Import.

b. Mesh Control Faces 1 (mcf1)

The geometry is divided into two domains, use a mesh control face to
remove this split when setting up the physics. This will reduce the number of
geometry entities that can be selected when setting up the physics. 1 On the
Geometry toolbar, click Virtual Operations and choose Mesh Control Faces.
2 On the object fin, select Boundaries 9–12 and 15 only. 3 On the Geometry
toolbar, click Build All. 4 Click the Transparency button on the Graphics
toolbar. 5 Click the Zoom Extents button on the Graphics toolbar. The
geometry should now look like Figure 1 (see chapter 4). Select Zoom Box
and a region closer to propeller. The zoomed in geometry should now look
like Figure 2 (see chapter 4).

3.5.1.2 Global Definitions

Parameters: Load the Model Parameters

1. In the Model Builder window, under Global Definitions click Parameters.

2. In the Settings window for Parameters, locate the Parameters section. 3.
Click Load from File. 4. Browse to the model’s Application Libraries folder
and double-click the file ship_hull_parameters.txt.

73
Definitions

Create explicit selections for the propeller base, propeller blades, shaft,
anode, reference electrode and hull surfaces. Then create a selection for the
ship hull surface by using a union. The selections will be used later on when
specifying the physics, setting up the mesh and when plotting and evaluating
the results.

Explicit 1

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 19-21 in the Selection text field. 6. Click OK. 7. Right-click
Explicit 1 and choose Rename. 8. In the Rename Explicit dialog box, type
Propeller base in the new label text field. 9. Click OK.

Explicit 2

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 22, 24-25, and 39-40 in the Selection text field. 6. Click
OK. 7. Right-click Explicit 2 and choose Rename. 8. In the Rename Explicit
dialog box, type Propeller blades in the new label text field. 9. Click OK.

Explicit 3

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 37, 38 in the Selection text field. 6. Click OK. 7. Right-click

74
Explicit 3 and choose Rename. 8. In the Rename Explicit dialog box, type
Shaft in the new label text field. 9. Click OK.

Explicit 4

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 17 in the Selection text field. 6. Click OK. 7. Right-click
Explicit 4 and choose Rename. 8. In the Rename Explicit dialog box, type
Anode in the new label text field. 9. Click OK.

Explicit 5

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 18 in the Selection text field. 6. Click OK. 7. Right-click
Explicit 5 and choose Rename. 8. In the Rename Explicit dialog box, type
Reference electrode in the new label text field. 9. Click OK.

Explicit 6

1. On the Definitions toolbar, click Explicit. 2. In the Settings window for

Explicit, locate the Input Entities section. 3. From the Geometric entity level
list, choose Boundary. 4. Click Paste Selection. 5. In the Paste Selection
dialog box, type 6-14, 16, 23, 26-36, 41, 43-46 in the Selection text field. 6.
Click OK. 7. Right-click Explicit 6 and choose Rename. 8. In the Rename
Explicit dialog box, type Hull surface in the new label text field. 9. Click
OK.

Union 1

75
1. On the Definitions toolbar, click Union. 2. In the Settings window for
Union, locate the Geometric Entity Level section. 3. From the Level list,
choose Boundary. 4. Locate the Input Entities section. Under Selections to
add, click Add. 5. In the Add dialog box, in the Selections to add list, choose
Propeller base, Propeller blades, Shaft, Anode, Reference electrode, and Hull
surface. 6. Click OK. 7. Right-click Union 1 and choose Rename. 8. In the
Rename Union dialog box, type Ship surface in the new label text field. 9.
Click OK.

Union 2

1. On the Definitions toolbar, click Union. 2. In the Settings window for

Union, locate the Geometric Entity Level section. 3. From the Level list,
choose Boundary. 4. Locate the Input Entities section. Under Selections to
add, click Add. 5. In the Add dialog box, in the Selections to add list, choose
Propeller base, Propeller blades, and Shaft. 6. Click OK. 7. Right-click
Union 2 and choose Rename. 8. In the Rename Union dialog box, type
Propeller and Shaft in the new label text field. 9. Click OK.

3.5.1.3 Secondary Current Distribution (Cd)

Now, set up the Secondary Current Distribution interface for the case of a
coated propeller. Start with the electrolyte conductivity.

Electrolyte 1

1. In the Settings window for Electrolyte, locate the Electrolyte section. 2.

From the σl list, choose User defined. In the associated text field, type
sigma.

Reference Electrode 1

76
The ICCP system will control the potential of the ship hull vs a reference
electrode, located at mid-ship. In this model we set all Equilibrium potential
with reference to Ag/AgCl. The equilibrium potential of this reference is
hence 0. 1. On the Physics toolbar, click Points and choose Reference
Electrode. 2. Select Point 49 only.

Electrolyte Potential 1

In this model we will not explicitly define the anode reaction kinetics.
Instead we will use a potential (primary) condition for the anode potential
and ground it to zero. The value of the anode electrolyte phase potential is
arbitrary since we will define the ship hull potential with respect to the
reference electrode. 1. On the Physics toolbar, click Boundaries and choose
Electrolyte Potential. 2. In the Settings window for Electrolyte Potential,
locate the Boundary Selection section. 3. From the Selection list, choose
Anode.

Electrode Surface 1

Now specify the electrode potential and the kinetics for the shaft surface. 1.
On the Physics toolbar, click Boundaries and choose Electrode Surface. 2. In
the Settings window for Electrode Surface, locate the Boundary Selection
section. 3. From the Selection list, choose Shaft. 4. Locate the Boundary
Condition section. From the Boundary condition list, choose Electrode
potential. 5. In the Evsref text field, type Evsref. 6. From the φs,ref list, choose
Electric reference potential (cd/refel1).

Electrode Reaction 1

1. In the Model Builder window, expand the Electrode Surface 1 node, then
click Electrode Reaction 1. 2. In the Settings window for Electrode Reaction,
locate the Equilibrium Potential section. 3. In the Eeq text field, type

77
Eeq_shaft. 4. Locate the Electrode Kinetics section. From the Kinetics
expression type list, choose Butler-Volmer. 5. In the i0 text field, type

i0_shaft. 6. In the αa text field, type alphaa_shaft. 7. In the αc text field, type
alphaa_shaft. 8. Select the Limiting current density check box. 9. In the ilim
text field, type ilim.

Definitions

The Electrode Surface node will declare a global variable (cd.phis_eebii1)

for the electron phase potential of the ship hull. Now add a variable to for the
ship hull potential as measured vs a reference electrode located in the
electrolyte. The variable will be used later for post processing of the
solution.

Variables 1

1. In the Model Builder window, under Component 1 (comp1) right-click

Definitions and choose Variables. 2. In the Settings window for Variables,
locate the Variables section. 3. In the table, enter the following settings:

Name Extension Unit Description

E_hull

4. Locate the Geometric Entity Selection section. From the Geometric entity
level list, choose Boundary. 5. From the Selection list, choose Ship surface.
6. Locate the Variables section. In the table, enter the following settings:

Name Extension Unit Description

E_hull .phis_eebii1-phil V Hull potential vs Ag/AgCl

Secondary Current Distribution (Cd)

78
 Add an Infinite Electrolyte to describe an infinite extension of the
electrolyte. Use symmetry planes to describe the ocean surface and the mid-
ship symmetry planes.

Infinite Electrolyte 1

1. On the Physics toolbar, click Boundaries and choose Infinite Electrolyte.

2. Select Boundaries 1–3 and 5 only. 3. In the Settings window for Infinite
Electrolyte, locate the Electrolyte section. 4. In the σl text field, type sigma.
5. Click to expand the Symmetry planes section. Locate the Symmetry
Planes section. Select the yz-plane check box. 6. Select the xy-plane check
box.

No more boundary conditions are needed for study with the coated propeller
since Insulation condition is applied by default, including the coated
propeller surfaces.

Initial Values 1

Provide an initial value for the electrolyte potential to reduce the

computational time. 1. In the Model Builder window, under Component 1
(comp1)> Secondary Current Distribution (cd) click Initial Values 1. 2. In
the Settings window for Initial Values, locate the Initial Values section. 3. In
the phil text field, type 0.5.

Mesh 1

Build a mesh with a finer resolution at the propeller, shaft and hull surface.
Mesh the domain around the propeller first.

Free Tetrahedral 1

79
1. In the Model Builder window, under Component 1 (comp1) right-click
Mesh 1 and choose Free Tetrahedral. 2. In the Settings window for Free
Tetrahedral, locate the Domain Selection section. 3. From the Geometric
entity level list, choose Domain. 4. Select Domain 2 only.

Size 1

1. Right-click Component 1 (comp1)>Mesh 1>Free Tetrahedral 1 and

choose Size. 2. In the Settings window for Size, locate the Element Size
section. 3. From the Predefined list, choose Extra fine. 4. Click the Custom
button. 5. Locate the Element Size Parameters section. Select the Maximum
element size check box. 6. In the associated text field, type 1.5. 7. Select the
Minimum element size check box. 8. In the associated text field, type 0.01.

Size 2

1. Right-click Free Tetrahedral 1 and choose Size. 2. In the Settings window

for Size, locate the Geometric Entity Selection section. 3. From the
Geometric entity level list, choose Boundary. 4. From the Selection list,
choose Propeller and Shaft. 5. Locate the Element Size section. From the
Predefined list, choose Extra fine.

Size 3

1. Right-click Free Tetrahedral 1 and choose Size. 2. In the Settings window

for Size, locate the Geometric Entity Selection section. 3. From the
Geometric entity level list, choose Boundary. 4. From the Selection list,
choose Propeller base. 5. Locate the Element Size section. From the
Predefined list, choose extremely fine. 6. Click Build Selected.

Size 1

80
1. In the Model Builder window, right-click Mesh 1 and choose Free
Tetrahedral. 2. Right-click Free Tetrahedral 2 and choose Size. 3. In the
Settings window for Size, locate the Element Size section. 4. From the
Predefined list, choose Finer.

Free Tetrahedral 2

1. In the Model Builder window, under Component 1 (comp1)>Mesh 1 click

Free Tetrahedral 2. 2. In the Settings window for Free Tetrahedral, click
Build Selected. The mesh should look like Figure 3 (see chapter 4) (toggle
the transparency button in order to see the mesh better).

Study 1

Now, solve the model for the coated propeller case. 1. In the Settings
window for Study, type Study: Coated Propeller in the Label text field. 2.
On the Home toolbar, click Compute.

Results

Several plots are added by default. Now, add a surface plot for hull potential
to the electrode potential versus adjacent reference plot.

Electrode Potential vs Adjacent Reference (cd)

1. In the Model Builder window, under Results click Electrode Potential vs

Adjacent Reference (cd). 2. In the Settings window for 3D Plot Group, locate
the Plot Settings section. 3. Clear the Plot data set edges check box. 4.
Locate the Color Legend section. From the Position list, choose Left.

Surface 1

1. In the Model Builder window, expand the Electrode Potential vs Adjacent

Reference (cd) node, then click Surface 1. 2. In the Settings window for

81
Surface, locate the Coloring and Style section. 3. Clear the Color legend
check box.

Electrode Potential vs Adjacent Reference (cd)

1. In the Model Builder window, under Results click Electrode Potential vs

Adjacent Reference (cd). 2. On the Electrode Potential vs Adjacent
Reference (cd) toolbar, click Surface.

Surface 2

1. In the Model Builder window, under Results> Electrode Potential vs

Adjacent Reference (cd) click Surface 2. 2. In the Settings window for
Surface, locate the Expression section. 3. In the Expression text field, type
E_hull. 4. On the Electrode Potential vs Adjacent Reference (cd) toolbar,
click Plot. The surface plot of the potential for the ship surface with the
coated propeller should look like Figure 6 (see chapter 4).

Electrolyte Current Density (cd)

Select Zoom Box and a region closer to propeller. The surface plot of the
total current density for the zoomed in region near the coated propeller
should look like Figure 7 (see chapter 4).

Secondary Current Distribution (CD)

Now, set up the problem for an uncoated propeller case by describing the
electrode kinetics at the propeller base surfaces using the Electrode Surface
boundary feature and at the propeller blade surfaces using the Thin Electrode
Surface boundary feature.

Electrode Surface 2

1. On the Physics toolbar, click Boundaries and choose Electrode Surface. 2. In the
Settings window for Electrode Surface, locate the Boundary Selection section. 3. From

82
the Selection list, choose Propeller base. 4. Locate the Boundary Condition section.
From the Boundary condition list, choose Electrode potential. The potential of the
electronic phase of the propeller base is the same as for the shaft. 5. In the Evsref text
field, type Evsref. 6. From the φs, ref list, choose Electric reference potential (cd/refel1).

Electrode Reaction 1

1. In the Model Builder window, expand the Electrode Surface 2 node, then click
Electrode Reaction 1. 2. In the Settings window for Electrode Reaction, locate the
Equilibrium Potential section. 3. In the Eeq text field, type Eeq_prop. 4. Locate the
Electrode Kinetics section. From the Kinetics expression type list, choose Butler-
Volmer. 5. In the i0 text field, type i0_prop. 6. In the αa text field, type alphaa_prop. 7.
In the αc text field, type alphac_prop. 8. Select the Limiting current density check box.
9. In the ilim text field, type ilim.

Thin Electrode Surface 1

1. On the Physics toolbar, click Boundaries and choose Thin Electrode

Surface. 2. In the Settings window for Thin Electrode Surface, locate the
Boundary Selection section. 3. From the Selection list, choose Propeller
blades. 4. Locate the Boundary Condition section. From the Boundary
condition list, choose Electrode potential. The potential of the electronic
phase of the propeller blade is the same as for the shaft. 5. In the Evsref text
field, type Evsref. 6. From the φs, ref list, choose Electric reference potential
(cd/refel1).

Electrode Reaction 1

1. In the Model Builder window, expand the Thin Electrode Surface 1 node,
then click Electrode Reaction 1. 2. In the Settings window for Electrode
Reaction, locate the Equilibrium Potential section. 3. In the Eeq text field,
type Eeq_prop. 4. Locate the Electrode Kinetics section. From the Kinetics
83
expression type list, choose Butler-Volmer. 5. In the i0 text field, type
i0_prop. 6. In the αa text field, type alphaa_prop. 7. In the αc text field, type
alphac_prop. 8. Select the Limiting current density check box. 9. In the ilim
text field, type ilim.

3.5.1.4 Study: Coated Propeller

Now, disable the Electrode Surface 2 and Thin Electrode Surface 1 boundary
nodes in study for the coated propeller and add a new study to solve the
model for the uncoated propeller case.

Step 1: Stationary

1. In the Model Builder window, under Study: Coated Propeller click Step 1:
Stationary. 2. In the Settings window for Stationary, locate the Physics and
Variables Selection section. 3. Select the Modify model configuration for
study step check box. 4. In the Physics and variables selection tree, select
Component 1 (comp1)> Secondary Current Distribution (cd)>Electrode
Surface 2. 5. Click Disable. 6. In the Physics and variables selection tree,
select Component 1 (comp1)> Secondary Current Distribution (cd)>Thin
Electrode Surface 1. 7. Click Disable.

Add Study

1. On the Home toolbar, click Add Study to open the Add Study window. 2.
Go to the Add Study window. 3. Find the Studies subsection. In the Select
Study tree, select Preset Studies>Stationary. 4. Click Add Study in the
window toolbar. Click Add Study again to close the Add Study frame. 5. On
the Home toolbar, click Add Study to close the Add Study window.

Study 2

3.5.1.5 Study Uncoated Propeller

84
1. In the Settings window for Study, type Study: Uncoated Propeller in the
Label text field. 2. On the Home toolbar, click Compute.

Results

Several plots are added by default for the uncoated propeller case. The
surface plot of the total current density for the zoomed in region near the
uncoated propeller should look like Figure 9 (see chapter 4). Now, add a
surface plot for hull potential to the electrode potential versus adjacent
reference plot.

Electrode Potential vs Adjacent Reference (cd) 1

1. In the Model Builder window, under Results click Electrode Potential vs

Adjacent Reference (cd) 1. 2. In the Settings window for 3D Plot Group,
locate the Plot Settings section. 3. Clear the Plot data set edges check box. 4.
Locate the Color Legend section. From the Position list, choose Left.

Surface 1

1. In the Model Builder window, expand the Electrode Potential vs Adjacent

Reference (cd) 1 node, then click Surface 1. 2. In the Settings window for
Surface, locate the Coloring and Style section. 3. Clear the Color legend
check box.

Electrode Potential vs Adjacent Reference (cd) 1

1. In the Model Builder window, under Results click Electrode Potential vs

Adjacent Reference (cd) 1. 2. On the Electrode Potential vs Adjacent
Reference (cd) 1 toolbar, click Surface.

Surface 4

1. In the Model Builder window, under Results> Electrode Potential vs

Adjacent Reference (cd) 1 click Surface 4. 2. In the Settings window for
85
Surface, locate the Expression section. 3. In the Expression text field, type
E_hull. 4. Click the Zoom Extents button on the Graphics toolbar. 5. On the
Electrode Potential vs Adjacent Reference (cd) 1 toolbar, click Plot. The
surface plot of the potential for the ship surface with the uncoated propeller
should look like Figure 8 (chapter 4).

1D Plot Group 9

Now, create a Line Plot along the keel of the hull potential for both the
coated and uncoated propeller cases. 1. On the Home toolbar, click Add Plot
Group and choose 1D Plot Group. 2. In the Settings window for 1D Plot
Group, type Potential along Keel in the Label text field. 3. Locate the Data
section. From the Data set list, choose none.

Line Graph 1

1. Right-click Potential along Keel and choose Line Graph. 2. In the Settings
window for Line Graph, locate the Data section. 3. From the Data set list,
choose Study: Coated Propeller/Solution 1 (sol1). 4. Select Edges 119, 121,
and 123–125 only. 5. Locate the y-Axis Data section. In the Expression text
field, type E_hull. 6. Locate the x-Axis Data section. From the Parameter
list, choose Expression. 7. In the Expression text field, type y. 8. Click to
expand the Legends section. Select the Show legends check box. 9. From the
Legends list, choose Manual. 10. In the table, enter the following settings:

Legends / Coated Propeller

Line Graph 2

1. Right-click Results>Potential along Keel>Line Graph 1 and choose

Duplicate. 2. In the Settings window for Line Graph, locate the Data section.
3. From the Data set list, choose Study: Uncoated Propeller/Solution 2

86
(sol2). 4. Locate the Legends section. In the table, enter the following
settings:

Legends / Uncoated Propeller.

Potential along Keel

1. In the Model Builder window, under Results click Potential along Keel. 2.
In the Settings window for 1D Plot Group, click to expand the Title section.
3. From the Title type list, choose Manual. 4. In the Title text area, type
Potential along keel. 5. On the Potential along Keel toolbar, click Plot. The
potential comparison plot for the coated and uncoated propellers should look
like Figure 10 (chapter 4).

Derived Values

Finally, evaluate the magnitude of the current imposed by the ICCP anode by
integrating the current density over the anode area.

Surface Integration 1

1. On the Results toolbar, click More Derived Values and choose Integration
> Surface Integration. 2. In the Settings window for Surface Integration,
locate the Data section. 3. From the Data set list, choose Study: Coated
Propeller/Solution 1 (sol1). 4. Locate the Selection section. From the
Selection list, choose Anode. 5. Click Replace Expression in the upper-right
corner of the Expressions section. From the menu, choose Component
1>Secondary Current Distribution>cd.nIl - Normal electrolyte current
density. 6. Click Evaluate.

Surface Integration 2

1. Right-click Surface Integration 1 and choose Duplicate. 2. In the

Settings window for Surface Integration, locate the Data section. 3.
From the Data set list, choose Study: Uncoated Propeller/Solution 2

87
(sol2). 4. Run the Program ICCP computation will take place Figure 5
(see chapter4).

88
 Chapter Four

Data Analysis and Discussions

4.1 Introduction

Impressed current cathodic protection (ICCP) is a commonly employed

strategy to mitigate ship hull corrosion, by which an external current is
applied to the hull surface, polarizing it to a lower potential. Although there
are various factors such as salinity, temperature, hull surface coating that
contribute to the demand for current, the area of bare metal (mainly
propeller) is the most governing parameter. This model example simulates
the effect of propeller coating on the current demand and is based on a paper
by Huber and Wang, however using slightly different geometry and
polarization data. Two different cases are investigated; a coated and an
uncoated propeller.

4.2 Results and Discussions

This part deals with the result of the data analysis, it shows the equations, the
ship hull geometries required for protection which were set in chapter 3. It
depicts the final output to calculate the current density for the hull protection
in both coated and uncoated situations.

4.2.1 Ship Hull Atmosphere

The geometry of the ship hull considered in this example is shown in Figure
(4.1). The model geometry is created by adding rectangular block outside the
hull geometry to represent the ocean. Figure (4.1) below shows the geometry
of the ship hull surface, which is exposed to the sea water.

89
 Figure (4.1) the Geometry of the Ship Hull Surface, which is exposed to
the Sea Water

The following shape which shows the zoomed-in model geometry

highlighting the propeller features is shown in Figure (4.2) where the anode,
shaft and propeller surfaces and the electrolyte (sea water) domain are
highlighted.

Figure (4.2) the Zoomed-in Model Geometry of the Ship Hull Surface
Highlighting Anode, Shaft, Propeller Surfaces and Electrolyte Domain

90
The Secondary Current Distribution interface is used to solve the electrolyte
potential, φl (SI unit: V), over the electrolyte domain according to:

il = - σl ∇ φl

∇ . il = 0

Where, il (SI unit: A/m2) is the electrolyte current density vector and σl (SI
unit: S/m) is the electrolyte conductivity of the sea water which is assumed
to be a constant at 4 S/m

The Electrode Surface boundary node at the shaft electrode surfaces is used
to add electrode reactions and set the boundary condition for the electrolyte
potential to

n. il = iloc

Where iloc (SI unit: A/m2) is the local individual electrode reaction current
density.

Butler-Volmer expression is used to model the electrode reaction at the hull

surface and the propeller surface in case of uncoated propeller. This sets the
local kinetic current density to

αc𝐹η
ikin = i0 ( exp ( αa𝐹η
𝑅𝑇
) – exp (
𝑅𝑇
))

Where the over potential is calculated as

η = φs, ext – φl – Eeq

The electrode reaction considered on the metal surfaces is oxygen reduction.

Also enable a limiting current density of 5 A/m2 to the electrode kinetics
expressions, since oxygen transport in the seawater is limited by the rate of
91
transport to the surface. This will result in the following local current density
expression

𝑖lim𝑖kin
iloc =
𝑖lim + 𝑖kin

The ICCP system controls the hull potential versus the reference electrode.
Describe this in the model by adding a Reference Electrode node, and then
setting the electrode phase potential, φs,ext, of the Electrode Surface nodes to
-850 mV versus the potential of the Reference Electrode. The propeller and
the shaft are considered to be made up of nickel aluminum bronze (NAB)
alloy and Alloy 625, respectively. The electrode kinetics parameters used in
the Butler-Volmer expression for the shaft and propeller are shown in Table
(4.1).

Table (4.1) Electrode Kinetics Parameters

Parameter Unit Nab Propeller Alloy 625 Shaft

Equilibrium potential, Eeq V vs Ag/AgCl -0.31 -0.18
Exchange current density, i0 mA/cm2 1.5·10-2 1.3·10-4
Anodic transfer coefficient, αa - 0.78 0.45
Cathodic transfer coefficient, - 0.44 0.57
αc

In case of uncoated propeller, use the Electrode Surface boundary node at the
propeller base surfaces and use the Thin Electrode Surface boundary node at
the propeller blades surfaces to add electrode reactions. Note that the Thin
Electrode Surface boundary feature allows to prescribe the electrode kinetics
at both the upside and downside of the propeller blades.

Since the anode kinetics of this model is not known (and of minor interest
for this analysis), use an Electrolyte Potential node for the anode surface and
set the potential to 0 V. Note that the choice of potential level is at this
92
boundary arbitrary and only serves to “boot strap” (ground) the potentials of
the model.

Use the default Insulation condition for all boundaries of the ship hull
surfaces:

n . il = 0
Where n is the normal vector, pointing out of the domain.

Use an Infinite Electrolyte condition on the external boundaries to the

Electrolyte domain to describe the infinite extension of the ocean. Specify
the ocean surface and mid ship plane as symmetry planes. This models the
current conduction outside the drawn geometry, using the boundary element
method. The mesh used in the model is shown in Figure (4.3), with a close-
up of the propeller shown in Figure (4.4).

Figure (4.3) the Mesh used in Model

93
 Figure (4.4) The Mesh used in Model, Zoomed-in around Propeller

4.2.2 Total ICCP Current Demand

The research is about an Impressed Cathodic Current Protection (ICCP) for a

naval vessel. In ICCP, an active anode electrode is used to impress a
cathodic current on the protected metal, thereby lowering the potential of the
surface into a regime wherein little or no corrosion occurs. The magnitude of
the impressed current is controlled by monitoring the potential of the
protected metal body versus a reference electrode, placed in the vicinity of
the protected body.

94
The designed program investigate the behavior of the ICCP system used to
protect the ship hull. When the ICCP system is operating as intended, the
only active electrode reaction on the hull, propeller, and shaft is oxygen
reduction:

1
H2O + O2 + 2-e → 2O H−
2

The hull is coated, whereas the propeller and shaft are bare,

implying that the governing factors for the ICCP behavior are the

kinetic parameters for oxygen reduction on the latter surfaces.

An important factor is also the limiting current for oxygen reduction

due to transport limitations of the dissolved oxygen molecules in sea

water. For instance, you would expect the limiting current density

on the propeller to rise when the propeller is rotating as compared to

when the ship is moored with the engine shut off.

The Ship Hull ICCP program lets you vary the following parameters:

1. Control potential of the ICCP system to protect the ship hull.

2. Sea water conductivity.

3. Limiting current for oxygen reduction.

4. Electrode kinetics of the propeller and shaft.

The objective is to keep the hull potential low, but at the same time

avoid excessively high impressed currents, since these induce wear

on the anode as well as increase the power demand of the system.

95
The figure below (Figure (4.5)) summarizes the graphical user

interface of the program.

Figure (4.5) Graphical User Interface of the Ship Hull ICCP Simulator

The program evaluates the total ICCP current demand at the anode.
Additionally, potential distribution across the ship hull surface and current
density distribution at the shaft and propeller surfaces are plotted.

For the default imposed ship hull potential of -0.85 V versus the reference
electrode, it can be seen that the surface plot of the potential distribution
across the ship hull surface is non-uniform, which may increase the risk of
portions of the hull being unprotected to corrosion or being subjected to
hydrogen evolution. Similarly, the hull potential plotted along the keel of the

96
ship shows that the largest potential difference along the keel is around 450
mV, which is within the maximum 500 mV difference that is considered
safe. A negative local current density seen in the surface plot for the shaft
and propeller surfaces confirms cathodic reaction at both of these surfaces.

4.2.3 Analysis of Hull Potential with Coated Propeller

A surface plot of the hull potential for the case with a coated propeller is
shown in Figure (4.6). It can be seen that the potential distribution across the
ship hull surface is quite uniform, except in the region close to the anode
surface and the propeller and shaft surfaces. The potential is higher near the
shaft compared to the rest of the ship hull surface, indicating that this part of
the hull is less protected compared to the other parts.

Figure (4.6) a Surface Plot of the Hull Potential for the Case with a Coated
Propeller
97
4.2.4 Analysis of Current Density to the Shaft for Coated Case

The following Figure (4.7) shows a streamline plot of electrolyte current

density and a surface plot of absolute value of the total current density over
the shaft surface for the case with the coated propeller. The ionic current
flow from the anode surface to the shaft surface can be seen in Figure (4.7)
below.

Figure (4.7) a Surface Plot of the Total Current Density for the Case with
a Coated Propeller

4.2.5 Analysis Hull Potential with Uncoated Propeller

Figure (4.8) below shows the potential for the case with an uncoated
propeller. It can be seen that the potential distribution across the ship hull
surface is less uniform compared to the coated propeller case.
98
 Figure (4.8) a Surface Plot of the Hull Potential for the Case of an Uncoated
Propeller

4.2.6 Analysis of Current Density to the Shaft for Uncoated

Case

A streamline plot of electrolyte current density and a surface plot of absolute

value of the total current density over the shaft and propeller surfaces for the
case of the uncoated propeller is shown in Figure (4.9). The ionic current
flow from the anode surface to the shaft and propeller surfaces can be seen in
Figure (4.9). The total current demand is found to be higher in case of the
uncoated propeller compared to the coated propeller case, which could be
attributed to the higher cathode surface area in case of the uncoated
propeller.

99
 Figure (4.9) a Surface Plot of the Total Current Density for the Case of an
Uncoated Propeller

4.2.7 Electrode Phase ICCP Potential Plot

Figure (4.10) shows the electrode phase potential along the keel of the ship
for both coated and uncoated propellers. It can be seen that the potential in
the regions closer to the anode and the propeller surfaces deviates
significantly from the potential at the rest of the ship hull surface in case of
uncoated propeller. This deviation is less significant in the case of a coated
propeller. Thus, the potential distribution across the length of ship hull
surface is found to be considerably uniform in case of coated propeller and
non-uniform in case of uncoated propeller.
100
 Figure (4.10) the Electrode Potential Variation along the Keel of the Ship for
both Coated and Uncoated Propellers

Finally, the integrated anode current is evaluated for the two cases. For the
coated case the current is 4 A, and for the uncoated case the current is 9 A.

101
 Chapter Five

Conclusions, Recommendations and Suggestions for Further

Studies

This chapter presents the conclusions of the study, recommendations and

suggestions for further studies.

5.1 Conclusions

The purpose of this study is to increase the ships' performance by reducing

the drag which is caused by fouling and corrosion. The researcher used two
ways to achieve this goals, first the vessel hull coating is used to eliminate
the drag caused by fouling and Impressed Current Cathodic Protection
system (ICCPS) is designed using 'comsol 5.3a ' multi physic software
program. The program calculated the current density for hull protection in
both coated and uncoated states. This experiment also provided an estimate
that the range of cathodic potentials. The system shows that the largest
potential difference along the keel is around 450 mV, which is within the
maximum 500 mV difference that is considered safe and can ensure hull
protection. For the coated propeller the demanded current for protection is 4
A. In this case the potential distribution across the ship hull surface is quite
uniform, except in the region close to the anode surface and the propeller and
shaft surfaces. For the uncoated case, the value of the total current density
over the shaft and propeller surfaces is 9A. The potential distribution across
the ship hull surface is less uniform compared to the coated propeller case.
There is high ionic current flow from the anode surface to the shaft and
propeller surfaces which lead to oxidization of the anode more than the
coated case. It could be true to say that the total current demand is found to

102
be higher in case of the uncoated propeller compared to the coated propeller
case. .

5.2 Recommendations

The findings of this study reveals some recommendations as following:

1. ICCP should be used in corrosion protection of the ship hull to increase

the ship performance and to prolong the vessel structure to its maximum
allocated lifetime.

2. The anode material is consumed base on the current density the higher
current the more consuming of anodes, therefore, the research recommend
for coated cases to reduce the amount of the protection current, this lead to
less consuming of anodes.

3. It is important to set a periodic time to check the serviceability of the

anodes to ensure the structure protection from corrosion.

4. The protection current density should be checked periodically to its limit

to ensure vessels' hull protection from corrosion.

5.3 Suggestion for Further Studies

1. It is suggested to perform study on bacterial attachment and viability on

metal surfaces to be controlled by potential polarization.

2. Since calcareous deposit is a significant feature of cathodic protection at

more negative potentials, it is proposed to study the mechanism of
calcareous deposition under cathodic protection and effects of bio-films on
this mechanism and vice-versa.

103
 References

Bardal. E. (2004), Corrosion and Protection, ed. B. Derby. Springer.

Bushman J. B. (2013): Corrosion and Cathodic Protection Theory. Available from:

http://www.bushman.cc/pdf/corrosion_theory.pdf

Cieri, A., and Elfont, M., Engineered Approach to Effective Maintenance

Management, Naval Engineers Journal, pp. 253-261, May 1991.

Craig. B. D. & Anderson D. S. (1995), Hand Book of Corrosion Data. ASM

International, Materials Park Ohio, pp 679

Dekker, R. (1996). "Applications of Maintenance Optimization Models: A Review and

Analysis." Reliability Engineering & System Safety 51(3): 229-240.

Durham. M.O & Durham, R. A. (2005), Cathodic Protection. Industry Applications

Magazine, IEEE, 11 (1): P.41-47.

Efrid. K. D. Lee T. S. (1979), Journal of Corrosion, Vol 35. P.79.

Fink. F. W. (1993). Transaction of Electrochemical Society. Vol 75. P 441.

H. P. Hack, “Atlas of polarization diagrams for naval materials in seawater,”

Naval Surface Warfare Centre Technical Report, CARDIVNSWC-TR-61-
94/44, April 1995.

Khayal, O.M.E.S. December (2018). FUNDAMENTALS OF HEAT

EXCHANGERS, INTERNATIONAL JOURNAL OF RESEARCH IN
COMPUTER APPLICATIONS AND ROBOTICS, ISSN 2320-7345, Vol.6,
Issue 12, PP. 1 – 11.

Khayal, O.M.E.S. January (1993). MANUFACTURING PROCESSES

TEXTBOOK, www.ektab.com.

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PETRONAS, (1987). Principals of Materials Engineering and Corrosion Control in E
&B Operations, p: 104-105.

Perez. N. (2004), Electrochemistry and Corrosion Science.

Roggers, T.H. (1968). The effect of biological activity on corrosion. Chapter 13 in

Marine Corrosion. Newnes Intl. Monograph on Corrosion Science and Technology. G.
Newnes Ltd., London.

Roggers, T. H. (1968), Marine Corrosion, Newnes, London. P. 120.

Shrier .L.L & Hayfield, (1986) Impressed Current Anode, ed. V Ashworth and C.J.L.
Booker, Chichester, UK: Ellis Horwood.

T. Huber and Y. Wang, “Effect of propeller coating on cathodic protection

current demand: Sea trial and modeling studies,” Corrosion, vol. 68, pp 441–
448, 2012.

Von Beckmann, W. et al (1998), Cathodic Corrosion Protection. Houston:Gulf

Publishing Company.

Wells. G. C. (1948), the Importance of Controlled Humidity in Long Time

Preservation. Journal of the American Society for Naval Engineers, 60 (2): p.127-138

Zakoski, K and Darowicki, (2004). Evaluation and Characterization of Individual

Components of System Cathodic Protection. Anti-Corrosion Methods Materials. 5(4):
p 253-258.

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 Appendices

Photographs of Marine Workshop Complex and Slipway

in PortSudan, Sudan

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