An Overview of Corrosion, Inhibitors and Journals

Copyright © 2023 Dr Benjamin Valdez Salas PhD Nelson Cheng PhD (HC), SRF Patrick Moe BSc, MSc, Grad. Dip. All rights reserved.

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ISBN: 978-1-5437-7294-4 (sc)

ISBN: 978-1-5437-7296-8 (hc)

ISBN: 978-1-5437-7295-1 (e)

03/20/2023

Acknowledgements

In gratitude for the help we received in publishing this book, we would like to thank God. We are thankful to all the authors for their valued contribution to this book.

The following people and institutions deserve special recognition:

Universidad Autónoma de Baja California (UABC), Mexicali, Baja California, Mexico

Benjamín Valdez Salas, Michael Schorr, Ernesto Beltran, Ricardo Salinas, Francisco Flores, R. Garcia, Roumen Zlatev Koytchev, Rogelio Ramos Irigoyen, Monica Carrillo Beltrán, Nicola Radnev Nedev, Mario Curiel Alvarez, J. S. Salvador-Carlos, R. G. Inzunza, A. Calderas, N. Santillan, and Jorge Ramirez.

Polytechnic University of Baja California, Calle de la Claridad S/N, Colonia Plutarco Elias Calles, 21376 Mexicali, BCN, Mexico Gustavo López Badilla

Navor Rosas Gonzalez

Proyecto Tropicorr—CYTED, CINVESTAV-IPN, Merida, Appl. Physics Dept., Carr. Ant. A Progreso, Km. 6, CP 97310, Merida, Yucatan, Mexico

Lucien Veleva

National Centre for Metallurgical Research, CSIC, Spain

Jose María Bastidas

Sami Shamoon College of Engineering—Beer-Sheeva, Israel

Amir Eliezer

Magna Chemical Canada Inc.

James Cheng

Our sincere thanks to the Patridge team for bringing this book to its final form.

Preface

According to NACE Impact Report dated March 2017, the global cost of corrosion is estimated to be US$2,505 billion (22 March 2017), which is equivalent to 3.4 per cent of the global GDP (2013). In addition, these costs typically do not include individual safety or environmental consequences.

This book covers an overview of the types of corrosion in each industry and the basics of corrosion inhibitors and their applications. It has been a challenge for mankind to deal with corrosion for ages, and it is one of the major catastrophes of the world.

It is extremely challenging and extremely important to protect metals from corrosion. Corrosion inhibitors are commonly used in various industries to combat corrosion. Chemicals such as these impede the corrosion of metals when added to corrosive media in traces. As they get adsorbed onto metal surfaces, they form a very thin film of molecules that protects them from further corrosion.

Corrosive environments and metal surfaces are retarded by this film. The reduction in corrosion can be attributed to the physical blockage effect, or to the inhibitor’s influence on corrosion mechanisms and kinetics. These corrosion inhibitors are primarily found in solutions or dispersions, but some are also found in paints and coatings. When corrosion inhibitors are used, the severity of the corrosion problem can be reduced. Advances in corrosion control methods and techniques remain a major concern for industry and academia. The purpose of this chapter is to provide a brief overview of corrosion inhibitors.

In the twenty-first century, one of the most important global challenges is the ability to prevent failures by managing corrosion. Most practicing engineers and technologists do not understand how to actively engage in this urgent economic and environmental issue.

This book provides an overview of a comprehensive range of corrosion inhibitors and their applications to combat different forms of known corrosion currently experienced by various industries.

This book is a valuable resource for students, academics, and corrosion engineers alike in combating corrosion.

Table of Contents

Chapter 1     An Overview of Corrosion

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

1.1. Mechanism of Corrosion

Chapter 2     An Overview of Types of Corrosion

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

2.1. Atmospheric Corrosion

2.1.1 The Mechanism of Atmospheric Corrosion

2.2. Galvanic Corrosion

2.2.1 The Mechanism of Galvanic Corrosion

2.3. Crevice Corrosion

2.4. Erosion Corrosion

2.5. Selective Corrosion

2.6. Uniform Corrosion

2.7. Pitting Corrosion

2.8. Fretting Corrosion

2.8.1 Mechanism of Fretting Corrosion

2.9. Stress Corrosion

2.9.1 The Mechanism of Stress Corrosion

2.10. Intergranular Corrosion

2.11 Corrosion Fatigue

2.11.1 Mechanism behind Corrosion Fatigue

Chapter 3     An Overview of Corrosion Inhibitors

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

3.1 How It Works

3.2 Classification of Corrosion Inhibitor (CIs)

3.3 Corrosion Inhibitor Inhibition Efficiency

3.4 Measurement of Corrosion Rate

3.5 How Anodic Corrosion Works

3.6 How Cathodic Corrosion Works

3.7 How Mixed Corrosion Works

3.8 How VCI Works

3.9 References

Chapter 4     An Overview of Types of Corrosion Inhibitors

Nelson Cheng, Benjamín Valdez Salas,and Patrick Moe

4.1 Types of Corrosion Inhibitors

4.1.1 Anodic Inhibitor

4.1.2 Cathodic Inhibitor

4.1.3 Mixed Inhibitors

4.1.4 Volatile Corrosion Inhibitor

4.2 Corrosion Inhibitors and Their Uses

4.2.1 A corrosion inhibitor can be classified according to its protection mode as follows:

4.3 Inhibitor Carriers

4.4 Selection of Corrosion Inhibitors Based on an Evaluation Process

4.5 An Overview of the Inhibitor Selection Process

4.6 Materials Used in the Testing Process

4.6.1 Performing Metal Testing

4.6.1 Methods for Measuring Metal Losses

4.6.1 Methods Based on Electrochemistry

4.7 Inhibitor Selection for Corrosion Inhibition

Chapter 5     Overview of Metal Corrosion Rate Calculation

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

5.1 Definition of Rate of Corrosion

5.2 Corrosion Rate Conversion

5.3 The Importance of Corrosion Rates

5.4 Inhibitor Efficiency

5.5 Calculation of Corrosion Rate

5.6 Acceptable Corrosion Rate of Materials

Chapter 6     Inhibition of Seawater Steel Corrosion via Colloid Formation

Nelson Cheng, James Cheng, Benjamín Valdez Salas, M. Schorr,and J. M. Bastidas

6.1 Abstract

6.2 Introduction

6.3 Seawater Corrosion

6.4 Corrosion Inhibitors

6.5 A Colloidal Corrosion Inhibitor

6.6 Results and Discussion

6.6.1 Weight Loss

6.6.1 Mild Steel Corrosion Reactions

6.7 Applications

6.8 Conclusions

6.9 References

Chapter 7     Technological Applications of Volatile Corrosion Inhibitors

Nelson Cheng, Benjamín Valdez Salas, Michael Schorr, Ernesto Beltran, and Ricardo Salinas

7.1 Abstract

7.2 Introduction

7.3 Volatile Corrosion Inhibitors

7.4 Green Corrosion Inhibitors

7.5 Applications of Volatile Corrosion Inhibitors

7.5.1 Atmospheric Corrosion

7.5.2 Water Supply

7.6 Acid Corrosion Inhibition

7.7 Corrosion Inhibitors Extracted from Vegetables

7.8 Electronics Industry

7.9 Petroleum Industry

7.10 Natural Gas Industry

7.11 Concrete Corrosion

7.12 Military Equipment

7.13 Coatings, Paints, and Films

7.14 Evaluation of VCI Performance

7.15 Conclusions

7.16 References

Chapter 8     Corrosion Inhibitors for Prolonged Protection of Military Equipment and Vehicles

Nelson Cheng, Patrick Moe, Benjamín Valdez Salas, Michael Schorr, Ernesto Beltran, Ricardo Salinas, and J. M. Bastidas

8.1 Abstract

8.2 Corrosion Inhibitors

8.3 Military Asset Protection

8.4 Ground Vehicles

8.5 Conclusion

8.6 References

Chapter 9     Application of Vapour Phase Corrosion Inhibitors for Silver Corrosion Control in the Electronics Industry

Benjamín Valdez Salas, Francisco Flores, M.Schorr, James Cheng, and Lucien Veleva

9.1 Abstract

9.2 Introduction

9.3 Environmental Conditions

9.4 Experimental Procedures

9.5 Environment Pollution and Corrosivity

9.6 Surface Analysis

9.7 Indoor Atmosphere Corrosion Categories

9.8 Evaluation of Vapour Phase Corrosion Inhibitors

9.9 Results

9.10 Conclusions

9.11 References

Chapter 10   Proposal Case History on Preservation of Caisson Leg against Corrosion Caused by SRB

Nelson Cheng, Benjamín Valdez Salas, Dr Ernesto Beltran, and Patrick Moe

10.1 Abstract

10.2 Findings from Magna International and UABC

10.3 Corrosion in Marine Environment

10.4 Needs Statement

10.4 Objective

10.5 Preservation Proposal

10.7 Annual Corrosion Monitoring System of Corrosion Coupons

10.8 Mechanism of VAPPRO 849 and VAPPRO Pouch

10.9 Sulphate-Reducing Bacteria and Hydrogen Sulphide Productions

10.10 VAPPRO SRB-X

10.11 Some Common Applications of the Product Are Described Below

10.11.1 Water Flood Injection Water

10.11.2 Drilling, Completion, Work Over, and Fracturing Fluids

10.11.3 Produced Waters

10.12 References

Chapter 11   The Process of Making VCI Paper, Using VAPPRO MBL 2200-Amino Carboxylate Corrosion Inhibitor (ACCI), and Ascertaining Its Impregnation Efficacy Dosage

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

11.1 Abstract

11.2 Introduction

11.3 Kraft Paper

11.4 Corrosion Caused by Moisture

11.5 Corrosion Caused by Sulphur

11.6 Vapour Corrosion Inhibitor

11.7 Applying Method

11.8 Impregnation

11.8.1 Roller Impregnation

11.8.2 Spraying Impregnation

11.9 Determining the Effectiveness of MBL 2200

11.10 Experiment

11.11 Determine the Amount of Mixture

11.11.1 Materials and Apparatus Used

11.11.2 Procedures

11.11.3 Observations

11.11.4 Table 1. Day 3 and day 5 corrosion rate

11.12 Conclusion

11.13 References

Chapter 12   Combating Corrosion in Marine and Concrete Structures Synergistically Using Dual Protection—Colloidal Inhibition and VCI Adsorption

Nelson Cheng, Benjamín Valdez Salas, and Patrick Moe

12.1 Abstract

12.2 Introduction

12.3 Seawater Corrosion

12.4 Corrosion Inhibitors

12.5 VAPPRO CRI 4600, a Colloidal Corrosion Inhibitor

12.6 Results and Discussion

12.7 Carbon Steel Corrosion Reactions

12.8 Applications

12.9 Conclusion

12.10 VCI Adsorption Test of VAPPRO CRI 4600 Using German TL 81305-002

12.11 German TL 8135-003 Test (GmbH 2017)

12.11.1 Test Object

12.11.2 Test Sample

12.11.3 Test Solution

12.11.4 Test Equipment and Material

12.11.5 Procedure of the Test

12.11.6 Test Result

12.11.7 The Requirement of TL 8135-0002 for the Corrosion Protection Effect

12.12 Conclusion

12.13 References

Chapter 13   Food Industry: Equipment, Materials, and Corrosion

B. Valdez, M. Schorr, R. Salinas, and A. Eliezer

13.1 Food Processing Corrosion

13.2 Food Taste and Corrosion

13.2.1 Water

13.2.2 Salt

13.2.3 Acids

13.2.4 Sweet

13.3 Food Industry Sectors

13.3.1 Dairy

13.3.2 Beverages

13.3.3 Canned Food

13.4 Cleaning and Sanitising

13.5 Conclusions

13.6 References

Chapter 14   Green Corrosion Inhibitors for Water Systems

B. Valdez, M. Schorr, R. Garcia, and A. Eliezer

14.1 Abstract

14.2 Water Systems

14.3 Corrosion Protection and Control

14.4 Corrosion Inhibitors

14.5 Conclusions

14.6 References

Chapter 15   Copper Corrosion by Atmospheric Pollutants in the Electronics Industry

Benjamin Valdez Salas, Michael Schorr Wiener, Roumen Zlatev Koytchev, Gustavo López Badilla, Rogelio Ramos Irigoyen, Monica Carrillo Beltrán, Nicola Radnev Nedev, Mario Curiel Alvarez, Navor Rosas Gonzalez, and Jose María Bastidas Rull

15.1 Introduction

15.2 H2S, a Corrosive, Toxic Pollutant

15.3 Experimental

15.4 Results

15.5 Discussion

15.6 Conclusions and Recommendations

15.7 References

Chapter 16   Optimization and Characterisation of Commercial Water-Based Volatile Corrosion Inhibitor

N. Cheng, B. Valdez-Salas, P. Moe, and J. S. Salvador-Carlos

16.1 Abstract

16.2 Introduction

16.3 Experimental

16.3.1 Preparation of Metal Samples

16.3.1 Determination of Corrosion Rate and Corrosion Inhibitor Efficiency

16.3.3 Formulation of VAPPRO 837

16.3.4 Elevated Temperature Drying

16.3.5 Freeze-Thaw Test

16.3.6 FTIR Analysis

16.4 Results and Discussion

16.4.1 Polarisation Curves

16.4.2 Corrosion Reduction Efficiency

16.4.3 Effect of Drying at Elevated Temperatures

16.4.4 Freeze-Thaw Tests

16.4.5 pH test for varying concentrations of CORPPRO

16.4.6 Functional Group Determination by FTIR

16.5 Conclusions

16.6 References

Annex 1

Annex 2

Chapter 17   The Natural Gas Industry: Equipment, Materials, and Corrosion

Benjamin Valdez, Michael Schorr, and Jose M. Bastidas

17.1 Abstract

17.2 Introduction

17.3 Natural Gas

17.4 Shale Gas

17.5 Natural Gas Industry

17.5.1 Infrastructure

17.5.2 Production Wells

17.5.3 Marine Petroleum Platforms

17.5.4 Natural Gas Pipelines

17.5.5 LNG Regasification Plants

17.6 Corrosion and Protection Control

17.6.1 Materials Selection

17.6.2 Paints and Coatings

17.6.3 Cathodic Protection

17.6.4 Corrosion Inhibitors

17.7 Discussion

17.8 Conclusions

17.9 References

Chapter 18   Corrosion Inhibitor Patents in Industrial Applications—a Review

R. G. Inzunza, Benjamín Valdez, and Michael Schorr

18.1 Abstract

18.2 Introduction

18.3 Corrosion Inhibition in Cooling Water Systems

18.4 Corrosion Inhibitors for Steel-Reinforced Concrete

18.5 Corrosion Inhibitors for Acid Solutions

18.6 Corrosion Inhibitors for the Oil Industry

18.7 Vapour Phase Corrosion Inhibitors (VCIs)

18.8 Corrosion Inhibition in Coatings

18.9 Corrosion Inhibitors in Other Applications

18.10 Current and Future Developments

18.11 References

Chapter 19   Corrosion Mitigation in Water Systems

R. García, B. Valdez, M. Schorr, and A. Eliezer

19.1 Abstract

19.2 Introduction

19.3 Water Systems

19.4 Corrosion Protection and Control

19.5 Corrosion Inhibitors

19.6 Conclusions

19.7 References

Chapter 20   Corrosion of Copper Coils in Air Conditioning Equipment

A. Calderas, N. Santillan, B. Valdez, and M. Schorr

20.1 Experimental Procedures

20.2 Corrosion Testing

20.3 Results

20.4 Conclusions

20.5 References

Chapter 21   Corrosion Assessment of Infrastructure Assets in Coastal Seas

Benjamín Valdez,a Jorge Ramirez,b Amir Eliezer,c Michael Schorr,a Rogelio Ramos,a and Ricardo Salinasa

21.1 Abstract

21.2 Introduction

21.3 Corrosion and Pollution Interaction

21.4 Climate Change

21.5 Seas and Rivers

21.6 Marine Infrastructure

21.7 Ports, Shipyards, and Ships

21.8 Ballast Water Technology (BWT)

21.9 Marine Corrosion

21.10 Marine Biofouling

21.1 Influence of Pollutants

21.12 Results

21.13 Corrosion Testing

21.14 Metals and Specimens

21.15 Corrosion Measurements

21.16 Conclusions

21.17 Acknowledgements

21.18 References

1

An Overview of Corrosion

Nelson Cheng,¹ Benjamín Valdez Salas,2 and Patrick Moe¹

¹Magna International Pte Ltd., 10H Enterprise Road, Singapore 629834

²Universidad Autónoma de Baja California (UABC), Mexicali, Baja California, Mexico

Corrosion is the gradual deterioration of metals caused by the action of air, moisture, or a chemical reaction (such as an acid) on their surface. Rusting of iron, or the forming of brown flaky material on iron objects when exposed to moist air, is the most common example of metal corrosion.

Corrosion is a natural process that creates a chemically stable oxide from a refined metal. Chemical or electrochemical reactions with the environment slowly destroy materials (usually metals).

In its most common usage, this refers to the electrochemical oxidation of metal in reaction with an oxidant such as oxygen, hydrogen, or hydroxide. A well-known example of electrochemical corrosion is rusting, which forms iron oxides. As a result of this type of damage, oxides or salts of the original metal are produced, resulting in distinctive orange colouration.

In addition to reducing strength, appearance, and permeability to liquids and gases, corrosion reduces the useful properties of materials and structures.

The corrosion process is greatly influenced by exposure to certain substances, but many structural alloys simply corrode from moisture in the air. Surface corrosion can occur uniformly over a wide area, or it can be concentrated locally to form a pit or crack. Surfaces exposed to corrosion are affected by this diffusion-controlled process. Because of this, passivation and chromate conversion can increase the corrosion resistance of a material by reducing the activity of its exposed surface. Some corrosion mechanisms, however, are less visible and less predictable.

Corrosion is an electrochemical phenomenon; its chemistry is complex. During corrosion, an anode occurs at a particular spot on the surface of an iron object. In moist air conditions, electrons from this anodic spot move through the metal to another spot on the metal and reduce oxygen there in presence of H+ (which is formed when carbon dioxide from the air dissolves into the water because of the dissolution of carbon dioxide from the air into water). In addition to hydrogen ions, other acidic oxides may dissolve into water, releasing hydrogen ions. The said spot acts as a cathode.

1.1. Mechanism of Corrosion

Corrosion, also known as rust, is a chemical or electrochemical degradation of metals that happens because of interactions with the environment. It is an oxidation-reduction process that destroys iron exposed to moisture in the air.

The reaction causes damage to equipment, which results in large costs for many companies to conduct maintenance and repair works.

When ferrous metals are exposed to O2 and H2O, a reaction will take place over time, which forms rust in a reaction described as follows:

Iron is first oxidised to iron (II) ions, Fe²+, and oxygen from the air is reduced to hydroxide ions (OH-). The oxidation-reduction reaction takes place via two separate but simultaneous half-reactions as shown:

Oxidation half-reaction: Fe (s) → Fe²+ (aq) + 2e-

Reduction half-reaction: O2 (g) + 2H2O (l) + 4e- → 4OH- (aq)

Combining the half-reactions from the first step gives a balanced chemical equation for the overall reaction between iron, oxygen, and water:

2Fe (s) + O2 (g) + 2H2O (1) → 2Fe²+ (aq) + 4OH- (aq)

Next, iron (II) hydroxide reacts further with oxygen and water to form hydrated iron (III) oxide (Fe2O3•n H2O), which is a flaky reddish-brown solid known as rust:

4Fe (OH)2 (s) + O2 (g) + XH2O (I)→ 2Fe2O3•(X+4) H2O (s) [Rust].

2

An Overview of Types of Corrosion

Nelson Cheng,1 Benjamín Valdez Salas,2 and Patrick Moe¹

¹Magna International Pte Ltd., 10H Enterprise Road, Singapore 629834

²Universidad Autónoma de Baja California (UABC), Mexicali, Baja California, Mexico

This chapter covers the different types of corrosion encountered in generally various types of industries.

Corrosion can be classified by the forms in which it manifests itself, based on the appearance of the corroded metal. Observation alone can identify each form. It is usually sufficient to use the naked eye in most cases, but sometimes magnification is helpful. Observing corrosion-damaged test specimens or failed equipment can often provide valuable information for solving corrosion problems. The importance of examination before cleaning cannot be overstated. There are thirteen types of corrosion, and some of them are unique, but all of them are interconnected in some way.

2.1. Atmospheric Corrosion

Atmospheric corrosion occurs when electrolytes interact with metals. As a result of the moisture present in the atmosphere, rainwater, etc., exposed metal surfaces begin to corrode.

2.1.1 The Mechanism of Atmospheric Corrosion

Metals and non-metals are corroded and eroded by different atmospheric substances. Iron oxide, more commonly known as rust, is formed when oxygen and condensed water vapour in the earth’s atmosphere slowly corrode iron and steel surfaces. The microstructure of metals is altered by corrosion, reducing their mechanical strength and useful life dramatically.

Atmospheric corrosion is primarily caused by moisture from fog, dew, precipitation, and relative humidity. Corrosion is not caused by oxygen or carbon dioxide in a completely dry atmosphere. The formation of electrolytes in industrial atmospheres can aggravate corrosion caused by sulphur and chlorine salts. There is also an effect of air pressure and ambient temperature on corrosion. High temperatures can cause some electrolytes to become highly reactive. There are factors specific to each metal that determine the critical humidity for corrosion.

There are several types of corrosion damage, but atmospheric corrosion is the most prevalent. The deterioration is widespread, and it affects both indoor and outdoor installations, such as utility lines, industry, vehicles, and residential buildings.

2.2. Galvanic Corrosion

When two dissimilar metals are immersed in a corrosive or conductive solution, there is a potential difference. This potential difference produces electron flow between these metals when they are placed in contact (or otherwise electrically connected). Usually, the corrosion rate of a less corrosion-resistant metal increases, while the attack rate of a more corrosion-resistant metal decreases when these metals are in contact. A metal that is less resistant becomes anodic, while a metal that is more resistant becomes cathodic. Usually, the cathode or cathodic metal corrodes very little or not at all in this type of couple. Galvanic corrosion is two-metal corrosion caused by electric currents and dissimilar metals. The corrosion is electrochemical; though, for clarity, we will refer to it as galvanic corrosion.

2.2.1 The Mechanism of Galvanic Corrosion

It is a galvanic cell’s potential difference between its two metals that make it work. This potential difference causes electrons to flow within the cell. An electrode’s oxidation potential refers to its ability to lose electrons and become oxidised. Metals with a higher oxidation potential give up their electrons more easily.

2.3. Crevice Corrosion

On metal surfaces exposed to corrosives, intense localised corrosion often occurs in crevices and other shielded areas. There are several causes of this type of attack, including holes, gasket surfaces, lap joints, surface deposits, and crevices under bolt and rivet heads. Therefore, this type of corrosion is called crevice corrosion