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corrosion engineering principles and practice

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When I carried out my first corrosion investigation, some 25 years ago, on what turned out to be a 90-10 copper-nickel tubing Type I pitting problem it never occurred to me that this was indeed to trigger an important transition in my career. Well, that seems to be how many corrosion engineers have stumbled onto what was later to become a central focus of their work. There are many reasons for this. One common factor that often attracts an investigator’s attention is the drastic contrast that exists between the importance and seriousness of a corrosion problem and the size of the damage itself.






When I carried out my first corrosion investigation, some 25 years ago, on what turned out to be a 90-10 copper-nickel tubing Type I pitting problem it never occurred to me that this was indeed to trigger an important transition in my career. Well, that seems to be how many corrosion engineers have stumbled onto what was later to become a central focus of their work. There are many reasons for this. One common factor that often attracts an investigator’s attention is the drastic contrast that exists between the importance and seriousness of a corrosion problem and the size of the damage itself.

In my first corrosion investigation a metallurgical microscope of reasonable magnification was required to examine the tubing samples provided. Yet, these microscopic pits were causing a major havoc to the air-cooling system of a relatively modern facility where my laboratory and office were located. Eventually the whole airconditioning system unit had to be replaced at a cost of over $200,000.

The precise root cause of the problem still remains a mystery since a few other systems operating with a common water intake and of the same design and vintage are still in operation today and never suffered Type I pitting problems.

My first case also revealed another aspect of many corrosion investigations that is quite fascinating. It has to do with the complexity of the interactions that eventually culminate in a failure or a need to repair. The belief was widespread at the time that many of the corrosion problems could be alleviated with the help of well-designed and calibrated expert systems. In many countries the development of these systems was funded on the premise that these software tools would artificially improve the level of expertise of technical personnel.

Of course, this optimistic view could not possibly consider many of the hidden factors that are behind many corrosion situations: Unreported system changes, rapid and frequent changes in technical personnel and many other factors that may remain invisibly at work on a micro scale for years before giving the final blow to a system.

As with many of my predecessors and many colleagues, I have come to the conclusion that the main line of defense against the multiheaded foe we call corrosion is by increasing awareness through education and training. In our modern world some of that training can be provided by various routes that are readily accessible almost anywhere via the Internet or the Web. However, textbooks and reference documents remain as precious today as they were a century ago when they were the main source of distributing information.

Most people are familiar with corrosion in some form or another, particularly the rusting of an iron fence and the degradation of steel pilings or boats and boat fixtures. Piping is another major type of equipment subject to corrosion. This includes water pipes in the home, where corrosion attacks mostly from the inside, as well as the underground water, gas, and oil pipelines that crisscross our land.

Thus, it would appear safe to say that almost everyone is at least somewhat familiar with corrosion, which is defined in general terms as the degradation of a material, usually a metal, or its properties because of a reaction with its environment.

This definition indicates that properties, as well as the materials themselves, may and do deteriorate. In some forms of corrosion, there is almost no visible weight change or degradation, yet properties change and the material may fail unexpectedly because of certain changes within the material. Such changes may defy ordinary visual examination or weight change determinations.

In a modern business environment, successful enterprises cannot tolerate major corrosion failures, especially those involving personal injuries, fatalities, unscheduled shutdowns, and environmental contamination. For this reason considerable efforts are generally expended in corrosion control at the design stage and in the operational phase. This is particularly true for industries where harsh chemicals are handled routinely.

Corrosion can lead to failures in plant infrastructure and machines which are usually costly to repair, costly in terms of lost or contaminated product, in terms of environmental damage, and possibly costly in terms of human safety. Decisions regarding the future integrity of a structure or its components depend upon an accurate assessment of the conditions affecting its corrosion and rate of deterioration.


corrosion engineering principles and practice



Preface 1 The Study of Corrosion

1.1 Why Study Corrosion?

1.2 The Study of Corrosion

1.3 Needs for Corrosion Education

1.4 The Functions and Roles ofa Corrosion Engineer

1.5 The Corrosion Engineer’s Education

1.6 Strategic Impact and Cost of

Corrosion Damage

References 2 Corrosion Basics

2.1 Why Metals Corrode

2.2 Matter Building Blocks

2.3 Acidity and Alkalinity (pH)

2.4 Corrosion as a Chemical Reaction

2.4.1 Corrosion in Acids

2.4.2 Corrosion in Neutral and

Alkaline Solutions

Reference 3 Corrosion Electrochemistry

3.1 Electrochemical Reactions

3.2 Anodic Processes

3.3 Faraday’s Law

3.4 Cathodic Processes

3.5 Surface Area Effect

Reference 4 Corrosion Thermodynamics

4.1 Free Energy

4.2 Standard Electrode Potentials

4.3 Nernst Equation

4.4 Thermodynamic Calculations

4.4.1 The Aluminum-Air Power Source

4.4.2 Detailed Calculations

4.4.3 Reference Electrodes

4.5 Reference Half-Cells (Electrodes)

4.5.1 Conversion between References

4.5.2 Silver/ Silver Chloride

Reference Electrode

4.5.3 Copper/ Copper Sulfate

Reference Electrode

4.6 Measuring the Corrosion Potential

4.7 Measuring pH

4.7.1 Glass Electrodes

4.7.2 Antimony Electrode

4.8 Potential-pH Diagram

4.8.1 E-pH Diagram of Water

4.8.2 E-pH Diagrams of Metals

References 5 Corrosion Kinetics and Applicationsof Electrochemistry to Corrosion

5.1 What Is Overpotential?

5.2 Activation Polarization

5.3 Concentration Polarization

5.4 Ohmic Drop

5.4.1 Water Resistivity Measurements

5.4.2 Soil Resistivity Measurements

5.5 Graphical Presentation of Kinetic Data (Evans Diagrams)

5.5.1 Activation Controlled Processes

5.5.2 Concentration Controlled


5.6 Examples of Applied Electrochemistryto Corrosion

5.6.1 Electrochemical Polarization

Corrosion Testing

5.6.2 Corrosion Monitoring

5.6.3 Cathodic Protection

5.6.4 Anodic Protection

5.6.5 Aluminum Anodizing

5.6.6 Chloride Extraction

References 6 Recognizing the Forms of Corrosion

6.1 Recognizing Corrosion

6.2 General or Uniform Attack

6.3 Localized Corrosion

6.3.1 Pitting Corrosion

6.3.2 Crevice Corrosion

6.3.3 Galvanic Corrosion

6.3.4 Intergranular Corrosion

6.3.5 Dealloying

6.3.6 Hydrogen-Induced Cracking

6.3.7 Hydrogen Blistering

6.4 Velocity Induced Corrosion

6.4.1 Erosion–Corrosion

6.4.2 Cavitation

6.5 Mechanically Assisted Corrosion

6.5.1 Stress Corrosion Cracking

6.5.2 Corrosion Fatigue

6.5.3 Fretting Corrosion

References 7 Corrosion Failures, Factors, and Cells

7.1 Introduction

7.2 Information to Look For

7.2.1 Temperature Effects

7.2.2 Fluid Velocity Effects

7.2.3 Impurities in the Environment

7.2.4 Presence of Microbes

7.2.5 Presence of Stray Currents

7.3 Identifying the Corrosion Factors

7.4 Examples of Corrosion Cells

7.4.1 Galvanic Cells

7.4.2 Concentration Cells

7.4.3 Differential Aeration

Oxygen Concentration Cells

7.4.4 Temperature Cells

7.4.5 Stray Current Cells

7.4.6 Stress Cells

7.4.7 Surface Film Cells

7.4.8 Microbial Corrosion Cells

7.5 Corrosion Avoidance

7.5.1 Pitting Mitigation

7.5.2 Crevice Corrosion Mitigation

7.5.3 Galvanic Corrosion Mitigation

7.5.4 Fretting Corrosion Mitigation

7.5.5 Mitigation of Stress

Corrosion Cracking

7.6 Visualizing Corrosion Cells

References 8 Corrosion by Water

8.1 Importance of Water

8.2 Corrosion and Water Qualityand Availability

8.2.1 Corrosion Impact

8.2.2 Corrosion Management

8.2.3 Condition Assessment


8.3 Types of Water

8.3.1 Natural Waters

8.3.2 Treated Waters

8.4 Cooling Water Systems

8.4.1 Once-Through Systems

8.4.2 Recirculated Systems

8.4.3 Heat Exchangers

8.5 Steam Generating Systems

8.5.1 Treatment of Boiler

Feedwater Makeup

8.5.2 Fossil Fuel Steam Plants

8.5.3 Supercritical Steam Plants

8.5.4 Waste Heat Boilers

8.5.5 Nuclear Boiling Water Reactors

8.5.6 Nuclear Pressurized

Water Reactors

8.5.7 Corrosion Coststo the Power Industry

8.6 Water Treatment

8.6.1 Corrosion Inhibitors

8.6.2 Scale Control

8.6.3 Microorganisms

8.7 Scaling Indices

8.7.1 Langelier Saturation Index

8.7.2 Other Indices

8.8 Ion-Association Model

8.8.1 Limiting Halite Deposition in a

Wet High-Temperature Gas Well

8.8.2 Identifying Acceptable Operating Rangefor Ozonated Cooling Systems

8.8.3 Optimizing Calcium Phosphate

Scale Inhibitor Dosage in a High-TDS

Cooling System

References 9 Atmospheric Corrosion

9.1 Introduction

9.2 Types of Corrosive Atmospheres

9.2.1 Industrial

9.2.2 Marine

9.2.3 Rural

9.2.4 Indoor

9.3 Factors Affecting Atmospheric Corrosion

9.3.1 Relative Humidityand Dew Point

9.3.2 Pollutants

9.3.3 Deposition of Aerosol Particles

9.3.4 Deicing Salts

9.4 Measurement of Atmospheric

Corrosivity Factors

9.4.1 Time of Wetness

9.4.2 Sulfur Dioxide

9.4.3 Airborne Chlorides

9.4.4 Atmospheric Corrosivity

9.5 Atmospheric Corrosivity

Classification Schemes

9.5.1 Environmental Severity Index

9.5.2 ISO Classification of Corrosivityof Atmospheres

9.5.3 Maps of Atmospheric Corrosivity

9.6 Atmospheric Corrosion Tests

9.7 Corrosion Behavior and Resistance

9.7.1 Iron, Steel, and Stainless Steel

9.7.2 Copper and Copper Alloys

9.7.3 Nickel and Nickel Alloys

9.7.4 Aluminum and Aluminum Alloys

9.7.5 Zinc and Zinc Alloys

9.7.6 Polymeric Materials


10 Corrosion in Soils and Microbiologically

Influenced Corrosion

10.1 Introduction

10.2 Corrosion in Soils

10.2.1 Soil Classification

10.2.2 Soil Parameters

Affecting Corrosivity

10.2.3 Soil Corrosivity Classifications

10.2.4 Auxiliary Effectsof Corrosion Cells

10.2.5 Examples of Buried Systems

10.2.6 Corrosion of Materials

Other Than Steel

10.3 Microbiologically Influenced Corrosion

10.3.1 Planktonic or Sessile

10.3.2 Microbes Classification

10.3.3 Monitoring Microbiologically

Influenced Corrosion


11 Materials Selection, Testing, and Design Considerations

11.1 Materials Selection

11.2 Complexity of Corrosion Conscious

Materials Selection

11.2.1 Multiple Forms of Corrosion

11.2.2 Multiple Material/

Environment Combinations

11.2.3 Precision of Corrosion Data

11.2.4 Complexity of Materials/

Performance Interactions

11.3 Selection Compromises

11.3.1 Life-Cycle Costing

11.3.2 Condition Assessment

11.3.3 Prioritization

11.4 Materials Selection Road Map

11.4.1 Identify Initial Slateof Candidate Materials

11.4.2 Screen Materials Basedon Past Experience

11.4.3 Conduct Environmental


11.4.4 Evaluate Materials Based on Potential

Corrosion Failure Modes

11.4.5 Select Corrosion Preventionand Control Methods

11.5 Design Considerations

11.5.1 Designing Adequate Drainage

11.5.2 Adequate Joiningand Attachments

11.6 Testing Considerations

11.6.1 Test Objectives

11.6.2 Test Standards

11.6.3 Cabinet Testing


12 Corrosion as a Risk

12.1 Risk Assessment

12.2 Risk Analysis

12.3 Risk and Corrosion Control

12.4 Key Performance Indicators

12.4.1 Cost of Corrosion

Key Performance Indicator

12.4.2 Corrosion Inhibition Level Key

Performance Indicator

12.4.3 Completed Maintenance

Key Performance Indicator

12.4.4 Selecting Key Performance


12.5 Risk Assessment Methods

12.5.1 Hazard and Operability

12.5.2 Failure Modes, Effects, and Criticality Analysis

12.5.3 Risk Matrix Methods

12.5.4 Fault Tree Analysis

12.5.5 Event Tree Analysis

12.6 Risk-Based Inspection

12.6.1 Probability of Failure


12.6.2 Consequence of Failure


12.6.3 Application of Risk-Based


12.7 Industrial Example

Transmission Pipelines

12.7.1 External Corrosion

Damage Assessment

12.7.2 Internal Corrosion

Damage Assessment

12.7.3 Hydrostatic Testing

12.7.4 In-Line Inspection


13 Cathodic Protection

13.1 Cathodic Protection Historical Notes

13.2 How Cathodic Protection Works in Water

13.2.1 Sacrificial Cathodic Protection

13.2.2 Impressed Current

Cathodic Protection

13.3 How Cathodic Protection Works in Soils

13.3.1 Sacrificial Cathodic Protection

13.3.2 Impressed Current

Cathodic Protection

13.3.3 Anode Beds

13.3.4 Anode Backfill

13.4 How Cathodic Protection

Works in Concrete

13.4.1 Impressed Current

Cathodic Protection

13.4.2 Sacrificial Cathodic Protection

13.5 Cathodic Protection Components

13.5.1 Reference Electrodes

13.5.2 Anodes

13.5.3 Rectified Current Sources

13.5.4 Other Current Sources

13.5.5 Wires and Cables

13.6 Potential to Environment

13.7 Current Requirement Tests

13.7.1 Tests for a Coated System

13.7.2 Tests for a Bare Structure

13.8 Stray Current Effects

13.9 Monitoring Pipeline Cathodic

Protection Systems

13.9.1 Close Interval Potential Surveys

13.9.2 Pearson Survey

13.9.3 Direct and Alternating Current

Voltage Gradient Surveys

13.9.4 Corrosion Coupons

13.10 Simulation and Optimizationof Cathodic Protection Designs

13.10.1 Modeling Ship Impressed

Current Cathodic Protection

13.10.2 Modeling Cathodic Protectionin the Presence of Interference


14 Protective Coatings

14.1 Types of Coatings

14.2 Why Coatings Fail

14.3 Soluble Salts and Coating Failures

14.4 Economic Aspects of Coatings

Selection and Maintenance

14.5 Organic Coatings

14.5.1 Coating Functionality

14.5.2 Basic Components

14.6 Temporary Preservatives

14.6.1 Jointing Compoundsand Sealants

14.6.2 Corrosion Prevention


14.6.3 Volatile Corrosion Inhibitors

14.7 Inorganic (Nonmetallic) Coatings

14.7.1 Hydraulic Cement

14.7.2 Ceramics and Glass

14.7.3 Anodizing

14.7.4 Phosphatizing

14.7.5 Chromate Filming

14.7.6 Nitriding

14.7.7 Passive Films

14.7.8 Pack Cementation

14.8 Metallic Coatings

14.8.1 Electroplating

14.8.2 Electroless Plating

14.8.3 Hot-Dip Galvanizing

14.8.4 Cladding

14.8.5 Metallizing (Thermal Spray)

14.9 Coating Inspection and Testing

14.9.1 Condition of the Substrate

14.9.2 Condition of the Existing

Coating System

14.9.3 Coating Inspection

14.9.4 Laboratory Testing

14.9.5 Holiday Detection

14.10 Surface Preparation

14.10.1 Principles of Coating Adhesion

14.10.2 Abrasive Cleaning

14.10.3 Water Jetting

14.10.4 Wet Abrasive Blasting

14.10.5 Other Surface

Preparation Methods


15 High-Temperature Corrosion

15.1 Introduction

15.2 Thermodynamic Principles

15.2.1 Standard Free Energyof Formation

15.2.2 Vapor Species Diagrams

15.2.3 2D Isothermal

Stability Diagrams

15.3 Kinetic Principles

15.3.1 Scale as a Diffusion Barrier

15.3.2 Basic Kinetic Models

15.3.3 Pilling-Bedworth Ratio

15.4 Practical High-Temperature

Corrosion Problems

15.4.1 Oxidation

15.4.2 Sulfidation

15.4.3 Carburization

15.4.4 Metal Dusting

15.4.5 Nitridation

15.4.6 Gaseous Halogen Corrosion

15.4.7 Fuel Ash and Salt Deposits

15.4.8 Corrosion by Molten Salts

15.4.9 Corrosion in Liquid Metals


A Historical Perspective


B Periodic Table

C SI Units Conversion Table

A. 1 How to Read This Table

A. 2 Using the Table





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