CORROSION TUTORIAL

Dated: June 14, 2004

Hota GangaRao
Eung H Cho
Sucharitha Bachanna
Srinivas Aluri
Robert Creese

Constructed Facilities Center

West Virginia University, Morgantown, WV 26506
 Corrosion Tutorial

FOREWORD

Corrosion is the result of chemical reaction between a metal and its environment.
It is the tendency of the refined metal to return to its mineral state. Corrosion engineers
study the corrosion mechanisms to determine the causes of corrosion and the methods
to minimize the resulting damage. Also, corrosion engineers design and apply various
methods to prevent corrosion by practical and economical means. The importance of
corrosion is not only related with economy, but also with safety issues. The loss of
material due to corrosion results in the failure of the machines, structures, bridges, etc.
resulting in damages worth billions of dollars. The annual direct cost of corrosion and of
protection against corrosion in the United States for Department of Transportation alone
is estimated to be around 276 billion in the year 2001. Direct costs mean the costs of
replacing corroded structures and machinery. Indirect costs resulting from actual or
possible corrosion are more difficult to evaluate and maybe more than $276 billion.
Some of the major industries affected by corrosion are 1) Defense, 2) Nuclear power
plants, 3) Aircraft, 4) Pipeline, 5) Storage Tanks, 6) Highways and bridges, 7) Water
systems, 8) Gas distribution, 9) Transportation, 10) Petroleum, 11) Oil and natural gas,
12) Chemical plants, etc.

In this tutorial, some of the basics issues dealing with corrosion are explained.
The essential elements of electrochemistry that are needed to understand the basics of
corrosion reactions are presented in Chapters 1 and 2. Corrosion has been classified
in many different ways. One way is to classify by the forms in which corrosion occurs.
The forms of corrosion are discussed in Chapter 3. Corrosion of composites is typically
called Aging. Composites have different mechanical properties compared to most
metals. Hence aging of composites is discussed in Chapter 4. Use of composites is
rapidly becoming prevalent in many applications. Some of the important applications
are discussed in Chapter 5. Although corrosion cannot be prevented, its rate can be
retarded using many different methods. Some of the important methods are discussed
in Chapter 6. Chapter 7 consists of brief information on typical metals and composites
that are used extensively in the industry. Chapter 8 deals with advanced electro-
chemical kinetics of the corrosion reactions.

i
 Corrosion Tutorial

TABLE OF CONTENTS

1 FUNDAMENTALS OF CORROSION 1

1.1 ELECTROCHEMICAL CELL 1

1.2 STANDARD ELECTROCHEMICAL POTENTIAL 3
1.3 NERNST EQUATION 5
1.4 FREE ENERGY AND ELECTRODE POTENTIAL 6
1.5 POTENTIAL MEASUREMENT OF HALF-CELL REACTION 7

2 PASSIVITY AND ELECTROCHEMICAL CORROSION MEASUREMENTS 9

2.1 PASSIVITY 9
2.2 TAFEL EXTRAPOLATION 12
2.3 LINEAR POLARIZATION RESISTANCE METHOD 13
2.3.1 DERIVATION OF THE POLARIZATION RESISTANCE 13
2.3.2 PRINCIPLE OF MEASUREMENT 14
2.3.3 ADVANTAGES OF POLARIZATION RESISTANCE MEASUREMENTS 15
2.3.4 ERRORS AND LIMITATIONS IN THE USE OF POLARIZATION RESISTANCE MEASUREMENTS 15
2.4 OTHER METHODS TO DETERMINE POLARIZATION RESISTANCE 16
2.4.1 ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 16
2.4.2 ELECTROCHEMICAL NOISE 16

3 FORMS OF CORROSION 18

3.1 UNIFORM CORROSION 18

3.1.1 ATMOSPHERIC CORROSION 20
3.1.1.1 Mechanism 20
3.1.1.2 Prevention of Atmospheric Corrosion 21
3.1.2 GALVANIC CORROSION 21
3.1.2.1 CORRODED END (ANODIC OR LEAST NOBLE) 26
3.1.2.2 PROTECTED END (CATHODIC OR MOST NOBLE) 28

ii
 Corrosion Tutorial

3.1.2.3 Factors Affecting Galvanic Corrosion 30

3.1.2.4 Galvanic Series 31
3.1.2.5 Prevention of Galvanic Corrosion 33
3.1.3 STRAY CURRENT CORROSION 33
3.1.3.1 Direct stray current corrosion 33
3.1.3.2 Alternating Stray Current Corrosion 34
3.1.3.3 Telluric Effects 34
3.1.4 GENERAL BIOLOGICAL CORROSION 36
3.1.4.1 Causes and Prevention of Biological Corrosion 36
3.1.4.2 Prevention of biological corrosion 37
3.1.5 MOLTEN SALT CORROSION 38
3.1.6 CORROSION IN LIQUID METALS 39
3.2 LOCALIZED CORROSION 39
3.2.1 PITTING CORROSION 39
3.2.1.1 Initiation of Pitting Corrosion 40
3.2.1.2 Propagation of Pitting Corrosion 40
3.2.1.3 Prevention of Pitting Corrosion 42
3.2.2 CREVICE CORROSION 43
3.2.2.1 Initiation and Propagation of Crevice Corrosion 43
3.2.2.2 Prevention of Crevice Corrosion 45
3.2.3 PACK RUST 45
3.2.4 FILIFORM CORROSION 46
3.2.4.1 Prevention of Filiform Corrosion 48
3.2.5 LOCALIZED BIOLOGICAL CORROSION 49
3.3 ENVIRONMENTALLY INDUCED CRACKING 49
3.3.1 STRESS CORROSION CRACKING 49
3.3.1.1 Metallurgical Effects 50
3.3.1.2 Electrochemical Effects 50
3.3.1.3 Prevention of Stress Corrosion Cracking 51
3.3.2 SULFIDE STRESS CRACKING 52
3.3.3 LIQUID METAL EMBRITTLEMENT 52
3.3.4 SOLID METAL INDUCED EMBRITTLEMENT 53
3.3.5 CORROSION FATIGUE CRACKING 54

iii
 Corrosion Tutorial

3.3.5.1 Comparison with Stress Corrosion Cracking 55

3.3.5.2 Prevention of Corrosion Fatigue Cracking 55
3.3.6 HYDROGEN INDUCED CRACKING 56
3.3.6.1 Comparison with Stress Corrosion Cracking 56
3.3.6.2 Prevention of Hydrogen Induced Cracking 57
3.4 MECHANICALLY ASSISTED DEGRADATION 57
3.4.1 EROSION CORROSION 57
3.4.1.1 Prevention of Erosion Corrosion 58
3.4.2 IMPINGEMENT CORROSION 58
3.4.2.1 Prevention of Impingement Corrosion 59
3.4.3 CAVITATION CORROSION 59
3.4.4 FRETTING CORROSION 60
3.5 METALLURGICALLY INFLUENCED CORROSION 61
3.5.1 INTERGRANULAR CORROSION 61
3.5.1.1 Exfoliation / Lamellar Corrosion 61
3.5.1.2 Weld Decay 62
3.5.1.2.1 Prevention of Weld Decay 63
3.5.1.3 Sensitization (Intergranular Corrosion of Austenitic Stainless Steels) 63
3.5.2 DEALLOYING 65
3.5.3 DEZINCIFICATION 65
3.5.3.1 Prevention of Dezincification 65
3.6 HIGH TEMPERATURE CORROSION 65
3.6.1 OXIDATION 66
3.6.2 SULFIDATION 66
3.6.3 CARBURIZATION 67

4 AGING OF COMPOSITES 69

4.1 INTRODUCTION 69
4.2 COMPOSITION 69
4.2.1 FIBER REINFORCEMENTS 70
4.2.2 RESIN SYSTEMS 71
4.2.3 FILLERS 71
4.2.4 ADDITIVES 71

iv
 Corrosion Tutorial

4.3 FIBER REINFORCED POLYMERS 72

4.3.1 CHARACTERISTICS OF FIBER REINFORCED COMPOSITES 75
4.3.2 SHORT-TERM MECHANICAL AND HYGRO-THERMAL BEHAVIOR 78
4.3.2.1 Thermal Coefficient and Conductivity 78
4.3.2.2 Moisture Diffusion/Plasticization 81
4.3.2.2.1 Diffusion Through Unreinforced Epoxy, Vinyl Ester, Polyestor and Phenolics 82
4.3.2.2.2 Effect of Moisture on Fiber-Matrix System 87
4.3.2.2.3 Effect of Temperature and Polymer Structural Variables on Sorption of Water 94
4.3.3 LONG TERM MECHANICAL AND HYGROTHERMAL BEHAVIOR (AGING) 104
4.3.3.1 Creep Theory 104
4.3.3.1.1 Effect of moisture and temperature on Creep 115
4.3.3.1.2 Effect of Physical Aging on Creep 119
4.3.3.1.3 Effect of Ultraviolet (UV) Radiation on Creep 120
4.3.3.2 Fatigue and Fracture 121
4.3.3.2.1 Fatigue Process 124
4.3.3.2.2 Fatigue in Unidirectional Composites 127
4.3.3.2.3 Fatigue in Multidirectional Composites 130
4.3.3.3 Aging Due to Environmental Factors 131
4.3.3.3.1 Environmental Factors Influencing the Durability of Composites 132
4.3.3.4 Knockdown Factors 144
4.3.3.5 Durability Models 147
4.3.3.5.1 Analytical Methods to Predict the Effects of Environment on Composite Materials 147
4.4 SUMMARY AND CONCLUDING REMARKS 155

5 APPLICATIONS OF COMPOSITES 156

5.1 APPLICATIONS OF COMPOSITES FOR DEFENSE PURPOSES 156

5.1.1 AIRCRAFT SYSTEMS 156
5.1.2 GROUND SYSTEMS 158
5.1.3 INDIVIDUAL AND CREW SERVED SYSTEMS 158
5.1.4 ROCKET AND MISSILE SYSTEMS 159
5.1.5 SHIPBOARD SYSTEMS 160
5.2 APPLICATIONS OF COMPOSITES FOR CIVILIAN PURPOSES 161
5.2.1 AUTOMOTIVE 161

v
 Corrosion Tutorial

5.2.2 INFRASTRUCTURE 162

5.2.3 CONSTRUCTION 162
5.2.4 TRANSPORTATION 163
5.2.5 BIOMEDICAL 164
5.2.6 COMPUTER PRODUCTS 164
5.2.7 CORROSION RESISTANT PRODUCTS 165
5.2.8 ELECTRICAL 165
5.2.9 RECREATIONAL 166
5.2.10 MARINE 166

6 RETARDATION METHODS FOR CORROSION 168

6.1 CATHODIC PROTECTION 168

6.1.1 SACRIFICIAL ANODE SYSTEM 168
6.1.1.1 Advantages of Sacrificial Anode Systems 170
6.1.1.2 Disadvantages of Sacrificial Anode Systems 170
6.1.2 IMPRESSED CURRENT CATHODIC PROTECTION 170
6.1.2.1 Advantages of Impressed Current Cathodic Protection 172
6.1.2.2 Disadvantages of Impressed Current Cathodic Protection 172
6.2 COATINGS 172
6.2.1 METALLIC 172
6.2.1.1 Hot Dipping 172
6.2.1.2 Chemical Vapor Deposition (CVD) 173
6.2.1.3 Ion Vapor Deposition (IVD) 173
6.2.1.4 Spraying 173
6.2.1.5 Electroplating 174
6.2.2 INORGANIC 175
6.2.2.1 Portland Cement Coatings 175
6.2.2.2 Ceramics 175
6.2.2.3 Chromate Filming 175
6.2.2.4 Phosphate Coatings 176
6.2.2.5 Nitriding 176
6.2.3 ORGANIC 176
6.2.3.1 Binders 176

vi
 Corrosion Tutorial

6.2.3.2 Pigments 176

6.2.3.3 Solvents 177
6.2.4 NONSTICK COATINGS 177
6.3 INHIBITORS 177
6.3.1 ANODIC INHIBITORS 178
6.3.2 CATHODIC INHIBITORS 179
6.3.3 MIXED INHIBITORS 179
6.3.4 APPLICATIONS 179
6.4 ANODIC PROTECTION 179

7 METALS AND COMPOSITES DICTIONARY 182

7.1 METAL ALLOYS 182

7.1.1 CAST IRON 182
7.1.1.1 White Cast Iron 182
7.1.1.2 Malleable Iron 183
7.1.1.3 Ductile Iron 183
7.1.1.4 Gray Cast Iron 183
7.1.1.5 High Silicon Cast Iron 183
7.1.2 STEELS 184
7.1.2.1 Plain Carbon Steels 184
7.1.2.2 Low Alloy Steels 184
7.1.2.3 Stainless Steels 185
7.1.3 ALUMINUM AND ITS ALLOYS 185
7.1.4 MAGNESIUM AND ITS ALLOYS 186
7.1.4.1 Lead and its Alloys 186
7.1.5 COPPER AND ITS ALLOYS 186
7.1.6 NICKEL AND ITS ALLOYS 187
7.1.7 ZINC AND ITS ALLOYS 187
7.1.8 CADMIUM 187
7.1.9 TITANIUM AND ITS ALLOYS 188
7.1.10 COATED ALLOYS 188
7.1.11 MOLYBDENUM 188
7.1.12 TANTALUM 188

vii
 Corrosion Tutorial

7.1.13 TUNGSTEN 189

7.1.14 ZIRCONIUM 189
7.1.15 GOLD 189
7.1.16 PLATINUM 189
7.1.17 SILVER 190
7.2 PLASTICS 190
7.2.1 THERMOSETS 190
7.2.2 THERMOPLASTICS 191
7.3 CERAMICS 191
7.4 COMPOSITE MATERIALS 191
7.4.1 ORGANIC MATRIX COMPOSITES (OMCS) 192
7.4.2 METAL MATRIX COMPOSITES (MMCS) 193
7.4.3 CERAMIC MATRIX COMPOSITES (CMCS) 193
7.4.4 PARTICULATE REINFORCEMENTS 193
7.4.5 WHISKER REINFORCEMENTS 194
7.4.6 CONTINUOUS FIBER REINFORCED COMPOSITES 194
7.4.7 BRAIDED FABRICS 194
7.4.8 HYBRID FABRICS 195
7.4.9 KNITTED OR STITCHED FABRICS 196
7.4.10 WOVEN COMPOSITES 196
7.4.11 CARBON FIBER REINFORCED PLASTICS 197
7.4.12 GLASS FIBER REINFORCED PLASTICS 197
7.4.13 ARAMID FIBER REINFORCED PLASTICS 197
7.5 MANUFACTURING PROCESSES OF COMPOSITES 197
7.5.1 OPEN-MOLD PROCESSES 197
7.5.1.1 Hand Lay Up 198
7.5.1.2 Tube Rolling 198
7.5.2 CLOSED-MOLD PROCESSES 199
7.5.2.1 Resin Transfer Molding (RTM) 199
7.5.2.2 Vacuum Assisted Resin Transfer Molding (VARTM) 200
7.5.2.3 Resin Injection Molding Process 200
7.5.2.4 Compression Molding 201
7.5.2.5 Pultrusion 202
7.5.2.6 Extrusion 203
7.5.2.7 Filament Winding Process 203

viii
 Corrosion Tutorial

7.6 COMPOSITES TERMINOLOGY 204

7.7 REAGENTS 212
7.7.1 SULFURIC ACID 212
7.7.2 HYDROCHLORIC ACID 212
7.7.3 NITRIC ACID 213
7.7.4 HYDROFLUORIC ACID 213
7.7.5 PHOSPHORIC ACID 214

8 CORROSION KINETICS 215

8.1 POLARIZATION 215

8.1.1 ACTIVATION POLARIZATION 215
8.1.2 CONCENTRATION POLARIZATION 220
8.2 MIXED POTENTIAL THEORY 222
8.3 EXPERIMENTAL POLARIZATION CURVES 224

LIST OF FIGURES

Figure 1-1: Electrochemical Cell _________________________________________________ 2

Figure 2-1: Schematic Active-Passive Behavior of the Anodic Polarization of a Metal _______ 9
Figure 2-2: Schematic Representation of Corrosion of Stainless Steel with Two Oxidation
Reagents ___________________________________________________________________ 10
Figure 2-3: Comparison of Galvanostatic and Potentiostatic Anodic Polarization Curves_ __ 11
Figure 2-4: Cathodic and Anodic Polarization Curves________________________________ 12
Figure 3-1: Uniform Corrosion 17
Figure 3-2: Example of uniform corrosion damage on a rocket assisted artillery projectile 18
Figure 3-3: Atmospheric corrosion of galvanized anti crash railing due to marine aerosol
condensation on wooden post 19
Figure 3-4: Galvanic Corrosion of Brass Coupled With Black Iron 20
Figure 3-5: Mechanism of Galvanic Corrosion of a Two Metal Couple 21
Figure 3-6: Galvanic cell showing corrosion process in its simplest form 22

ix
 Corrosion Tutorial

Figure 3-7: Corrosion rate determination for a two electrode process system 23
Figure 3-8: Corrosion rate determination for a three electrode system 24
Figure 3-9. The introduction of a less noble metal will decrease the corrosion rate of the more
noble metal. 25
Figure 3-10: Effect of cathode to anode ratio in galvanic corrosion 28
Figure 3-11: Occurrence of Stray current corrosion in pipelines. 33
Figure 3-12: Ionic current flow onto the pipeline 34
Figure 3-13: Current flow onto pipeline at coating discontinuities 35
Figure 3-14: External stray current sources. 36
Figure 3-15: Corroded surface of carbon steel in its natural condition 37
Figure 3-16: Pitting in Aluminum 39
Figure 3-17: Propagation of Pitting Corrosion 41
Figure 3-18: Crevice Corrosion 43
Figure 3-19: Mechanism of Crevice Corrosion 44
Figure 3-20: crevice corrosion in rivets 45
Figure 3-21: A crevice formed into an open atmosphere 46
Figure 3-22: Example of Pack Rust 46
Figure 3-23: Mechanism of Filiform Corrosion 47
Figure 3-24: “worm like” filiform corrosion tunnels. 48
Figure 3-25: Filiform Corrosion Causing Bleed Through a Welded Tank 49
Figure 3-26: Stress Corrosion Cracking Showing Branched Cracks in Aluminum Plates 50
Figure 3-27: Schematic of Active-Passive Behavior of the Anodic Polarization of a Metal 51
Figure3-28: Liquid Metal Embrittlement 53
Figure 3-29: Solid Metal Induced Embrittlement of a cadmium plated B7 bolt 54
Figure 3-30: Brittle crack in a cadmium plated B7 bolt from solid metal induced embrittlement
____________________________________________________________________________55
Figure 3-31 Impingement corrosion in a bent tube 59
Figure 3-32: Exfoliation of Aluminium 62
Figure 3-33:Exfoliation of aircraft component 63
Figure 3-34:Intergranular corrosion in stainless steel 64
Figure 3-35: Intergranular Corrosion of 7075-T6 aluminum adjacent to steel fastener 65

x
 Corrosion Tutorial

Figure 4-1: Fibers as reinforcement a) Random Fibers________________________________70

Figure 4-1: Fibers as reinforcement b) Continuous Fibers (Long)______________________ _70
Figure 4-2: The combined effect on modulus of the addition of fibers to the resin matrix_____ 73
Figure 4-3: Typical Sorption Curve (Vijay et al., 2001)______________________________ 83
Figure 4-4: The Sorption Curves for Epoxy, Vinyl ester, and Isopolyester Resin When Exposed to
the 3 Different Solutions (Chin et al., 1999)_________________________________________84
Figure 4-5: Fickian Diffusion Curves for Epoxy in (a) Water, (b) Salt Solution, and (c) Concrete
Pore Solution at 22 °C (Chin et al., 1999)__________________________________________ 86
Figure 4-6: Thermal Expansion Measured by Stokes (Stokes, 1990)_____________________ 88
Figure 4-7: Moisture-Induced Thermal Expansion vs. Temperature (Stokes, 1990)_________ 88
Figure 4-8: (A) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen as a
function on the humidity of conditioning environment. (Stokes, 1990) ___________________ 90
Figure 4-8: (B) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in Across
Ply Direction (Stokes, 1990)_____________________________________________________91
Figure 4-8: (C) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in Ply
Direction (Stokes, 1990)________________________________________________________92
Figure 4-8: (D) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in Wrap
Direction (Stokes, 1990)________________________________________________________93
Figure 4-9: Difference Between (a) Diamine and (b) Aniline Hardener __________________ 99
Figure 4-10: Bonds Between Glass Fiber and Coupling Agent. _______________________ 102
Figure 4-11: Typical Creep Behavior of Plastics (GangaRao, 2001) ___________________ 105
Figure 4-12: Maxwell's Model__________________________________________________ 108
Figure 4-13: Kelvin Model_____________________________________________________110
Figure 4-14: Four Element Model _______________________________________________111
Figure 4-15: Behavior of creep and stress relaxation in four element model ______________112
Figure 4-16: Behavior of creep when subjected to a series of stresses ___________________113
Figure 4-17: Schematic Representation of the Effects of Time, Temperature, and Moisture on
Creep Compliance (Liao,1998) ________________________________________________ 116
Figure 4-18: Moisture Absorption Behavior_______________________________________ 118
Figure 4-19: Effect of Physical Aging on Creep_____________________________________120

xi
 Corrosion Tutorial

Figure 4-20: Fatigue Damage Mechanism in Unidirectional Composites Under Loading Parallel
to Fibers: (a) Fiber Breakage, Interfacial Debonding; (b) Matrix Cracking; (c) Interfacial Shear
Failure [Talreja, 1987]________________________________________________________125
Figure 4-21: Two-Stage Strength Degradation Model for Fatigue Reliability of Composites
[Talreja, 1987] _____________________________________________________________ 127
Figure 4-22: Comparison of S-N Curve for Three Different Unidirectional Composite Materials
[Curtis and Dorey, 1986] _____________________________________________________ 128
Figure 4-23: Comparison of S-N curve for Four Different Materials with Different Carbon
Fibers in Same Epoxy Resin [Curtis and Dorey, 1986] ______________________________ 129
Figure 4-24: Fatigue Life Diagram of Unidirectional Composites Under (a) Loading Parallel to
Fibers, (b) Off-Axis Loading (Dotted line correspond to on-axis loading) [ Talreja, 1987] __ 130
Figure 4-25: Normalized S-N Curves for (0/±45) CFRP Laminates with Varying Percentage of
0o Fibers [Curtis and Dorey, 1986] _____________________________________________ 131
Figure 5-1: F-22 Raptor Aircraft -Tactical Fighter Aircraft __________________________ 157
Figure 5-2: RAH-66 Comanche ________________________________________________ 157
Figure 5-3: a.GAU –19A b. F18C/D ____________________________________________ 158
Figure 5-4: Reactive Armor and XM-301 Gun ____________________________________ 158
Figure 5-5: Objective Crew Served Weapon ______________________________________ 159
Figure 5-6: Delta II _________________________________________________________ 160
Figure 5-7: Missiles from the Hydra 70 Family____________________________________ 160
Figure 5-8: Destroyers _______________________________________________________ 161
Figure 5-9 Goalkeeper: In-Ship Defense System ___________________________________ 161
Figure 5-10: Composite Fire Truck Panels _______________________________________ 162
Figure 5-11: All Composite Bridge, Laurel Lick, CFC-WVU _________________________ 162
Figure 5-12: Energy Plant Towers ______________________________________________ 163
Figure 5-13: Third Rail Protection in Monorail System _____________________________ 163
Figure 5-14: MRI Units ______________________________________________________ 164
Figure 5-15: Composite Computer Chip _________________________________________ 164
Figure 5-16: Waste Water Plant________________________________________________ 165
Figure 5-17: Telecommunication Towers_________________________________________ 166
Figure 5-18: Recreational Products_____________________________________________ 166

xii
 Corrosion Tutorial

Figure 5-19: Sheet Piling and Fender Applications_________________________________ 167

Figure 6-1: Steel Tank Protected by Sacrificial Anode System ________________________ 169
Figure 6-2: Mechanism of Anodic Protection System _______________________________ 170
Figure 6-3: Steel Tank Protected by Impressed Current System _______________________ 171
Figure 6-4: Mechanism of Impressed Current Systems Explained Using Anodic Polarization
Curves ____________________________________________________________________ 171
Figure 6-5: Mechanism of Electroplating ________________________________________ 174
Figure 6-6: Effects of Applied Anodic Current on the Behavior of Active-Passive Alloy ____ 181
Figure 7-1: Particulate Reinforcement___________________________________________ 193
Figure 7-2: Whisker Reinforcement _____________________________________________ 194
Figure 7-3: Continuous Fiber Reinforcement _____________________________________ 194
Figure 7-4: Braided Fabrics___________________________________________________ 195
Figure 7-5: Hybrid Fabrics ___________________________________________________ 195
Figure 7-6: Knitted or Stitched Fabrics __________________________________________ 196
Figure 7-7: Woven Fabric ____________________________________________________ 196
Figure 7-8: Hand Lay Up _____________________________________________________ 198
Figure 7-9: Tube Rolling _____________________________________________________ 199
Figure 7-10: Resin Transfer Molding Machine (CFC-WVU) _________________________ 200
Figure 7-11: VARTM –Tabletop Model of VARTM and Schematic Process of Manufacture _ 200
Figure 7-12: Injection Molding Machine (CFC-WVU) ______________________________ 201
Figure 7-13: Compression Molding Machine (CFC-WVU)___________________________ 202
Figure 7-14: Schematic Representation of Pultrusion Process (Bedford Plastics) ____________ 202
Figure 7-15: Basic Extruder___________________________________________________ 203
Figure 7-16 a: Winding Machine Showing Carriage and Mandrel b: Filament Winding____ 204
Figure 8-1: Activation Polarization _____________________________________________ 216
Figure 8-2: Butler-Volmer Equation and Tafel Equation ____________________________ 220
Figure 8-3: Combined Polarization _____________________________________________ 222
Figure 8-4: Behavior of Metal M in Acid Solution__________________________________ 223
Figure 8-5: Behavior of Coupled Metals in Acid Solutions ___________________________ 224
Figure 8-6: Showing Cathodic and Anodic Polarization Curves_______________________ 226

xiii
 Corrosion Tutorial

LIST OF TABLES
Table 1-1: E0 Values for Metals __________________________________________________ 4
Table 1-2: E0 Values for Common Oxidation Reagents ________________________________ 5
Table 3-1: Galvanic Series of Metals/Alloys in Seawater _____________________________ 32
Table 4-1: Diffusion Coefficients of Epoxy, Vinyl Ester, and Isopolyester Resins___________ 85
Table 4-2: Variation of Equilibrium Moisture Content with Degree of Cure ______________ 98
Table 4-3: Effect of Hardener on Equilibrium Moisture Content ______________________ 100
Table 4-4:Calculated Values of Gth _____________________________________________ 103
Table 4-5: Knockdown Factors (Vijay,1998) ______________________________________ 146

xiv
 Corrosion Tutorial

1 FUNDAMENTALS OF CORROSION

In the design and fabrication of machines and structures, the choice of the
material depends on many factors, including its corrosion behavior. Although corrosion
resistance is an important factor, the final choice frequently depends on many other
factors like economics, availability, etc. In the case of applications that require aesthetic
appeal, appearance is the most important consideration.

Corrosion resistance or chemical resistance of a material depends primarily on

thermodynamics, electro-chemistry, and metallurgy among others. Thermodynamics
can determine whether or not the material is prone to corrosion. Electro-chemistry along
with environmental factors, design, etc., can predict the approximate rate of corrosion.
Metallurgical factors influence the corrosion resistance of the material. Physical
chemistry and its various disciplines are very useful for studying the mechanisms of
corrosion reactions, the surface conditions of metals, and other basic properties. This
chapter introduces the fundamentals of the electro-chemistry needed to understand the
basic corrosion mechanism. The electrochemical cell, standard electrochemical
potential, Nernst equation, and free energy and electrode potential are briefly discussed.

1.1 Electrochemical Cell

Corrosion is an electrochemical reaction between the metal and its environment.
In order to determine how corrosion occurs, we must understand the formation of a
corrosion cell. The corrosion cell consists of an anode, a cathode, an electrolyte, and an
anionic membrane.

Figure 1.1 shows an electrochemical cell, which consists of a steel anode, a

platinum cathode, sulfuric acid catholyte and an anionic membrane (allows only
negatively charged ions to pass through the membrane).

1
 Corrosion Tutorial

Figure 1-1: Electrochemical Cell

At the anode, iron is oxidized and dissolved into the electrolyte.

Fe = Fe2+ + 2e- …(1.1)
Equation (1.1) is an anodic reaction and it is also called half-cell reaction. This
reaction cannot occur alone; it needs a partner cathodic reaction. The cathodic reaction
takes place on the surface of the platinum electrode according to:
2H+ + 2e- = H2 (g = ‘gas’) …(1.2)
This cathodic reaction is also called half-cell reaction. We can see that cathodic
reaction is a reduction of H+ to H2 (g).
The anionic membrane allows only the anions (negatively charged ions) of the sulfate
ions to pass through. This transfer of anions is needed to maintain the electrical
neutrality of the solutions at both anodic and cathodic compartment. For example, the
dissolution of Fe introduces Fe++ ions into the anodic compartment. So, one mole of
Fe++ introduced needs one mole of SO42- transferred from the cathodic compartment to
maintain the electrical neutrality.

2
 Corrosion Tutorial

1.2 Standard Electrochemical Potential

Standard electrochemical potential is defined as the potential under standard
conditions, i.e., 25 °C and 1 atmosphere pressure and when the reactants of the
reaction have unit activity.

The list of E0 values for various metals is provided in Table 1.1. Table 1.2 shows
the E0 values for common oxidation reagents. The E0 values for both tables are given
for cathodic reaction, as per the international convention.

3
 Corrosion Tutorial

Table 1-1: E0 Values for Metals

Reaction Standard Potential E0 (volts vs. SHE)

Au3+ + 3e- = Au +1.498 Noble

Ag+ + e- = Ag +0.799

Hg22+ + 2e- = 2Hg +0.799

Cu2+ + 2e- = Cu +0.342

Pb2+ + 2e- = Pb -0.126

Sn2+ + 2e- = Sn -0.138

Ni2+ + 2e- = Ni -0.250

Co2+ + 2e- = Co -0.277

Cd2+ + 2e- = Cd -0.403

Fe2+ + 2e- = Fe -0.447

Cr3+ + 3e- = Cr -0.744

Zn2+ + 2e- = Zn -0.762

Al3+ + 3e- = Al -1.662

Mg2+ + 2e- = Mg -2.372

Na+ + e- =Na -2.71

K+ + e- = K -2.931 Active

Note: SHE = Standard Hydrogen Electrode

4
 Corrosion Tutorial

Table 1-2: E0 Values for Common Oxidation Reagents

Reactions Standard Potential E0 (volts vs. SHE)

Cl2 + 2e- = 2Cl- +1.358

O2 + 4H+ + 4e- = 2H2O (pH 0) +1.229

NO3- +4H+ + 3e- = NO + 2H2O +0.957

O2 + 2H20 + 4e- = 4OH- +0.82

Fe3+ + 3e- = Fe +0.771

O2 + 2H2O + 4e- = 4OH- (pH 14) +0.401

Sn4+ + 2e- = Sn2+ +0.15

2H+ + 2e- = H2 0.000

2H2O + 2e- = H2 + 2OH- (pH 7) -0.413

2H2O + 2e- = H2 + 2OH- (pH 14) -0.828

The E0 values can be calculated from ΔG0 (GFE = Gibbs Free Energy) value of
the reaction. For example, the reverse reaction of reaction (1.1) is:

Fe2+ + 2e- = Fe …(1.3)

The GFE change for reaction (1.3) is 20.30 kcal/mole. But,

ΔG0 = - nFE0 …(1.4)

where F is the Faraday constant and is 23.06 kcal/equivalent-volt and n is the number
of electrons or equivalents/mole. Then, the E0 of reaction (1.3) will be -0.44 eV.

1.3 Nernst Equation

Nernst equation is used to calculate E values from the E0 values. The E values
are under the conditions that deviate from the standard condition as defined in section
1.2. The Nernst equation can be derived from:

5
 Corrosion Tutorial

ΔG=ΔG0+RTln(K) …(1.5)

where R is the gas constant (=1.987cal/mole-K), T is the absolute temperature, K is the

equilibrium constant, and F is the Faraday constant (=23060 cal/equivalent-volt).
Substitution of equation (1.4) and the similar term for ∆G into Equation (1.5) yields:

E=E0–(RT/nF)*ln(K) …(1.6)

Substitution of R, F, and T (=2980K) into Equation (1.6) and converting ln (log to

the base e) to log (log to the base 10) yields:

1.987 * 298 * 2.303

E = E0 − log( K )
n * 23060

0.059
E = E0 − log( K ) …(1.7)
n

Equation (1.7) is called the Nernst Equation.

1.4 Free Energy and Electrode Potential

The overall electrochemical reaction is a combination reaction of cathodic and
anodic reactions. If the number of electrons is not identical in both half-cell reactions,
mathematical arrangement should be made to equate the number of electrons, so that
the overall electrochemical reaction results in no electrons.

Since potential is an intensive (having same potential value for every subdivision
of a system) property, the potentials of the half-cell reactions cannot be added in order
to determine the free energy of the overall reaction. The free energy of the overall
reaction can be determined as follows: First E value of the half-cell reactions should be
calculated using the Nernst equation. Then, these values should be converted to free
energy, ΔG. In this procedure, n for each half-cell reaction should be determined to give
no electrons in the overall reaction. Then the free energies of the half-cell reaction can
be added to obtain the free energy of the overall reaction.

6
 Corrosion Tutorial

For example, the overall reaction for Figure 1.1 can be written as:

Fe + 2H+ = Fe++ + H2 …(1.8)

The cathodic reaction is Equation (1.2) and the anodic reaction is Equation (1.1).
To calculate the free energy of reaction (1.8) when [Fe++] = 10-2 molar, H+ = 10-1 molar
and PH 2 = 1 atmosphere

The E value for cathodic reaction is:

0.059 PH
E = 0− log +2 2 = −0.059 …(1.9)
2 [H ]

Then the ΔG = -2F(-0.059) = 2.72 kcal/mole.

Similarly the E value for reaction (1.3) is:

0.059 1
E = −0.44 − log = −0.499 …(1.10)
2 [ Fe ++ ]

This E value is the potential for the cathodic reaction. Since we need the
potential of the anodic reaction, its potential should be 0.499 eV. Then the free energy
is:

ΔG = -2F(0.499) = -23.01 kcal/mole.

Now the free energy of the overall reaction (1.8) is the sum of those for the half-
cell reactions, which is -20.29 kcal.

The sign of this free energy indicates that the overall reaction is spontaneous. If
ΔG is negative, the reaction is spontaneous because the energy level at the final state is
lower than that of initial state. Also the reverse is true. When ΔG is zero, the reaction is
at equilibrium.

1.5 Potential Measurement of Half-Cell Reaction

The reference electrode is needed to measure the potential of the half-cell
reaction. Since the potential of reference electrode is known and we measure the

7
 Corrosion Tutorial

potential difference between the half-cell reaction and the reference electrode, we can
measure the potential of the half-cell reaction. The measurement should be conducted
in a circuit with a high impedance value. Otherwise, a significant current flows through
the circuit and then the potential changes to give a wrong value of the half-cell reaction.

There are several types of reference electrodes. The standard electrode is

prepared with platinum wire immersed in a chamber, which contains 1 molar H+ ion, and
pure hydrogen gas is bubbled through the solution. The potential of this reference
electrode is given as:

2H+ + 2e- = H2 E0 = 0 eV …(1.11)

Thus, the standard hydrogen electrode is not practical because it involves

flammable hydrogen gas. Thus, other reference electrodes are used. One of them is
calomel electrode and it has the following half-cell reaction:

Hg2Cl2 + 2e- = 2Hg + 2Cl- E0 = 0.241 eV …(1.12)

The potential at the saturation of chloride ion is 0.241 eV.

The next reference electrode is copper-copper sulfate electrode and it has the
following half-cell reaction:

CuSO4 + 2e- = Cu + SO4- E0 = 0.318 eV …(1.13)

The potential at the saturation of copper ion is 0.318 eV.

The next reference electrode is silver-silver chloride electrode and it has the
following half-cell reaction:

AgCl + e- = Ag + Cl- E0 = 0.222 eV …(1.14)

8
 Corrosion Tutorial

2 PASSIVITY AND ELECTROCHEMICAL CORROSION

MEASUREMENTS

2.1 Passivity
When an oxidizer such as ferric ion is added to a solution in which a metal (e.g.,
iron, nickel, chromium, titanium) is immersed, a typical polarization curve as shown in
Figure 2.1 is produced.

ipass (passive
current) Oxygen evolution
Etp
transpassive

passive
E
icc (critical
current)

Epp
(passivation
active
potential)
Ecorr (corrosion
potential)

Log i

Figure 2-1: Schematic Active-Passive Behavior of the Anodic Polarization of a Metal

In the active zone, the curve follows Tafel behavior. However, when the voltage
increases (by adding more oxidizer), the current starts decreasing until it reaches ipass
(passive current). This passive current is retained until the potential reaches Etp

9
 Corrosion Tutorial

(transpassive potential). Above Etp, the current starts increasing again like in the active
zone.

The passive zone has the lowest current due to the formation of metal
hydroxide/oxide film. This film is usually impermeable for the corrosion reagents such
as oxygen and water thus reducing the metal corrosion drastically. At Etp the film
becomes unstable making the film break down, and the current starts increasing above
its potential.

The passivity is one of the important aspects in corrosion. Passive films are
intentionally produced to control the corrosion rates. For example, in anodic protection,
applying a potential to form a passive film protects acid storage tanks. Titanium alloys
are frequently used in an aggressive environment to induce passive film. Since titanium
is an active metal, it induces passive film easily. Stainless steels are generally immune
to atmospheric corrosion where oxygen is involved but they are not immune to acid
environment. The mechanism is illustrated in Figure 2.2. It can be seen from Figure
2.2 that the higher potentials with oxygen can induce passivity while the lower potential
with acid induces higher corrosion rate.

2H2O+O2+4e-

2H++2e-=H2

Log i
Figure 2-2: Schematic Representation of Corrosion of Stainless Steel with Two Oxidation Reagents

10
 Corrosion Tutorial

There are two methods to generate anodic polarization curves. Figure 2.3
compares both methods. The dotted line is produced by galvanostat where potential is
measured at each increment of current. Thus, the passivity cannot be revealed by this
method. However, since the potentiostat measures current at each increment of
potential, the passive zone will be revealed. This potentiostat should be used to
measure the passivity.

Galvanostat
E

Potentiostat

Log i

Figure 2-3: Comparison of Galvanostatic and Potentiostatic Anodic Polarization Curves

The methods available for measurement of corrosion by electrochemical

polarization are as follows:

1. Tafel extrapolation

2. Polarization resistance

Polarization measurements are found to be useful in engineering and research

applications due to its inherent advantages such as accuracy, speed, continuous
monitoring and non-destructive measurements.

11
 Corrosion Tutorial

2.2 Tafel Extrapolation

The Tafel extrapolation technique uses the data obtained from the cathodic
polarization measurements. Consider a metal M in de-aerated acid solution. In Figure
2.4, the solid lines represent the experimentally measured cathodic polarization and
anodic polarization data. As the current density increases, the region is found to be
linear compared to less current density values. This linear region is referred to as Tafel
region. To determine the corrosion rate from this measurement, the Tafel region is
extrapolated to obtain the corrosion potential. The accuracy of this technique is better
than the conventional techniques. The disadvantage of this system is that it cannot be
applied for systems having more than one reduction reactions.

2H++2e-=H2(g)
Experimental

Ecorr icorr Tafel

equation
E

Fe=Fe2++2e-

Log i

Figure 2-4: Cathodic and Anodic Polarization Curves

12
 Corrosion Tutorial

2.3 Linear Polarization Resistance Method

Linear Polarization Resistance Method (LPR) is the only corrosion monitoring
method that allows corrosion rates to be measured directly in real time. The response
time and data quality makes this technique superior to other methods. This method is
limited to electrolytically conducting liquids.

2.3.1 Derivation of the Polarization Resistance

It is experimentally observed that iapp is almost linearly related to applied potential
within a few millivolts of polarization from Ecorr. Stern and Geary simplified the kinetic
expression to provide an approximation to the charge transfer controlled reaction
kinetics given by Equation (2.1) for the case of small overvoltage with respect to Ecorr.

2.3( E − Ecorr ) 2.3( E − Ecorr )

iapp = I corr [exp( ) − exp( )] …(2.1)
βa βc

where βa = anodic Tafel slope

βc = cathodic Tafel slope

Icorr / icorr = corrosion rate/corrosion current density

Ecorr = corrosion potential

Equation (2.1) can be approximated mathematically by taking its series

expansion (e.g., ex = 1 + x + x2/2! + x3/3! +….) and by neglecting higher terms when
ΔE/β < 0.1. This simplified relationship has the following form

E βa * βc
Rp = [ ](E - Ecorr )→0 = ...(2.2)
iapp 2.3icorr ( β a + β c )

Rearranging

βa * βc B
icorr = = …(2.3)
2.3R p ( β a + β c ) R p

Rp is the polarization resistance

13
 Corrosion Tutorial

βa = anodic Tafel slope

βc = cathodic Tafel slope

B is the proportionality constant

The units of Rp are ohms as obtained from E-Iapp data when the applied current is
not normalized by electrode area (such data must be multiplied by electrode area to
yield Rp (Ω-cm2)). If the electrode area is doubled, the measured Rp value in ohms is
halved, and this intrinsic polarization resistance value remains the same. This gives the
result that corrosion rate per unit area is independent of electrode area. However, the
working electrode area must be known to calculate the corrosion rate.

The B factor is dominated by the smaller of the two anodic and cathodic Tafel
slopes (βa, βc), if unequal. Therefore, cathodic mass transport control results in B =
βa/2.3 and similarly anodic mass transport control results in B = βc/2.3. Knowledge of
Rp, βa, and βc enables direct determination of the corrosion rate at any instant in time
using equation (2.3). iapp is approximately linear with potential within ± 5 mV to 10 mV
of Ecorr . Consequently the method is called linear polarization method (LPR). The
extent of approximately linear E – iapp region can vary considerably among corroding
systems. It can be infered that corrosion rate is inversely proportional to the Rp.

2.3.2 Principle of Measurement

Before making any measurements, residual potential difference between the
reference electrode (R) and the test electrode (T) should be nullified. After which,
current will flow from the auxiliary electrode (A) onto the test electrode. The flow of
current between the auxiliary electrode and test electrode will increase until the test
electrode potential is shifted 10 mV with respect to the reference electrode. The current
(ΔI) required to sustain the 10 mV potential shifts is proportional to the corrosion rate of
the test electrode.

14
 Corrosion Tutorial

2.3.3 Advantages of Polarization Resistance Measurements

• Rapid Measurement.
• Accuracy of the measurement of even smaller corrosion values.
• Can be used to monitor corrosion continuously which cannot be inspected
visually or by other methods.

2.3.4 Errors and Limitations in the Use of Polarization Resistance

Measurements
• The Stern-Geary relationship is only mathematically valid only when ΔE is equal
to zero
• Curvature of polarization curves about the corrosion potential, Ecorr can cause
errors in the measurement of polarization resistance when linearization
techniques are involved.
• This equation is valid only for activation controlled process
• This method is not applicable under the special non-Tafel conditions
corresponding to passivity or cathodic diffusion limiting current densities.
• The corrosion rate icorr must be much larger than any other exchange currents of
half-cell reactions, or the latter rates will dominate the polarization resistance
measurement.
• Resistances from the presence of films on the electrodes and the electrolyte
resistance between the working and reference electrode in high resistivity media
can produce an underestimation of corrosion rates due to IR (current times
resistance) losses on ΔE and must be compensated to obtain accurate
measurements.

15
 Corrosion Tutorial

2.4 Other Methods to Determine Polarization Resistance

2.4.1 Electrochemical Impedance Spectroscopy

Electrochemical impedance spectroscopy is a well-established laboratory
technique used to determine the electrical impedance of the metal-electrolyte interface
at various AC frequencies. Impedance measurements combine the effects of DC
resistance with capacitance and inductance. In order to make impedance
measurements, it is necessary to have a corrosion cell of known geometry, a reference
electrode, and instrumentation capable of measuring and recording electrical response
of the test corrosion cell over a wide rate of AC excitation frequencies. Again, with the
evolution of more rugged computers, some investigation of this method is now being
made in the field. AC impedance is capable of characterizing the corrosion interface
more comprehensively and with good quality equipment specifications of achieving
measurements in lower conductivity solution or high resistivity coatings. AC impedance
measurements can be used to predict corrosion rates and characterize systems under
study and are commonly used for performance studies of chemical inhibitors and
protective coatings to evaluate the resistance of alloys to specific environments etc.

2.4.2 Electrochemical Noise

Electrochemical noise is a monitoring technique, which directly measures
naturally occurring electrochemical potential and current disturbances due to ongoing
corrosion activity. It has the same media conductivity limitations and requirement for a
known electrode area as other electrochemical techniques. It is generally less
quantitative than linear polarization resistance for corrosion rate calculations; it is useful
in detecting transient effects in marginally conductive situations. Laboratory and field
interpretations are still under development. One advantage is that this technique can
provide a large quantity of information, which can be useful in determining what is
actually happening in real time with corrosion activity in piping or equipment being
monitored. One disadvantage is that there is too much information to analyze,

16
 Corrosion Tutorial

especially, when there is a contact but acceptable level of corrosion activity in the
system or another source of potential electrical disturbance in the system.

17
 Corrosion Tutorial

3 FORMS OF CORROSION

The various forms of corrosion that are prevalent in metals are discussed in
terms of their characteristics, mechanisms, and preventive measures in this chapter.

3.1 Uniform Corrosion

Uniform (or general) corrosion is a form of corrosion where there is uniform
reduction of thickness over the surface of a corroding material. This is the most
important form of corrosion on the basis of tonnage wasted. Uniform corrosion can be
easily measured and predicted. This leads disastrous failures relatively rare. The
breakdown of protective coating systems on structures often leads to this form of
corrosion.

Figure 3-1: Uniform Corrosion.

(Reference:http://corrosion.ksc.nasa.gov/html/unifcor.htm )

18
 Corrosion Tutorial

Figure 3-2: Example of uniform corrosion damage on a rocket assisted artillery projectile
(Reference: http://www.corrosion-doctors.org/Forms/projectile.htm)

By selecting suitable materials and protective coatings, uniform corrosion can be

controlled. Cathodic protection and corrosion inhibitors are other preventive methods.

“It is relatively easy to monitor uniform corrosion; generally the simplest methods
suffice (coupons, ER, NDT techniques for thickness measurements). Much data on
uniform corrosion has been published that can be used for design purposes and
estimating a corrosion allowance".

In most practical cases, corrosive environments tend to differ from "textbook"

cases (even small differences can be very significant). Furthermore, actual uniform
corrosion rates tend to vary with time; this variability is not accounted for by single
"textbook values". Corrosion monitoring is therefore advisable.

Unexpected rapid uniform corrosion failures can occur if the material's surface
changes from the passive (low corrosion rate) to the active (high corrosion rate) state.
The resultant increase in uniform corrosion rate is typically several orders of magnitude.
This undesirable transition can occur if the passive surface film is disrupted by
mechanical effects, flow rate changes, a chemical change in the environment etc. Real-
time corrosion monitoring systems can detect such transitions.” (This excerpt is taken
from www.corrosion-club.com)

19
 Corrosion Tutorial

3.1.1 Atmospheric corrosion

Atmospheric corrosion is defined as the corrosion or degradation of the material
exposed to the air and its pollutants. This has been identified as one of the oldest forms
of corrosion and has been reported to account for more failures in terms of cost and
tonnage than any other single environment. The rate at which the corrosion takes place
and the severity is primarily dependant upon the properties of the surface formed
electrolyte, which in turn depends upon the factors such as relative humidity, climatic
conditions, temperature, atmospheric pollutants etc.

3.1.1.1 Mechanism of Atmospheric Corrosion

Atmospheric corrosion is an electrochemical process, which takes place in the
presence of an electrolyte. Depending upon the climatic conditions, relative humidity
and temperature, a certain humidity level is reached which tends to form a thin
electrolyte on the metallic surfaces. The following reactions take place.

Anodic reaction 2M Æ 2M2+ + 4e-

Cathodic reaction O2 + 2H2O + 4e- Æ 4OH-

Figure 3-3: Atmospheric corrosion of galvanized anti crash railing due to marine aerosol condensation on
wooden post
(Reference: http://www.corrosion-doctors.org/AtmCorros/AtmCorr.htm)

20
 Corrosion Tutorial

It is an established principle that if a change occurs under which a system is in

equilibrium, the system will tend to adjust itself so as to nullify the effect of that change.
Therefore, in the presence of an electrolyte, atmospheric corrosion proceeds by
balancing cathodic and anodic reaction. The anodic reaction involves the dissolution of
the metal in the electrolyte, while the cathodic reaction involves reduction. Oxygen from
the atmosphere is readily supplied to the electrolyte in thin film conditions.

3.1.1.2 Prevention of Atmospheric Corrosion

There are two approaches to prevent Atmospheric corrosion. The first is a
temporary one which is used during storage and which consists of lowering of
atmospheric humidity by using a desiccant, heating devices, or by treating the surface
with vapor phase or surface inhibitors. Permanent solution is by applying organic,
inorganic and metallic coatings effectively.

3.1.2 Galvanic Corrosion

When two dissimilar metals are coupled and immersed in an electrolyte solution,
a galvanic cell is formed. In a galvanic cell, the more active metal is corroded while the
noble metal is protected. Corrosion of active metal is increased and of noble metal is
decreased upon galvanic coupling. Figure 3.4 shows galvanic corrosion between the
pipe made of black iron and a brass valve.

Figure 3-4: Galvanic Corrosion of Brass Coupled With Black Iron

(Reference: http://www.eci-ndt.com/gallery_a.htm)

21
 Corrosion Tutorial

When two dissimilar metals M and N, with N being more active, are connected
and immersed in an acid solution, the corrosion mechanism may be depicted in a
graphical representation as shown in Figure 3.5.

2H+ H2

M N N2+
2e-

Figure 3-5: Mechanism of Galvanic Corrosion of a Two Metal Couple

The more noble metal M undergoes the cathodic reaction while the active metal
N undergoes the anodic reaction. The electrons produced by the dissolution of N are
consumed by the cathodic reaction that takes place on the noble metal surface. Thus,
corrosion of the noble metal retards while that of the active metal accelerates because
of the galvanic effect generated on the metal surface.

The magnitude of the galvanic current flow is controlled by the potential

difference and the total resistance to current flow as shown in the Figure 3-6, which can
be broken down further into the following resistance components.

Resistance to current flow of the electrolyte.

Resistance to current flow in the conducting materials and in the

connection between them.

Resistance associated with polarization behavior of the anode and

cathode.

The Figure 3-6 illustrates a cell showing the corrosion process in its simplest
form. This cell includes the following essential components: a metal cathode, metal
anode, a metallic conductor between anode and the cathode and an electrolyte in

22
 Corrosion Tutorial

contact with the anode and the cathode. They are so arranged to form a closed electric
path.

Figure 3-6: Galvanic cell showing corrosion process in its simplest form

(Reference: http://www.edstrom.com/Resources.cfm?doc_id=131)

The cathode is positively charged and anode is negatively charged. The

difference in charge provides potential voltage which is the driving force for the current
to flow in the cell.

Hydrogen gas is produced at the cathode and no destruction will occur while the
anode gives off its ions in the form of rust, this is where the corrosion occurs. The rate
of which depends upon the relative sizes of the anode and cathode and also the
potential difference between cathode and anode.

If, for instance, the anode is very small compared to the cathode, the rate of
corrosion would be very rapid. The opposite would be true if there was a very large
anode compared to the cathode.

When contact with a dissimilar metal is made, however, the self-corrosion rates
will change: corrosion of the anode will accelerate; corrosion of the cathode will
decelerate or even stop.

23
 Corrosion Tutorial

This is shown in Figures 3-7 to 3-9. Figure 3-7 shows the corrosion rate for a
single metal in solution.

E
(V)

Cathodic Reaction 1

Ecorr

Anodic reaction 2

log Current Density

2 icorr
μA/cm

Figure 3-7: Corrosion rate determination for a two electrode process system

(Reference: http://www.egr.uri.edu/che/course/CHE534w/chapter3EnivronmentalCorrosion.htm)

Figures 3-8 and 3-9 shows the rate determination when a third electrode process
is added at a potential between the first two electrode reactions. The rule that must be
applied is that the ‘total oxidation rate must be equal to the total reduction rate.’

24
 Corrosion Tutorial

E
(V)
Cathodic Reaction 1

Anode Reaction 3

Ecorr 1+2
Total Cathode 1+3
Cathode Reaction 3

Anodic Reaction 2

log Current Density

2 icorr 1+2
μA/cm

Figure 3-8: Corrosion rate determination for a three electrode system.

(Reference: http://www.egr.uri.edu/che/course/CHE534w/chapter3EnivronmentalCorrosion.htm)

From Figure 3-8, it is seen that the corrosion rate for electrode 2 has increased
from icorr to icorr 1+2 as it is the only anodic reaction. Two cases are shown in Figures 3-8
and 3-9; when the corrosion potential for three electrodes is above the two electrode
potential and when the three electrode corrosion potential is below the two electrode
potentials respectively. In Figure 3-8 the resulting corrosion potential is more negative
than the third electrode reverse potential, thus contributing to the cathodic reaction and
protecting the third electode from corrosion. The second electrode dissolution rate
increased significantly by the introduction of the third electrode processes.

In Figure 3-9, the resulting corrosion potential from the three electrodes is more
negative than the double electrode potential. In this case both the second and third
electrodes are corroding, but the third electrode corrodes at a lower rate than the
second electrode.

25
 Corrosion Tutorial

E
(V)
Cathodic Reaction 1

Anode Reaction 3

Ecorr 1+2

Cathode Reaction 3 Total Anode 1+3

Anodic Reaction 2

log Current Density

2 icorr 1+2
μA/cm

Figure 3-9. The introduction of a less noble metal will decrease the corrosion rate of the more noble metal.

(Reference: http://www.egr.uri.edu/che/course/CHE534w/chapter3EnivronmentalCorrosion.htm)

Both these Figures 3-8 and 3-9 show that introducing a more anodic metal will
decrease the corrosion rate in a more noble metal. This is the process behind galvanic
corrosion. It can also be used for protection by galvanizing.

The seawater Galvanic Series, shown in table 3-1 below can be used to predict
which metal will become the anode and how rapidly it will corrode. The metals below
are arranged according to their tendency to corrode galvanically. Metals with negative
voltage charges (anodic–least noble) are listed first, followed by metals with positive
charges (cathodic–more noble).

3.1.2.1 CORRODED END (ANODIC OR LEAST NOBLE)

• MAGNESIUM
• MAGNESIUM ALLOYS
• ZINC
• ALUMINUM 5052, 3004, 3003, 1100, 6053

26
 Corrosion Tutorial

• CADMIUM
• ALUMINUM 2117, 2017, 2024
• MILD STEEL (1018), WROUGHT IRON
• CAST IRON, LOW ALLOY HIGH STRENGTH STEEL
• CHROME IRON (ACTIVE)
• STAINLESS STEEL, 430 SERIES (ACTIVE)
• 302, 303, 304, 321, 347, 410,416, STAINLESS STEEL (ACTIVE)
• NI - RESIST
• 316, 317, STAINLESS STEEL (ACTIVE)
• CARPENTER 20 CB-3 STAINLESS (ACTIVE)
• ALUMINUM BRONZE (CA 687)
• HASTELLOY C (ACTIVE) INCONEL 625 (ACTIVE) TITANIUM (ACTIVE)
• LEAD - TIN SOLDERS
• LEAD
• TIN
• INCONEL 600 (ACTIVE)
• NICKEL (ACTIVE)
• 60 NI-15 CR (ACTIVE)
• 80 NI-20 CR (ACTIVE)
• HASTELLOY B (ACTIVE)
• BRASSES
• COPPER (CA102)
• MANGANESE BRONZE (CA 675), TIN BRONZE (CA903, 905)
• SILICON BRONZE
• NICKEL SILVER
• COPPER - NICKEL ALLOY 90-10
• COPPER - NICKEL ALLOY 80-20
• 430 STAINLESS STEEL
• NICKEL, ALUMINUM, BRONZE (CA 630, 632)
• MONEL 400, K500

27
 Corrosion Tutorial

• SILVER SOLDER
• NICKEL (PASSIVE)
• 60 NI- 15 CR (PASSIVE)
• INCONEL 600 (PASSIVE)
• 80 NI- 20 CR (PASSIVE)
• CHROME IRON (PASSIVE)
• 302, 303, 304, 321, 347, STAINLESS STEEL (PASSIVE)
• 316, 317, STAINLESS STEEL (PASSIVE)
• CARPENTER 20 CB-3 STAINLESS (PASSIVE), INCOLOY 825
• NICKEL - MOLYBDEUM - CHROMIUM - IRON ALLOY (PASSIVE)
• SILVER
• TITANIUM (PASS.) HASTELLOY C & C276 (PASSIVE), INCONEL 625(PASS.)
• GRAPHITE
• ZIRCONIUM
• GOLD
• PLATINUM

3.1.2.2 PROTECTED END (CATHODIC OR MOST NOBLE)

From the list 3.1.2.1, it is true that each metal has a different electrical potential
when immersed in the same electrolyte (an electrically conductive fluid such as sea
water). As a result, if two dissimilar metals are placed in the same electrolyte, their
different electrical potentials will produce a voltage that can be measured on the two
pieces of metal. According to the potential difference of these two metals, the current
flows from higher voltage metal to the lower one. This action raises the voltage of the
lower-voltage metal above its natural potential. To establish the equilibrium, the lower-
voltage metal discharges a current in to the electrolyte. The current passes through the
electrolyte back to the higher-voltage metal and completes the electrical circuit between
the two pieces. The current flowing through the electrolyte is generated by an
electrochemical reaction that steadily consumes the lower-voltage metal a process
known as galvanic corrosion.

28
 Corrosion Tutorial

In couple A, the aluminum rivet is comparatively small, and the C/A ratio is large.
In couple B, the situation is reversed: the stainless steel rivet is small, and the C/A ratio
is also small. Corrosion of the aluminum rivet in couple A will be severe. However,
corrosion of the large aluminum plate in couple B will be much less, even though the
potential difference is the same in each case.

The two major factors affecting the severity of galvanic corrosion are (1) the
voltage difference between the two metals on the Galvanic Series, and (2) the size of
the exposed area of cathodic metal relative to that of the anodic metal. Corrosion of the
anodic metal is both more rapid and more damaging as the voltage difference increases
and as the cathode area increases relative to the anode area.

Figure 3-10: Effect of cathode to anode ratio in galvanic corrosion

(Reference: http://www.ocean.udel.edu/seagrant/publications/corrosion.html)

The effect of the second factor, the cathode-to anode area ratio, C/A, is
illustrated in Figure 3-10 for a rivet in a plate. In both couples A and B, aluminum is the
anode, and stainless steel is the cathode. In couple A, the aluminum rivet is
comparatively small, and the C/A ratio is large. In couple B, the situation is reversed: the
stainless steel rivet is small, and the C/A ratio is also small. Corrosion of the aluminum
rivet in couple A will be severe. However, corrosion of the large aluminum plate in
couple B will be much less, even though the potential difference is the same in each
case.

29
 Corrosion Tutorial

3.1.2.3 Factors Affecting Galvanic Corrosion

Area Effect
The current flowing between anode and cathode will be the same independent of
the surface area of each electrode. For the anodic and cathodic reactions, it is the
current rather than current density which is equal. Since the corrosion occurs at anode,
the rate of corrosion depends on the current density in the anode. To minimize the
galvanic corrosion, the anode area should be very large compared to the cathode area.
Inorder to protect the system from galvanic corrosion, the cathode of the system should
be painted. If the paint is damaged, then small cathode to large anode area ratio is
formed which results in minimizing corrosion rates. Conversely, if the anode is painted,
then the damage to the paint causes large cathode to small anode ratio resulting in
large corrosion rates in the anode and thus penetrating into the metal. The anode to
cathode area effect is an important characteristic. It is important in several other forms
of corrosion including pitting corrosion, crevice corrosion, stress corrosion cracking and
corrosion fatigue.

Distance Effect
Distance effect is another important factor for galvanic corrosion. Galvanic
corrosion rates are the largest at the interface between the anode and cathode and
decrease with distance away from the contact region. The transportation of the ions
becomes more difficult when the distance between anodic and cathodic reaction site
increases thus decreasing the corrosion rate. Essentially the resistance of the
electrolyte increases with distance. This is an important factor in determination of the
form of corrosion. If a galvanic corrosion is suspected, then according to the rule as
explained, the rate of corrosion adjacent to the galvanic contact region should be
higher. If the corrosion rate is far away from this area then different type of corrosion
may be involved. For example if corrosion appears at a constriction some distance from
a galvanic contact, then erosion corrosion was the cause and not the galvanic
corrosion.

30
 Corrosion Tutorial

Distance Apart in the Galvanic Series

Galvanic series is an empirical listing of the corrosion resistance of metals. Its
advantage over the Redox series is that it refers to alloys in a real environment. Metal at
the top of the system are highly cathodic while metals at the bottom highly anodic. For
selection purposes metals close together on the list are desirable as there is little driving
force for corrosion to be accelerated. Clearly, it is undesirable to connect metals widely
spaced on the galvanic series.

3.1.2.4 Galvanic Series

Galvanic series is a list of metals/alloys according to their corrosion potentials.
The list is formed by polarization of two or more half-cell reactions to a common mixed
potential, Ecorr on the corroding surface. Corrosion potentials in the galvanic series are
measured in real or simulated service conditions. The galvanic series gives only
tendencies for galvanic corrosion, not the rate. In the galvanic series, the potential
changes due to changes in electrolyte composition and temperature. For every change
in environmental conditions, a new series needs to be established. Table 3.1 lists some
of the metals/alloys for the galvanic series in seawater. In Table 3.1, titanium is a
noteworthy element. Titanium is a very active metal with E0 value being -1.63 V for the
reduction of:

Ti2+ + 2e- = Ti …(3.1)

However, it has a very noble corrosion potential. This may be due to the fact that
titanium surface is easily covered with passive film with normal potential oxidizing
reagents such as oxygen.

31
 Corrosion Tutorial

Table 3-1: Galvanic Series of Metals/Alloys in Seawater

Noble Platinum

⇑ Gold

Titanium

Silver

Hastelloy C (62 Ni, 17 Cr, 15 Mo)

18-8 Stainless steel (passive)

Inconel (passive) (80 Ni, 13 Cr, 7 Fe)

Cast Iron

Wrought Iron

Copper

Red Brass

Cadmium

Manganese Bronze

Aluminum 52SH

Tin

Lead

Zinc

⇓ Magnesium Alloys

Active Magnesium

32
 Corrosion Tutorial

3.1.2.5 Prevention of Galvanic Corrosion

• Coupling of two dissimilar metals should be avoided when they are much apart in
the galvanic series.
• In the case where such coupling is necessary, break the electrical contact
between the two metals by using insulation such as gaskets and rubber.
• Do not paint anodic area because if the paint is ruptured in a small area, the
corrosion rate in the area will increase drastically. Instead, paint the cathodic
area.

3.1.3 Stray Current Corrosion

Stray current corrosion is the current flowing through unintended paths due to
some kind of leakage from extraneous sources. The damage caused to the metal
components due to this unwanted current refers to stray current corrosion. Metals like
aluminum under soil or water are affected due to this kind of corrosion. This current
mostly originates due to bad earthen systems of electrical equipments and eventually
leaks through the metal structures or other conductive systems. The common sources
of these stray current include electric railway systems, cathode protection systems of
nearby equipment or pipelines, DC-driven elevators, etc.

The mechanism involved in stray current corrosion is that an electrolysis cell is

formed that forces the metal structure through which it passes to act as an anodic site.
Thus local oxidation occurs and the metal is consumed rapidly.

3.1.3.1 Direct Stray Current Corrosion

This type of corrosion occurs due to direct current from sources like rail transit
system, DC welding equipment. Again this type of corrosion can be classified as
dynamic current corrosion when the current is not steady or flows irregularly and as
static current corrosion when the flow is steady. The effects of direct stray current are
very severe compared with alternative currents.

33
 Corrosion Tutorial

3.1.3.2 Alternating Stray Current Corrosion

This type of corrosion is caused due to alternate currents from sources like
overhead AC power lines.

3.1.3.3 Telluric Effects

The disturbances in the earth’s magnetic field called geomagnetic activity may
lead to the production of dynamic stray currents. These currents induced naturally due
to the geomagnetic activity are called telluric effects.

These may flow onto a buried pipeline varying the magnitude of current flow and
the position of current pick-up. The discharge areas will also fluctuate with time.

Figure 3-11: Occurrence of Stray current corrosion in pipelines.

(Reference:http://www.corrosion-club.com/stpickup.htm)

Basic Theory
A protective coating is used as the primary form of protection for buried
pipelines. Additionally, cathodic protection is designed to provide protection at coating
discontinuities. Thus a combination of a protective coating system and cathodic

34
 Corrosion Tutorial

protection system is used to reduce the corrosion risk factor. Figure 3-12 schematically
illustrate current flow in an impressed current cathodic protection system (the principle
is similar for a sacrificial anode system). Under these idealized conditions, current flows
through the electrolyte (soil) onto the pipeline, in the form of ionic current.

Figure 3-12: Ionic current flow onto the pipeline.

(Reference:http://www.corrosion-club.com/sttheory.htm)

The schematic diagram in Figure 3-13 details the current flow onto the pipeline at
coating discontinuities, under the protective influence of the cathodic protection system.

Figure 3-13: Current flow onto pipeline at coating discontinuities.

(Reference:http://www.corrosion-club.com/sttheory.htm)

Current flow in the electrolyte that does not originate from the cathodic protection
system designed to protect the pipeline is referred to as stray current. Such external
stray current sources interfere with the normal operation of the cathodic protection
system leading to corrosion problems.

35
 Corrosion Tutorial

Figure 3-14: External stray current sources.

(Reference:http://www.corrosion-club.com/sttheory.htm)

3.1.4 General Biological Corrosion

Microorganisms such as Iron Related Bacteria (IRB), Sulfate Reducing Bacteria
(SRB) and Heterotrophic Aerobic Bacteria (HAB) grow on iron and steel pipes that lead
to the corrosion of these metals. This type of corrosion can occur through aerobic and
anaerobic corrosion. The other name for this corrosion is Biofouling.

3.1.4.1 Causes of Biological Corrosion

Bacteria
Bacteria may be either aerobic or anaerobic, aerobic bacteria sustains only when
oxygen is present. Sulfur is oxidized to produce sulfuric acid and thus corrosion is
accelerated. Metals are subject to corrosion when the bacteria deplete the oxygen
supply or releases metabolic products. On the other hand, anaerobic bacteria, can
survive only when free oxygen is not present. The metabolism of these bacteria requires
them to obtain part of their sustenance by oxidizing inorganic compounds, such as iron,
sulfur, hydrogen, and carbon monoxide. The resultant chemical reactions cause
corrosion.

36
 Corrosion Tutorial

Fungi
Microorganism feed on organic materials and this leads to the growth of fungi.
Low humidity does not kill microbes; it slows their growth and may prevent damage due
to corrosion. Temperatures between 68 F and 108 F and relative humidity between 85
and 100 percent are ideal conditions for the growth of most of the microorganisms.

3.1.4.2 Prevention of Biological Corrosion

Microbial growth must be removed completely to avoid corrosion. Microbial
growth should be removed by hand with a firm non-metallic bristle brush and water.
Removal of microbial growth is easier if the growth is kept wet with water. Microbial
growth may also be removed with steam at 100 psi. Protective coating is used when
using the steam for removing microbial growth.

A simple, yet effective method for monitoring the population size and/or activity of
specific groups of bacteria is Biological Activity Reaction Test.

Below is an image of a carbon steel plate section that is bio-corroded. In the

analysis chamber of the ESEM XL30 TMP Philips Electron Microscope, the image was
obtained in high vacuum. The corrosion product is brown. Bacteria produce tubercles
and, under the tubercles a small hole. Bacteria collect inside the holes and produce
FeS. Biological corrosion also affects copper and aluminum alloys.

Figure 3-15: Corroded surface of carbon steel in its natural condition.

(Reference: http://www.esemir.it/images/bcorr2_i.htm)

37
 Corrosion Tutorial

3.1.5 Molten Salt Corrosion

The corrosion of metal containers by molten or fused salts is known as molten
salt corrosion. This phenomenon mostly occurs at high temperatures.

3.1.5.1 Mechanism of Molten Salt Corrosion

Metal dissolution and Metal oxidation are the two common mechanisms involved
in this corrosion. Molten salt corrosion can be identified as the intermediate form of
corrosion between molten metal and aqueous corrosion. Many principles that apply to
aqueous corrosion also apply to molten salt corrosion, such as anodic reactions leading
to metal dissolution and cathodic reduction of an oxidant. The corrosion process is
mainly electrochemical in nature, due to the ionic conductivity of most molten salts.
Molten salts are partially electronic conductors as well as ionic conductors. This fact
allows for reduction reactions to take place in the melt. Cathodic reactions increase
causing a substantial increase in corrosion growth. Molten salt systems operate at
higher temperatures than aqueous systems.

3.1.5.2 Types of Molten salts

ƒ Molten Fluorides

ƒ Chloride Salts

ƒ Molten Nitrates

ƒ Molten Sulfates

ƒ Hydroxide Melts

ƒ Carbonate Melts

In nuclear reactor cooling systems, fluoride melts are used. Corrosion in fluoride
molten-salt melts is enhanced because protective surface films are not formed. Nickel-

38
 Corrosion Tutorial

base alloys show better corrosion resistance than iron-base alloys. Chloride salts attack
steels rapidly with preferential attack of carbides.

In order to prevent molten salt corrosion, a material should be selected that will
form a passive non-soluble film in the melt. Minimizing the entry of oxidizing elements
such as oxygen and water into the melt is important.

3.1.6 Corrosion in Liquid Metals

Liquid metals are widely used in nuclear reactors and nuclear power systems.
Liquid lithium, mercury, potassium and cesium are some of the examples of liquid
metals, used in the above said applications. Liquid metal corrosion may be formed due
to the dissolution of the solid metal. The metal surface may react with the liquid metal
due to the presence of some impurities, to form an alloy or due to compound reduction.

3.2 Localized corrosion

Localized corrosion is defined as the selective removal of material by corrosion at
small areas and zones in contact with corrosive environment. It usually takes place
when there is intense attack at the localized sites than at the rest of the original surface.
It is mostly accompanied with other destructive processes such as stress, fatigue,
erosion and other forms of chemical attack. The following are different types of localized
corrosion.

3.2.1 Pitting Corrosion

When passive metal surface is exposed to a chloride solution, corrosion is
initiated by forming pits on the metal surface. Pitting is a form of extremely localized
attack that results in holes in the metal. Pits are difficult to determine because they are

39
 Corrosion Tutorial

smaller in size and they will be covered with the corrosion products. Figure 3-16 shows
pitting corrosion on aluminum surface.

Figure 3-16: Pitting in Aluminum

(Reference: http://www.clihouston.com/pitting.htm)

3.2.1.1 Initiation of Pitting Corrosion

Pitting corrosion is initiated when the passive film is attacked by chloride ions in
solution. Most of the metal oxide/hydroxide films are soluble by chloride ions. Further,
hydrogen ions are produced by the hydration of metal chloride. These hydrogen ions
further attack the substrate of the metal matrix, because there would not be passive
films formed in the presence of chloride ions.

Stainless steel is well known to be susceptible to pitting corrosion. The reason is

that upon hydration of CrCl3, very low pH is produced. D. A. Jones and B. E. Wilde
observed that upon hydration of 1 N CrCl3 (N=normality) produced a pH of 1.1 while 1 N
of FeCl2 and NiCl2 produced pH of 2.1 and 3.0, respectively. These results show that
stainless steel, which contains chromium, is most susceptible and nickel alloys are least
susceptible to pitting corrosion.

3.2.1.2 Propagation of Pitting Corrosion

Once the pits are initiated in the presence of chloride ions, the metal ions
produced by corrosion attract more chloride ions by Coulomb forces into the pits,

40
 Corrosion Tutorial

making the pit solution more concentrated. Since the solubility of oxygen is virtually
zero in concentrated solutions, no oxygen reduction occurs within a pit. The metal ions
are hydrated and the aqueous metal hydroxide is transported to outside of the pit where
it is further oxidized in the case of steel. The growth of the pit is by two distinct
mechanisms. One is by acid produced upon the hydration of metal ions. The other is
formation of an electrical circuit between an anodic reaction of metal dissolution which
takes place at the pit and the cathodic reaction of oxygen reduction reaction which takes
place outside the pit. These mechanisms can be seen graphically in Figure 3.17 in the
case of steel.

The hydration of ferrous ion is given by

Fe2+ + 2H2O = Fe(OH)2(aq) + 2H+ …(3.2)

We can see that the hydration produces an acid, which further corrodes the pit.
The reaction is:

Figure 3-17: Propagation of Pitting Corrosion

Fe + 2H+ = Fe2+ + H2 …(3.3)

The other mechanism where iron is dissolved with oxygen can be written as:

2Fe + 2H2O + O2 = 2Fe2+ + 4OH- …(3.4)

41
 Corrosion Tutorial

Finally the oxidation of Fe(OH)2 to Fe(OH)3 can be written also:

4Fe(OH)2(aq) + O2 + 2H2O = 4Fe(OH)3(s) …(3.5)

Pitting corrosion occurs when a passive film or another protective surface layer
breaks down locally. After this initiation (local breakdown of the film) an anode forms
where the film has broken, while the unbroken film (or protective layer) acts as a
cathode. This will accelerate localized attack and pits will develop at the anodic spots.
The electrolyte inside the growing pit may become very aggressive (acidification) which
will further accelerate corrosion. Pitting occurs mainly in the presence of neutral or
acidic solutions containing chlorides or other halides. Chloride ions facilitate a local
breakdown of the passive layer, especially if there are imperfections in the metal
surface. Initiation sites may be non-metallic inclusions, e.g. sulfides, micro crevices
caused by coarse grinding, or deposits formed by slag, suspended solids, etc.

When the metal corrodes in the pit, dissolved metal ions generate an
environment with low pH and chloride ions migrate into the pit to balance the positive
charge of the metal ions. Thus the environment inside a growing pit gradually becomes
more aggressive and repassivation becomes less likely. As a result, pitting attacks often
penetrate at a high rate, thereby causing corrosion failure in a short time. The pits often
appear to be rather small at the surface, but may have larger cross-section areas
deeper inside the metal. Since the attack is small at the surface and may be covered by
corrosion products, a pitting attack often remains undiscovered until it causes
perforation and leakage.

3.2.1.3 Prevention of Pitting Corrosion

Selection of an alloy, which is resistant to pitting corrosion in the
chloride medium (e.g. Nickel Alloy).

Elimination of stagnant areas because this area can be a cathodic site.

Equipment should be designed for complete drainage avoiding areas

that retain standing solution.

42
 Corrosion Tutorial

3.2.2 Crevice Corrosion

Crevice corrosion is similar to pitting corrosion in the initiation and propagation
mechanisms. But these two are differentiated. Pit corrosion occurs on the open
surface of metal while crevice corrosion occurs on hidden areas of the metal surface.
The crevice corrosion is usually associated with small volumes of stagnant solution
retained on gasket surfaces, lap joints, and surface deposits under bolt and rivet heads
(Figure 3-18). This form of corrosion is called crevice corrosion or deposit or gasket
corrosion.

Figure 3-18: Crevice Corrosion

(Reference: http://corrosion.ksc.nasa.gov/html/corr_forms.htm)

Environmental factors affecting crevice corrosion are sand, dirt, corrosion

products and other solids. These deposits act as a shield and create a stagnant
condition. The deposit could also be a permeable corrosion product. Contact between
metallic and non-metallic surfaces can cause crevice corrosion as in the case of a
gasket. Wood, plastics, rubber, glass, concrete, asbestos, wax and fabrics are
examples of materials that can cause this type of corrosion.

3.2.2.1 Initiation and Propagation of Crevice Corrosion

43
 Corrosion Tutorial

The basic mechanism of initiation and propagation of crevice corrosion are

basically the same as those of pitting corrosion. The difference is that the cathodic site
of the crevice corrosion is a small amount of water retained by gasket or similar
materials.

The mechanism of crevice corrosion is illustrated in Figure 3-19.

O2 OH-

-
e

Crevice
Fe2++2H2O=Fe(OH)2+2H+
Fe+2H+=Fe2++H2
Fe=Fe2++2e-

Figure 3-19: Mechanism of Crevice Corrosion

Figure 3-19 shows a connection of two plates by a bolt. The upper left hand side
corner retains a small amount of water, which can serve as a cathode site. Oxygen is
dissolved into water and reduced to consume electrons supplied by the anodic reaction
of steel corrosion at the hidden crevice site.

After initiation of crevice corrosion, more chloride ions are attracted and help
propagate the crevice corrosion. Otherwise, the anodic half-cell reactions cannot take
place because of the formation of passive film. This anodic site has high concentration
of iron and is unsuitable for cathodic site because oxygen cannot be dissolved in the
high concentrated solution.

44
 Corrosion Tutorial

Figure 3-20: crevice corrosion in rivets

(Reference:http://www.corrosion-doctors.org/Localized/Crevice.htm)

3.2.2.2 Prevention of Crevice Corrosion

Crevice corrosion should be prevented at the design stage itself.

• Design vessels for complete drainage to avoid sharp corners and stagnant areas.
• Inspection of equipment and removing deposits frequently.

3.2.3 Pack Rust

Pack rust is a form of corrosion typical in steel components that develop crevice
in to an open atmospheric environment. This particular form of corrosion is often used in
relation to bridge inspection to describe built-up members, of steel bridges which are
already showing signs of rust between steel plates.

Figure 3-21: A crevice formed into an open atmosphere

45
 Corrosion Tutorial

Figure 3-22: Example of Pack Rust

(Reference:http://www.corrosion-doctors.org/Bridges/Pack-rust.htm)

3.2.4 Filiform Corrosion

Filiform Corrosion is a special type of crevice corrosion. Filiform corrosion has
been observed on steel, magnesium and aluminum surfaces covered by tin, silver, gold,
phosphate, enamel and lacquer coatings. Filiform corrosion is an unusual type of
attack, since it does not weaken or destroy metallic components but only affects the
surface appearance. It appears under thin coatings. It initiates on the scratched
defects of the coatings and propagates in the form of thread like filaments. The filament
has two ends: one is head and the other is tail. The head is anodic site where metal is
dissolved while the tail is cathodic where oxygen is reduced. The mechanism of filiform
corrosion is depicted in Figure 3-23.

O2+H2O
OH-
O2+H2O

Fe2++2H2OÆ
+ e-
Fe(OH)2+2H
Fe2+ H+ Fe2+ Fe(OH)2 OH-
Fe(OH)3 O2+H2O

Steel e-
e-

Figure 3-23: Mechanism of Filiform Corrosion

46
 Corrosion Tutorial

A special form of oxygen concentration cell is formed on metal surfaces having

an organic coating leading to filiform corrosion. This corrosion starts under the painted
surface when moisture permeates the coating on the metal. It has a distinguished
pattern and is known by its characteristic worm-like trace. Filiform corrosion occurs
when the relative humidity of the air is between 78 and 90 percent and the surface is
slightly acidic. The most important environmental variable in filiform corrosion is the
relative humidity of the atmosphere. If the relative humidity is lower than 65 percent, the
metal is unaffected; and for relative humidity higher than 90 percent, corrosion primarily
appears as blistering.

Filiform corrosion normally begins as small, microscopic defects in the coating

and then grows out into a network. The paint or plating should have certain properties
that could sustain or avoid any causes that lead to this type of corrosion. Lacquers and
"quick-dry" paints are most susceptible to this problem. Their use should be avoided
unless absence of an adverse effect has been proven by field experience. Low water
vapor transmission and excellent adhesion are some of the characteristics that are to be
exhibited by the coatings that are to be used.

Polyurethane finishes are especially susceptible to filiform corrosion. This

corrosion usually attacks steel and aluminum surfaces. The traces never cross on steel,
but they will cross under one another on aluminum which makes the damage deeper
and more severe for aluminum. . Zinc-rich coatings should also be considered for
coating carbon steel because of their cathodic protection quality. The effected area
should be treated properly and a good protective finish should be applied. If the
corrosion is not removed and allowed to grow, the corrosion can lead to intergranular
corrosion. This could be seen especially around fasteners and at seams.

Filiform corrosion can be removed using glass bead blasting material with
portable abrasive blasting equipment or sanding. Zinc-rich coatings should be
considered for coating carbon steel because of their cathodic protection quality.

Filiform corrosion can be prevented by storing aircraft in an environment with a

relative humidity below 70 percent, using coating systems having a low rate of diffusion

47
 Corrosion Tutorial

for oxygen and water vapors, and by washing the aircraft to remove acidic contaminants
from the surface.

Figure 3-24: “worm like” filiform corrosion tunnels.

(Reference:http://www.faa.gov/avr/afs/300/pdf/2g-CH6_2.pdf)

Figure 3-25: Filiform Corrosion Causing Bleed Through a Welded Tank

(Reference: http://corrosion.ksc.nasa.gov/html/filicor.htm)

3.2.4.1 Prevention of Filiform Corrosion

• Controlling the humidity to lower values (e.g. less than 65%).
• Corrosion resistant substrates of stainless steel, titanium or copper do not exhibit
filiform corrosion.

48
 Corrosion Tutorial

• Coatings and inhibitors eventually retard corrosion to some extent, but not
completely.

3.2.5 Localized Biological Corrosion

In this case, biological organisms are the sole cause or accelerating factor in the
localized corrosion. The reason behind this is that organisms do not form continuous
film on the metal surface.

The large fouling organisms in marine environments settle as individuals, and it is

often a period of months or even years before a complete cover is built up. Microscopic
organisms also tend to settle on the metal surfaces in the form of discrete colonies or
spots rather than continuous films.

3.3 Environmentally Induced Cracking

Environmentally Induced Cracking (EIC) is due to brittle mechanical failures that
result in presence of tensile stress and a corrosive environment. EIC includes stress
corrosion cracking (SCC), corrosion fatigue cracking (CFC) and hydrogen embrittlement
or hydrogen induced cracking (HIC).

3.3.1 Stress Corrosion Cracking

Stress corrosion cracking (SCC) is due to the low static tensile stress of an alloy
exposed to a corrosive environment. Three conditions must be present together to
produce SCC: a critical environment, a susceptible alloy and some component of tensile
stress. Figure 3.9 shows SCC of aluminum plate with branched cracks.

49
 Corrosion Tutorial

Figure 3-26: Stress Corrosion Cracking Showing Branched Cracks in Aluminum Plates

(Reference: http://corrosion.ksc.nasa.gov/html/corr_forms.htm)

3.3.1.1 Metallurgical Effects

Pure metals are more resistant to SCC than alloys of the same base metal, but
they are not completely immune. Higher strength alloys are more susceptible to SCC.

The cracks are usually produced by SCC by normal to the tensile component of
stress. Transgranular failures are less common than intergranular ones, but both may
exist in the same system, or even in the same failed part, depending on the conditions.
Intergranular failure suggests that some inhomogeneity exists at the grain boundaries.

Sometimes, specific chemicals react with alloy components to make the alloy
more brittle which develops cracks. For example, ammonia reacts with copper in brass
to cause SCC because ammonia can form various complex ions with cupric ion.
Hydrofluoric acid may react with nickel and copper in the nickel-copper alloy (Monel
alloy 400) because fluoride forms compounds of NiF2 and CuF2. Chloride ions cause
SCC to austenite stainless steels, probably because chromium in the alloy may react
with chloride ions to form CrCl3.

3.3.1.2 Electrochemical Effects

Electrochemical potential has a critical effect on stress corrosion cracking (SCC).
SCC usually occurs where the passive films are less stable. The regions near the two
ends of the passive zone as shown in Figure 3.27

50
 Corrosion Tutorial

ipass (passive
current) Oxygen evolution
Etp
transpassive

passive
E
icc (critical
current)

Epp
(passivation
active
potential)
Ecorr (corrosion
potential)

Log i

Figure 3-27: Schematic of Active-Passive Behavior of the Anodic Polarization of a Metal

In the upper zone, SCC and pitting are associated in adjacent or overlapping
potential ranges. In lower zone, SCC occurs where passive film is relatively weak.

3.3.1.3 Prevention of Stress Corrosion Cracking

Prevention of SCC requires elimination of one of the three factors: tensile stress,
environment or susceptible alloy.

• When a tensile stress is applied, the magnitude will be reduced by the

shotpeening. Shotpeening is a process in which small, hard particles of 0.1 to
1.0 mm are projected at high velocities onto the surface to increase the
compressive stress.

51
 Corrosion Tutorial

• Removal of residual stress may be accomplished by stress-relief annealing.

Annealing may be impractical for some stainless steels, which sensitize and
become susceptible to intergranular attack.
• Reducing the oxidizing agents.
• Inhibitors are also effective in limited situations.
• Changing the composition of the alloying elements for lower strength.
• Choosing an alloy, which is resistant to the particular environment.
• Cathodic protection will usually stop SCC, but will accelerate HIC. Caution must
be exercised with higher strength alloys, which may fail by HIC when cathodic
protection is applied.

3.3.2 Sulfide Stress Cracking (SSC)

When metals and metal alloys come into contact with moist hydrogen sulfide,
sulfidic environments undergoes corrosion damage, commonly known as sulfide stress
cracking. This causes brittle failures in steels and other high strength alloys. The acidic
effect of the sulfides combined with stress in the environment leads to this type of
corrosion. SSC is also called hydrogen sulfide cracking, sulfide cracking and sulfide
corrosion cracking.

3.3.3 Liquid Metal Embrittlement (LME)

When liquid metal comes into contact with a metal, there will be decrease
in its ductility. This phenomenon is called liquid metal embrittlement. The decrease in
ductility can result in brittle failure of a normally ductile material. Tensile strength can
also be reduced along with the ductility of the metal. Small amounts of liquid metal are
sufficient to result in embrittlement. LME shows many characteristics of both stress
corrosion cracking and hydrogen embrittlement corrosion. Like local de-passivation prior
to stress corrosion cracking, LME requires an incubation period for the liquid metal to
penetrate the oxide or passive layers.

52
 Corrosion Tutorial

Liquid metal embrittlement can occur at loads below yield stress and thus failure
can occur without significant deformation or obvious deterioration of the component.

Figure3-28: Liquid Metal Embrittlement

(Reference:http://www.hgtech.com/Corrosion/Hg%20LME.htm)

Intergranular or transgranular cleavage fracture is the common fracture modes

associated with liquid metal embrittlement. However reduction in mechanical properties
due to de-cohesion can occur. Hence a ductile fracture mode results occurring at
reduced tensile strength. Some events that may permit liquid metal embrittlement
under the appropriate circumstances are brazing, soldering, welding, heat treatment
and hot working.

In addition to an event, it is also required to have the component in contact with

a liquid metal that will embrittle the component.

3.3.4 Solid Metal Induced Embrittlement

The embrittlement caused above the melting point of the embrittler is Liquid
metal embrittlement and the same phenomena below the melting point are pertained as
Solid metal embrittlement. LME can be considered as a prerequisite for the occurrence
of SMIE. Notched tensile specimens of various steels are embrittled by solid cadmium.
Intimate contact between the solid and the embrittler, the presence of tensile stress,
crack initiation at the interface is the necessary conditions for SMIE to occur. The
susceptibility to SMIE is stress and temperature sensitive and does not occur below a

53
 Corrosion Tutorial

specific threshold value. In LME, a single crack usually propagates to failure. But SMIE
requires multiple cracks to propagate.

Figure 3-29: Solid Metal Induced Embrittlement of a cadmium plated B7 bolt.

(Reference:http://www.hghouston.com/x/56.html)

Figure 3-30: Brittle crack in a cadmium plated B7 bolt from solid metal induced embrittlement

(Reference:http://www.hghouston.com/x/57.html)

3.3.5 Corrosion Fatigue Cracking

Corrosion fatigue cracking (CFC) is a brittle failure of an alloy caused by
fluctuating stress in corrosive environment. This type of corrosion occurs because the
cyclic stresses do not give enough time for the metal to recover its structural integrity.
The crack propagation rate depends on the frequency and cyclic amplitude of the

54
 Corrosion Tutorial

stress. The frequency of cyclic stress is important in CFC. Lower frequency leads to
greater crack propagation per cycle. Very high frequencies eliminate the effects of the
corrosive environment. CFC cracks propagate perpendicular to the principal tensile
stress. Increasing the ratio R, of the minimum to the maximum stress in the cycle
generally decreases the resistance to corrosion fatigue cracking. At ambient
temperature the stress ratio R has no effects, but at high temperatures when creep is
possible, R has its effects. The susceptibility to corrosion fatigue cracking increases
due to stress raisers such as notches.

3.3.5.1 Comparison with Stress Corrosion Cracking

• CFC is similar to SCC in that a corrosive solution induces brittle fracture in an
alloy that is normally ductile in non-corrosive environment.
• CFC occurs due to cyclic stress whereas SCC occurs due to static stress.
• CFC cracks propagate perpendicular to the principal tensile stress whereas SCC
cracks propagate normal to the tensile stress.
• CFC cracks are usually transgranular and blunt whereas SCC cracks are usually
transgranular or intergranular and sharp.
• Corrosion products are usually absent in case of SCC whereas it is present in
CFC.

3.3.5.2 Prevention of Corrosion Fatigue Cracking

Corrosion fatigue cracking (CFC) can be minimized using inhibitors, cathodic
protection, and reduction of oxidizers or increase in pH. Removal of cyclic stress by
designing will prevent CFC. Shotpeening increases the resistance to CFC.

55
 Corrosion Tutorial

3.3.6 Hydrogen Induced Cracking

HIC usually occurs in hardened or high stressed steels. The presence of atomic
hydrogen results in decrease in the toughness or ductility. HIC has been recognized
classically as being of two types. The first is known as blistering. When hydrogen builds
up at metallurgical inhomogeneities (traps), nascent hydrogen (H atom) which will
recombine to form molecular hydrogen gas. Accumulations of this gaseous molecular
hydrogen develop high pressures sufficient to rupture inter-atomic bonds, forming
microscopic voids (blisters).

The second type of HIC results from hydrogen being absorbed by solid metals.
This type is especially prevalent in iron alloys because of the solubility difference of
hydrogen in ferrite (BCC) and austenite (FCC). The solubility of hydrogen in austenite
is higher than that in ferrite. Upon forming ferrite from austenite below their phase
transformation temperature of 723 °C, hydrogen in the ferrite is supersaturated and thus
leads to embrittlement of the metal, which causes HIC.

However, the face centered cubic (FCC) stainless steels and FCC alloys of
copper, aluminum and nickel are more resistant to HIC because of their inherent high
ductility and low diffusivity for hydrogen. But reactive alloys of titanium, zirconium,
vanadium, niobium and tantalum, which are embrittled by insoluble hydrides, are
susceptible to HIC.

3.3.6.1 Comparison with Stress Corrosion Cracking

HIC is similar to stress corrosion cracking in that brittle fracture occurs in a
corrosive environment under constant tensile stress. Cathodic protection aggravates
HIC but suppresses or stops SCC. SCC cracks are usually branched, whereas CFC
cracks are unbranched. SCC cracks are mostly intergranular whereas the HIC cracks
are usually transgranular. If the alloys are cold worked, the cracks will be intergranular
for HIC. Failures by HIC are usually maximized at/or near room temperature.

56
 Corrosion Tutorial

3.3.6.2 Prevention of Hydrogen Induced Cracking

• Selection of alloys, which are more resistant to HIC such as FCC stainless steel
and copper.
• Stop cathodic protection.

3.4 Mechanically Assisted Degradation

Mechanically assisted degradation of metals is defined as the degradation which
involves both corrosion mechanism and a wear or fatigue mechanism. In this velocity,
abrasion, hydrodynamics, etc. play a major role and has a significant effect in the
corrosion behavior.

3.4.1 Erosion Corrosion

Erosion corrosion is due to the relative movement between a corrosive fluid and
the metal surface. Erosion corrosion is characterized in appearance by grooves,
gullies, waves, rounded holes, and valleys, and usually exhibits a directional pattern.
Sometimes passive films are developed on the metal surface, which has high corrosion
resistance such as aluminum, lead and stainless steels. Erosion corrosion results when
these protective surfaces are damaged. Metals that are soft such as copper and lead
are quite susceptible to erosion corrosion. The corrosive media, which cause erosion
corrosion, are gases, aqueous additions, organic systems, and liquid metals.

All types of equipment exposed to moving fluids are subject to erosion corrosion.
Some of these are piping systems, such as bends, elbows and tees, valves, pumps,
blowers, centrifugals, propellers, impellers, agitators etc and equipments subjected to
spray.

57
 Corrosion Tutorial

3.4.1.1 Prevention of Erosion Corrosion

• Choose materials with better resistance to erosion corrosion such as aluminum
and stainless steel.
• Avoid sharp elbows and angles in the design of equipment.

3.4.2 Impingement Corrosion

Impingement is a process resulting in a continuing succession of impacts
between particles and a solid surface. Impingement corrosion is a form of erosion
corrosion associated with impingement action of liquids. It may be accelerated by
entrained gas bubbles. More specifically it is caused by the impingement action of water
carrying entrained gas bubbles and striking the metal surface at an angle. It is not the
result of mechanical erosion of the metal itself but is the result of removal of the film of
corrosion products by erosion which is ordinarily protective at lower velocities.

Figure 3-31 Impingement corrosion in a bent tube

(Reference:http://www.alu-info.dk/Html/alulib/modul/A00115.htm)

58
 Corrosion Tutorial

Impingement corrosion is usually seen at or near the entrance of the tubes and in
bends. It takes the form of pitting or grooving and eventual perforation of the wall at that
location while the remainder of the tube shows no sign of corrosion. Parts like pump
casings, pump shafts and impellers, nozzles and valve seats, tubes are some of the
examples where impingement corrosion can be seen.

3.4.2.1 Prevention of Impingement Corrosion

Suitable resistant material (harder materials) is to be chosen.

Design, shape and geometry are some of the aspects that are to be
considered.

Inhibitors and coatings are to be applied.

It is desirable to separate out solids, water or gas early in a flow

system in order to avoid two phase flow.

3.4.3 Cavitation Corrosion

Cavitation corrosion occurs under conditions of severe turbulent flow and rapid
pressure changes. The cavitation process is responsible for the breakdown of the
protective surface film on the metal. This depassivation results in an accelerated
corrosion and causes gas pockets and bubbles to form and collapse. High flow
velocities and the entrainment of solid particles are the main causes of erosion
corrosion. Bubble implosions are responsible for the breakthrough of the passive film in
cavitation corrosion. These bubbles may result from boiling phenomena or may arise
because of the release of dissolved gases from the fluid as a result of pressure drops.

This type of corrosion can be seen at the suction of a pump, at the discharge of a
valve or regulator, at pipe elbows and expansions. This form of corrosion will eat out the
volutes and impellers of centrifugal pumps. Cavitation should be designed out by
reducing hydrodynamic pressure gradients and designing to avoid pressure drops

59
 Corrosion Tutorial

below the vapor pressure of the liquid and air ingress. Resilient coatings and cathodic
protection can be considered as control methods.

Large pressure changes should be avoided and surface layers should be hard to
prevent from cavitation corrosion.

3.4.4 Fretting corrosion

The rapid corrosion that occurs at the interface between contacting highly loaded
metal surfaces which are enhanced through slight vibratory motions. It is caused by the
combination of corrosion and the abrasive effects of corrosion product debris often seen
in component with moving or vibrating parts. Pits or grooves and oxide debris
characterize this damage. Bolted assemblies and ball bearings are most vulnerable
cases of fretting corrosion. Contact surfaces exposed to vibration during transportation
undergo the effects of fretting corrosion. The metal surface gets exposed to the
atmosphere, while the oxide film is removed due to this effect. This rubbing occurs at
small amplitudes. While the rubbing motion continues, fatigue cracks are initiated by
high shear stresses. As a result of surface initiated fatigue, wear particles break out of
the material, become trapped between the surfaces and oxidize. Apart from causing
dismounting problems, these oxidized particles prevent free axial displacement and
introduce increased load in the bearing, which in severe cases may lead to immediate
bearing failure.

Parameters that need to be controlled in fretting corrosion evaluations include

corrosive environment, contact load, amplitude and frequency of load fluctuations,
temperature and availability of moisture.

Increased surface hardness and use of lubricants are some of the preventive
methods to be used for fretting corrosion. Bearing loads has to be reduced on mating
surfaces.

60
 Corrosion Tutorial

3.5 Metallurgically Influenced Corrosion

This is classified as a result of the significant role that metallurgical factors affect
corrosion. The metallurgical influences considered are the relative stability of the
component alloys, metallic phases, metalloid phases and local variations in composition
in a single phase.

3.5.1 Intergranular Corrosion

Intergranular corrosion (IGC) can be caused by depletion of one of the alloying
elements in the grain boundary areas. An example is stainless steel upon extended
exposure to temperatures between 400 and 510 °C, typically during welding. In this
case, chromium precipitates as chrome carbide in the grain boundaries, which depletes
the element and thus causes intergranular corrosion along the grain boundaries. This is
because chromium is the element that can reduce the corrosion by forming the passive
film.

3.5.1.1 Exfoliation / Lamellar Corrosion

Exfoliation corrosion is a special form of intergranular corrosion. It is usually seen
in high strength aluminum alloys and carbon steels. By the force of expanding corrosion
products at the grain boundaries, the metallic surface grains get lifted up and results in
this form of corrosion. Corrosion products building up along these grain boundaries
exert pressure between the grains. Thus a leafing effect can be observed eventually
giving a layered appearance to the metal.

Alloys that have been extruded or worked heavily undergo this type of damage.
The damage often begins at end grains seen in machined edges, holes and grooves. It
may progress through an entire section.

61
 Corrosion Tutorial

Figure 3-32: Exfoliation of Aluminium

(Reference:http://corrosion.ksc.nasa.gov/html/intercor.htm)

Figure 3-33:Exfoliation of aircraft component

(Reference:http://www.corrosion-doctors.org/Forms/exfol-examp.htm)

3.5.1.2 Weld Decay

Sensitization of austenitic stainless steels during welding is known as weld
decay. During welding of austenitic stainless steel, at the interface of base metal and
weld the temperature was too high to sensitize the alloy. However, areas next to the

62
 Corrosion Tutorial

base metal/weld are sensitized since it reaches the critical temperature range of 425 °C
to 815 °C. Thus IGC occurs along this weld decay zone.

3.5.1.2.1 Prevention of Weld Decay

• Solution annealing is heat treatment of an alloy to high temperature just below its
melting point to dissolve the alloying elements, followed by quenching to prevent
the precipitation of chromium carbides.
• Low carbon alloy modifications allow a minimum reduction of chromium by
precipitation along the grain boundaries.
• Stabilized alloys containing niobium and titanium in austenitic stainless steels will
not reduce chromium content because these elements will react with carbon in
the sensitization temperature range.

3.5.1.3 Sensitization (Intergranular Corrosion of Austenitic Stainless

Steels)
Numerous failures of 18-8 stainless steels have occurred because of
intergranular corrosion. This happens in environments where the alloy should exhibit
excellent corrosion resistance. When these steels are heated in approximately the
temperature range of 425 °C to 815 °C (800 to 1500 °F), they become sensitized or
susceptible to intergranular corrosion. Here sensitizing means that chromium
precipitates as chromium carbide leaving the grain boundary areas with less chromium.
Above 815 °C, the chromium carbides are soluble and below 425 °C, the diffusion rate
of carbon is too low to permit the formation of carbides. However, in the temperature
range between these two temperatures, conditions are optimum to precipitate chromium
with carbon.

63
 Corrosion Tutorial

Figure 3-34: intergranular corrosion in stainless steel

Figure 3-34 shows a stainless steel which corroded in the heat affected zone a
short distance from the weld. This is typical of intergranular corrosion in austenitic
stainless steels. This corrosion can be eliminated by using stabilized stainless steels
(321 or 347) or by using low-carbon stainless grades (304L or 3I6L). Heat-treatable
aluminum alloys (2000, 6000, and 7000 series alloys) can also have this problem.

Figure 3-35: Intergranular Corrosion of 7075-T6 aluminum adjacent to steel fastener

(Reference:http://www.faa.gov/avr/afs/300/pdf/2g-CH6_2.pdf)

64
 Corrosion Tutorial

3.5.2 Dealloying
Dealloying or selective leaching is the removal of one or more active element(s)
from the alloy. Dealloying is a form of corrosion found in copper alloys, gray cast iron,
and some other alloys. Dealloying can be controlled by the use of more resistant alloys
such as inhibited brasses and malleable or nodular cast iron.

3.5.3 Dezincification
Dezincification occurs when the more active element of zinc in an alloy is
preferentially leached in a corrosive environment leaving the copper behind. Common
yellow brass consists of 30% zinc and 70% copper. Dezincification is readily observed
with the naked eye because the alloy assumes a red or copper color contrasting with
the original yellow. There are two types of dezincification and both are readily
recognizable. One is uniform or layer type and the other is localized or plug-type.

3.5.3.1 Prevention of Dezincification

Dezincification can be minimized by reducing the aggressiveness of the
environment or by cathodic protection, but in most cases these methods are not
economical. A preferable method is to select a resistant brass. Usually when the zinc
content is less than 15 weight percent, the brass is immune due to dezincification. For
example, red brass (15% Zn) is almost immune. Another method is the development of
better brasses with the addition of 1% tin to a 70-30% brass. Further improvement can
be obtained by adding small amounts of arsenic, antimony or phosphorus as inhibitors.

3.6 High Temperature Corrosion

Corrosion can occur when metal is exposed to an oxidizing gas at high
temperatures. This form of corrosion that does not require the presence of a liquid

65
 Corrosion Tutorial

electrolyte is known as high temperature corrosion. It is also called as dry corrosion,

tarnishing, high temperature oxidation and scaling. As temperature increases, rate of
attack also increases. The surface film thickens as a result of reaction at the scale-gas
or metal-scale interface due to the ion transfer through the scale. This behaves as a
solid electrolyte. High temperature scales are usually thought of as oxides, but also be
sulfides, possibly carbides, or a combination of these.

High temperature corrosion is a widespread problem in various industries such

as heat treating, aerospace and gas turbine, power generation (nuclear and fossil fuel)
etc.

3.6.1 Oxidation
Oxidation is the most important high temperature corrosion reaction. Alloys
intended for high-temperature applications are designed to have the capability of
forming protective oxide layers. Regardless of the predominant mode of corrosion,
oxidation participates in the high temperature corrosion reactions. Depending on the
base alloy composition and the intended service temperature, alloying requirements for
the production of specific oxide scales have been translated into minimum levels of
scale-forming elements.

These protective oxide scales are formed at all the surface discontinuities,
wherever the alloy surface is exposed to the ambient environment. Hence there is a
possibility that notches of oxides are formed at occluded angles in the surface, which
may eventually serve to initiate or propagate cracks under thermal cycling conditions.

3.6.2 Sulfidation
Sulfidation is defined as the reaction of a metal or alloy with a sulfur-containing
species to produce a sulfur compound that forms on or beneath the surface on the
metal or alloy. When sulfur activity of the gaseous environment is sufficiently high,

66
 Corrosion Tutorial

sulfide phases, instead of oxide phases can be formed. Sulfidation attack mainly occurs
at sites where the protective oxide has broken down.

If sufficient sulfur enters the alloy so that the available chromium and aluminum is
converted to sulfides, then the less stable sulfides of the base may form due to different
morphological and kinetic reasons. These base metal sulfides are responsible for the
accelerated attack as they grow much faster than the chromium or aluminum oxides or
sulfides and have low melting points.

As long as the sulfur is present in small amounts as sulfides, there is little danger
of accelerated attack. Once sulfides have formed alloys they have a tendency to get
oxidized to form new sulfides in grain boundaries or at the sites of chromium or
aluminum, which act to localized stress or reduce the load-bearing section.

3.6.3 Carburization
Carburization is defined as the increase of the carbon content of steel due to
interactions at elevated temperatures with the environment. It occurs kinetically in many
carbon-containing environments like carbon, carbon monoxide and hydrocarbons.

Carbon has large influence on the mechanical properties of the steel like
hardness, strength etc. Carburization therefore results in the formation of a hard top
layer that is more brittle than the core material.

Carbon forms carbides (like Cr23C6, Cr3C 2 or Cr7C3), depleting the metal
matrix locally of chromium and making it more sensitive to corrosion.

Minor alloying elements can exert an influence on the susceptibility to

carburization of various alloys. In particular silicon (1.5 to 2.0%), niobium, tungsten,
titanium, nickel and the rare earths have been noted as promoting resistance to
carburization, whereas lead, molybdenum, cobalt, zirconium and borium are considered
detrimental.

Carburization is based on carbon transport across the metal/gas interface which

is very slow, and alloy pretreatments likely to promote such scales forms smooth

67
 Corrosion Tutorial

surfaces or pre-oxidation. This oxide film will decrease the carburization attack.
Because of the high solubility of carbon in austenite, austenitic steels carburize more
readily than ferritic steels.

68
 Corrosion Tutorial

4 AGING OF COMPOSITES

4.1 Introduction
A composite material is a complex solid material, composing of atleast two
materials, that, when combined, remain discrete but function interactively to form a
useful material. The composite is designed to exhibit the best properties that cannot be
predicted by simply summing the properties of its constituents. This combination of
materials is done by physical means unlike the chemical bonding that takes place in the
alloys of monolithic materials etc.

Composites are made of fiber reinforcements, resin, fillers, and additives. The
fibers provide stiffness and strength. The resin offers high compressive strength and
binds the fibers together into a matrix. The fillers serve to reduce cost and shrinkage.
The additives help to improve not only the mechanical and physical properties of the
composites but also workability. A true composite might be considered to have a matrix
material completely surrounding its reinforcing material. The matrix holds the
reinforcement to form the desired shape while the reinforcement improves the overall
mechanical properties of the matrix. After designed properly, the combined material
produces characteristics not attainable by either constituent acting alone.

4.2 Composition
Composites are composed of resins, reinforcements, fillers, and additives. Each
of the above mentioned constituents play a vital role in the processing of the final
product. Resin holds the composite together thus influencing the physical properties of
the final product, while the reinforcement provides the mechanical strength. The fillers
and additives are used to impart special properties to the final product.

69
 Corrosion Tutorial

4.2.1 Fiber Reinforcements

The fiber is an important constituent in composites. The fiber generally occupies
30% - 70% of the matrix volume in the composites. The primary function of fibers is to
carry load along the length of the fiber to provide strength and stiffness in one direction.
The fibers can be chopped, woven, stitched, and/or braided. They are usually treated
with sizing such as starch, gelatin, oil or wax to improve the bond as well as binders to
improve the handling. The most common types of fibers used in advanced composites
for structural applications are the fiberglass, aramid, and carbon. The fiberglass is the
least expensive and carbon being the most expensive. The cost of aramid fibers is
about the same as the lower grades of the carbon fiber.

a. Random fiber (short fiber) reinforced composites

b. Continuous fiber (long fiber) reinforced composites

Figure 4-1: Fibers as the reinforcement (Fibrous Composites)

(Ref: http://www.efunda.com/formulae/solid_mechanics/composites/comp_intro.cfm)

70
 Corrosion Tutorial

4.2.2 Resin Systems

The resin is another important constituent in composites. The primary function of
resin is to transfer stress between the reinforced fibers and protect them from
environmental damage. A thermoplastic remains solid at room temperature and
becomes soft when heated. It may be shaped or molded while in a heated semi-fluid
state and become rigid when cool. On the other hand, thermoset resins are liquids or
low melting point solids in their initial form. Once cured, solid thermoset resins cannot
be converted back to their original liquid form. Thermosetting resin will cure permanently
at elevated temperatures. This characteristic makes the thermoset resin composites
very desirable for structural applications. The most common resins used in composites
are the unsaturated polyesters, epoxies, vinyl esters polyurethanes and phenolics.

4.2.3 Fillers
It is cost effective to fill the voids in a composite matrix purely with resin as the
resins are expensive. Hence fillers are added to the reisn matrix to control the material
thus improving its mechanical and chemical properties. The three major types of fillers
used in the composite industry are the calcium carbonate, kaolin, and alumina
trihydrate. Some other common fillers are mica, feldspar, wollastonite, silica, talc, and
glasses.

4.2.4 Additives
Different varieties of additives are used to improve the material properties,
aesthetics, manufacturing process and performance. The additives are divided into
different groups – catalysts, promoters, and inhibitors; coloring dies; and releasing
agents.

The most common man-made composites can be divided into three main groups:

71
 Corrosion Tutorial

Polymer Matrix Composites (PMC’s) – These are also known as Fiber

Reinforced Polymers (or Plastics). They use a polymer based resin as the matrix, and
variety of fibers such as glass, carbon, and aramid as the reinforcement. These ate the
most common used composites.

Metal Matrix Composites (MMC’s) – These materials use a metal such as

aluminum as the matrix and fibers such as silicon carbide is used as the reinforcement.
This is mainly used for automotive industry.

Ceramic Matrix Composites (CMC’s) - Used in very high temperature

environments, these materials use a ceramic as the matrix and reinforce it with short
fibers, or whiskers such as those made from silicon carbide and boron nitride.

4.3 Fiber Reinforced Polymers

The mechanical properties of resins such as epoxies, polyesters are not very
high when compared to metals and hence they have limited use for the manufacture of
their own structure. But their ability of ease formation into complex shapes makes them
more desirable. Glass, aramid and boron have high tensile and compressive strengths
but in solid form, these properties are not apparent because when stressed, surface
flaws will cause the material to crack and fail before its breaking point. In order to
overcome this problem, the material is produced in the fiber form, thus restricting the
flaws to a small number of fibers while the remaining exhibiting the material’s strength.
Therefore a bundle of fibers reflect the optimum performance more accurately.
However, fibers alone can only exhibit tensile properties along the fiber’s length.

Inorder to obtain exceptional properties, resin systems are combined with

reinforced fibers such as glass, aramid, carbon etc. The resin matrix protects the fibers
from damage caused by abrasion and impact and also distributes the load applied to
the composite between each of the individual fibers. Since the Fiber Reinforced
Composites combine a resin system and reinforcing fibers, the properties of the
resulting composite will combine some properties of the resin on its own with that of the
fibers, which are summarized as shown in the Figure 4-2.

72
 Corrosion Tutorial

Fiber

Tensile
FRP Composite
Stress

Resin

Strain

Figure 4-2: The combined effect on Modulus of the addition of fibers to a resin matrix.

The mechanical properties and composition of FRP composites can be tailored

for their intended use. In addition to the manufacturing process to fabricate the product,
the type and quantity of materials will also affect the mechanical properties and
performance.

Important considerations for the design of composite products are as follows:

• Type of fiber reinforcement

• Fiber volume fraction
• Orientation of fiber (0o, 90o, +/- 45 o or a combination of these)
• Type of resin
• Cost of product
• Manufacturing process
• Volume Production
• Service conditions

Composites are manufactured using two major processes. They are: open mold
process and closed mold process. Types of open mold processes are hand lay up and

73
 Corrosion Tutorial

tube rolling. Closed mold processes include, resin transfer molding (RTM), vacuum
assisted resin transfer molding (VARTM), resin injection molding, compression molding,
pultrusion, extrusion and filament winding process. Composites when compared to
conventional materials are expensive, but are still widely used in various applications.
They are used in defense equipments, infrastructure, medical equipment etc. This is
because of the advantages offered by composites in comparison to conventional
materials.

• They have high stiffness, strength, or dimensional stability.

• They increase toughness (impact strength).
• They increase heat-deflection temperature.
• They increase mechanical damping.
• They reduce permeability to gases and liquids.
• They increase some electrical properties (e.g., increase electrical
resistivity).
• They decrease water absorption.
• They decrease thermal expansion.
• They increase chemical wear and corrosion resistance.
• They maintain strength/stiffness at high temperatures while under strain
conditions in a corrosive environment.
• They increase secondary uses and recyclability, and to reduce any
negative impact on the environment.
• They improve design flexibility.
• They have low density.
• They are easy to handle.
• They have good fatigue response and damage tolerance.
• They are tailored to loading conditions to optimize structural performance.
• Radar Transparency.
• They are non-magnetic and have high dielectric strength (insulator).
• Tailored surface finish.
• Potential for real-time monitoring.

74
 Corrosion Tutorial

4.3.1 Characteristics of Fiber Reinforced Composites

Fiber-reinforced polymer (FRP) composites offer many advantages, such as
enhanced corrosion resistance and high specific mechanical properties, over traditional
structural materials. However, composite laminates also have inherent weaknesses,
such as susceptibility to impact damage and long-term aging. Aging of composites may
depend on environmental factors on the composite material when exposed for a period
of time and type of liquids. This may occur as a result of the matrix degradation, fiber
degradation, or fiber-matrix interface degradation. Some of the causes of
corrosion/aging of composites are absorption of solvents, oxidation, UV radiation, and
thermal degradation, etc. An FRP component may sustain constant or repeated loading
under environmental exposure for a prolonged period of time. These service conditions
render environmental effects, creep, fatigue, and weathering effects on FRPs, which are
to be considered in design.

The physical or chemical weathering conditions occur when a composite material

is subjected to mechanical loadings such as static load, fatigue and creep or when it is
exposed to chemical solutions like alkaline, acid or aqueous solutions. As a result of the
above mentioned environmental factors, changes with exposure time take place in the
mechanical properties such as strength, stiffness, creep, and fatigue life and chemical
properties such as glass transition temperature.

Short term behavior of FRP composites are determined to establish parameters

such as mechanical resistance (axial, bending, shear and combinations), thermal
behavior (thermal coefficient and conductivity), and moisture diffusion/plasticization.
Long-term responses of composite materials are determined to establish the properties
of aging in composites due to sustained loads, cyclic loads and environmental
conditions.

The response of a composite has been classified in terms of its short-term

behavior and long-term behavior.

75
 Corrosion Tutorial

Short term Mechanical and Hygro-Thermal Behavior

Thermal Coefficient and Conductivity: A lower coefficient of thermal
expansion of glass fibers in relation to resin produces residual stresses within the
material microstructure during temperature drop. In cold regions, the difference in curing
and operating temperatures of the composite material may be as high as 2000F; thus
resulting in residual stresses that are high enough to cause microcracking within the
matrix and the matrix-fiber interfaces. Matrix tensile strength reductions up to 50% may
be possible because of residual stress build-up under low temperature effects.
Temperature affects the rate of moisture absorption as well as the mechanical
properties of a composite. Mechanical properties of fiber reinforced composites change
when the material is exposed to elevated temperatures (370C to 1900C). Increase in
temperature may accelerate time-dependent effects such as creep and stress
relaxation. Similarly, evaluation of composite systems at low temperatures is essential
since high strength and stiffness degradation rate under thermal cycling is observed in
cold region structures. The increase in stiffness at low temperature is attributed to
crystallization and instantaneous thermal stiffening, which is dependent upon polymer
type and temperature. The decrease in temperature can lead to possible increase in: 1)
modulus; 2) tensile and flexural strength; 3) fatigue strength and creep resistance; and
4) adhesive strength. Also, decrease in temperature can lead to possible reduction in: 1)
elongation and deflection; 2) fracture toughness and impact strength; 3) compressive
strength; and 4) thermal coefficient. These and other mechanical properties that are
functions of temperature will be evaluated.

Moisture Diffusion / Plasticization: Water penetrates FRPs through two

processes: diffusion through the resin, and flow through cracks or other material flaws.
During diffusion absorbed water is not in the liquid form, but consists of molecules or
groups of molecules that are linked together by hydrogen bonds to the polymer. The
molecules dissolved in the surface layer of the polymer migrate into the bulk of the
material under a concentration gradient. Water penetration into cracks or other flaws
occurs by capillary flow. Water also penetrates at the fiber-matrix interface. It is reported
that the primary mechanism of moisture through the cracks is an after effect. Moisture

76
 Corrosion Tutorial

pickup leads to loss of chemical energy, which is attributed to hydrolytic scission of

ester groups. However, increased hydrostatic pressure reduces water uptake due to
closing of micro cracks. Diffusion of water into the resin causes swelling stresses. The
equilibrium content of water determines the magnitude of swelling stresses. The
chemical composition of resin influences the solubility of water in the resin and its
susceptibility to hydrolysis. Exposure of composites to moisture for longer duration
results in resin (matrix) plasticization and interface bond strength reduction.

In this report, diffusion coefficients, rate of hydrolysis and property degradation

are reviewed as a function of different parameters such as moisture concentration,
humidity level, composite thickness, fabric configuration and temperature. The effects of
moisture on long-term strength and stiffness of the FRP composites and hybrids are
discussed.

Long Term Mechanical and Hygro-Thermal Behavior (Aging)

Creep: Creep of composites is significant as compared to fibers particularly

when sustained stress levels exceed particular threshold levels. For example, maximum
sustained stress for GFRP reinforcement embedded in concrete is limited to 20% of the
failure stress. The relationship between survival probability (creep-rupture probability)
and logarithm of creep-rupture time will be included in addition to the effects of initial
sustained strains with respect to moisture absorption and fracture. Different creep
models are also discussed.

Fatigue and Fracture: This section mainly focuses on the models that predict
the fatigue life of composites and hybrids, and fracture initiation. The review consists of
empirical fatigue strength theories, strength and stiffness based degradations under
fatigue.

77
 Corrosion Tutorial

Aging due to Environmental Effects: In-service FRP composites and hybrids

exposed to harsh environments may lose strength, stiffness, and bond, thus
compromising structural integrity and safety. Change in properties of polymers in the
absence of load is referred to as ‘aging’. Since different factors influence mechanical
properties of polymer composites, aging is a complex phenomenon. Aging phenomenon
can be very significant during the service life of strengthened concrete-frame or
masonry wall, i.e., over its 75-year service life. Review on durability and aging in this
report includes effects of different pH conditions, temperature and sustained stress level
on structural composites.

4.3.2 Short-Term Mechanical and Hygro-Thermal Behavior

4.3.2.1 Thermal Coefficient and Conductivity

A lower coefficient of thermal expansion of glass fibers in relation to resin
produces residual stresses within the material microstructure during temperature drop.
In cold regions, the difference in curing and operating temperatures of the composite
material may be as high as 200°F; thus resulting in residual stresses that are high
enough to cause microcracking within the matrix and matrix-fiber interfaces. Matrix
tensile strength reductions up to 50% may be possible because of residual stress build-
up under low temperature effects.

Temperature affects the rate of moisture absorption as well as the mechanical

properties of a composite. Mechanical properties of fiber reinforced composites,
change when the material is exposed to elevated temperatures (37°C to 190°C).
Increase in temperature may accelerate time-dependent effects such as creep and
stress relaxation. Similarly, evaluation of composite systems at low temperatures is
essential since high strength and stiffness degradation rate, under thermal cycling is
observed in cold region structures. For example, high stiffening (50 to 100 times over
ambient temperature of 78°F) of resins at low temperatures reduces the desirable
movement of elastomeric bearing pads under bridge seats, leading to serious
malfunction of the pads and consequent failure of the structure. The increase in

78
 Corrosion Tutorial

stiffness at low temperature is attributed to crystallization and instantaneous thermal

stiffening, which is dependent upon polymer type and temperature.

The decrease in temperature can lead to possible increase in: 1) modulus; 2)

tensile and flexural strength; 3) fatigue strength and creep resistance; and 4) adhesive
strength. Also, decrease in temperature can lead to possible reduction in: 1) elongation
and deflection; 2) fracture toughness and impact strength; 3) compressive strength; and
4) thermal coefficient.

Thermal Coefficient
Temperature effects can induce the dimensional change of a composite, in
addition to its mechanical deformations. Composites have two coefficients of thermal
expansion. α1 refers to expansion in the direction of the fibers, while α2 is the
expansion in the direction perpendicular to the fibers. The resins used have thermal
expansion coefficients that are positive (~10 to 20x10-6/C), and the fibers can have
either a low value of α or even a negative value, as is the case with carbon fibers. The
thermal expansion in the direction of the fibers, α1 is computed according to Schapery,
1968.

1
α1 = [α f E f (T )Vf + αmEm (T )Vm ] …..(4.1)
E1 (T )

and in the direction perpendicular to the fibers

α 2 = (1 + Vf )α f Vf + (1 + Vm )α m Vm − α1V12 ……(4.2)

where vf, vm, and v12 are the values of the respective Poisson’s ratio. It is
noteworthy to point out that the moduli of elasticity of the constituent parts are shown as
function of time, T, to account for creep.

Thermal mismatch between fiber and matrix may cause matrix cracks in
composites under severe temperature fluctuations. Such stresses can be predicted by
complex FEA of the microstructure or by complex micro-mechanical models of the same

79
 Corrosion Tutorial

(Bowles, 1991). Propagation of such mode of damage has been observed only for very
high or very low temperature applications.

Thermal and Electrical Conductivity

Transport Properties
The properties of materials (such as heat conduction, permeation, electrical
conduction, etc.,) are grouped together and termed the transport properties, because
they deal with diffusion through the composite. Equations are suggested by [Hashin,
1968; Halpin, 1984; and Springer, 1981] for both the longitudinal and transverse
directions in an FRP composite. The longitudinal properties are computed through the
rule of mixtures as follows:

k 1 = Vf k f + Vmk m …(4.3)

where k1, kf, and km are the transport properties of the composite in the
longitudinal direction, in the fiber, and in the matrix, respectively.

For the transverse coefficient, the property k2 is computed by the Halpin-Tsai

equation:

k 2 1 + ξηVf
= ….(4.4)
km 1 − ηVf

where

⎛ Kf ⎞
⎜⎜ − 1⎟⎟
K
η= ⎝ m ⎠ ……(4.5)
⎛ Kf ⎞
⎜⎜ + ξ ⎟⎟
⎝ Km ⎠
⎛a⎞
log(ξ) = 3 log⎜ ⎟ ……(4.6)
⎝b⎠

and a and b are the dimensions of the fiber along and perpendicular to the
direction of measurement of the transport coefficient. These equations accurately
predict the thermal and electrical conductivities of carbon-epoxy composites for Vf up to
60%.

80
 Corrosion Tutorial

4.3.2.2 Moisture Diffusion/Plasticization

Water penetrates FRPs through two processes: diffusion through the resin, and
flow through cracks or other material flaws. During diffusion, absorbed water is not in
the liquid form, but consists of molecules or groups of molecules that are linked together
by hydrogen bonds to the polymer. The molecules dissolved in the surface layer of the
polymer migrate into the bulk of the material under a concentration gradient. Water
penetration into cracks or other flaws occurs by capillary flow. Water also penetrates at
the fiber-matrix interface. It is reported that the primary mechanism of moisture pickup
is diffusion through resin, and transfer of moisture through the cracks is an after effect.
Moisture pickup leads to loss of chemical energy, which is attributed to hydrolytic
scission of ester groups. However, increased hydrostatic pressure reduces water
uptake due to closing of micro cracks.

The rate of degradation of the polymer composite exposed to fluid environment is

related to the rate of sorption of the fluid. The sorption behavior depends on the type of
fluid, fluid concentration, temperature, externally applied stress, hydrostatic pressure,
the state of the material, and the chemical structure of the polymer and fiber/matrix
interface. It is governed in the most part by the chemical structure of the resin, the
degree and type of cross-linking and the presence of voids. The sorption rate depends
on the properties of the constituents, volume fraction and orientation of the fibers, and
process variables. Temperature increases the rate of absorption. Diffusion coefficients
have been found to increase with temperature.

The damage done in FRP due to the diffusion of fluids depending on the
exposure time may be plasticization and swelling of the matrix, which can be restored
by drying. It could also result in irreversible damage such as matrix cracking,
debonding of the fiber/matrix interface region, damage to fibers, and delamination
caused by swelling or internal stresses.

Improved bonding between fiber and matrix, particularly the chemical bonding
tends to delay the corrosion process. Moisture decreases the glass transition
temperature, Tg, of the polymer matrix, due to Plasticization of the matrix as a result of
the disturbance of the Van der Walls bonds between the polymer chains.

81
 Corrosion Tutorial

The tensile strength and modulus, compressive strength and modulus, flexural
strength and modulus, transverse tensile strength and modulus, short beam shear
strength and modulus, impact strength and interlaminar strength are reduced due to
exposure to moisture. Fracture energy or fracture toughness seems to increase in
some cases and reduce in some cases.

4.3.2.2.1 Diffusion Through Unreinforced Epoxy, Vinyl Ester,

Polyestor and Phenolics

Chin et al. [1999] studied the sorption and diffusion of water, salt water and
concrete pore solution in epoxy (EPON 828 RS), vinyl ester (Derakane 411-350PA) and
polyester (Aropol 7240-T15) matrices. Typical dimensions of the polymer film used in
the experiments were 25mm X 25mm and the thickness of the vinyl ester and polyester
film ranged from 230 to 260 microns whereas the thickness of epoxy film was 300
microns. They observed Fickian diffusion in all the resins and solutions.

When a concentration gradient exists in a material, such as a solid polymer,

there is a natural tendency for the concentration difference to be reduced and
eliminated by the process of mass transfer. The mass flux is generally proportional to
the local concentration gradient; this is often known as Fick’s first law, and the constant
of proportionality is called the diffusivity or the diffusion coefficient.

82
 Corrosion Tutorial

Figure 4-3: Typical Sorption Curve (Vijay et al., 2001)

The Figure 4-3 shows sorption curves for epoxy, vinyl ester and isopolyester
resins. The curves for moisture content ratio show an initial linear region up to about
Mt/M∞ = 0.6 followed by a region concave to the abscissa. Uptake was rapid for the first
10 hours, and then slowed between 10 and 100 hours as equilibrium was attained. The
epoxy resin has a higher concentration of hydrophilic hydroxyl groups located along the
backbone thus exhibiting higher moisture uptake than other resins.

83
 Corrosion Tutorial

Figure 4-4: The Sorption Curves for Epoxy, Vinyl ester, and Isopolyester Resin When Exposed to the 3
Different Solutions (Chin et al., 1999)

84
 Corrosion Tutorial

Table 4-1: Diffusion Coefficients of Epoxy, Vinyl Ester, and Isopolyester Resins

Diffusion Coefficient, D

Matrix Sorbent (x 10-9 cm2 s-1)

22 °C 60 °C

Distilled water 0.53 13.6

Epoxy Salt solution 1.04 8.54

Pore solution 0.67 9.82

Distilled water 6.88 19.0

Vinyl Ester Salt solution 8.75 24.5

Pore solution 8.72 24.3

Distilled water 41.9

Isopolyester Salt solution ---

Pore solution 8.89 ---

The sorption curves for epoxy, vinyl ester, and isopolyester resin when exposed
to the 3 different solutions are shown in the Figure 4-4.

85
 Corrosion Tutorial

Figure 4-5: Fickian Diffusion Curves for Epoxy in (a) Water, (b) Salt Solution, and (c) Concrete Pore
Solution at 22 °C (Chin et al., 1999)

86
 Corrosion Tutorial

Although vinyl ester resin exhibited the lowest equilibrium moisture uptake, it had
higher diffusion coefficients than epoxy. Since diffusion coefficient is a function of both
permeability and solubility, it is concluded that the permeability of vinyl ester is greater
than epoxy.

Moisture sorption into polymeric material lowers the glass transition temperature
(Tg); Hence reduces the maximum working temperature of the material. Hiltz and
Keough [1992] studied the influence of absorbed water on the Tg of a poly amideimide
using dynamic mechanical analysis (DMA) and DSC. The results indicate a decrease in
Tg from 568 K to 477 K as the weight of absorbed water increased from 0% to 4.25%.
This established a clear correlation between Tg and amount of water absorbed. The
reduction in Tg is due to plasticization of the resin, where the chemical structure was not
affected. Decrease in Tg is also attributed to increase in the chain mobility and voids.

A reduction in Tg is also accompanied by swelling of the sample. Both swelling

and plasticization are reversible and the thickness and properties of the dried sample
are restored. Wong and Broutman [1985] found the epoxy EPON 828 samples to regain
their initial thickness and Tg upon drying them after saturation.

Especially in vinyl ester resins, hydrolysis of the matrix is observed for long
periods (>4000 h) [Buck et al., 1998]. Water causes the ester linkages to break into acid
and alcohol groups. Ghorbel and Valentin [1993] studied the changes in structure with
time of aging and found that the above reactions were contributing to hydrolysis of the
resin.

4.3.2.2.2 Effect of Moisture on Fiber-Matrix System

Stokes [1990], in his work made cylindrical specimens of FM5055 carbon

phenolic, which was heated uniformly at a constant rate of 5.50C/sec. The specimens
were 0.635 cm in diameter and 2.54 cm in length and were fabricated such that the
direction transverse to the fabric plane was aligned with the axial direction of the
specimen. As the specimens were heated, strain in the axial direction was measured as

87
 Corrosion Tutorial

a function of temperature. The oven chamber in which the specimens were heated was
maintained at zero percent relative humidity. Stokes measured the transverse thermal
expansion strain for specimens containing three different initial moisture contents: 0%,
4%, 8% initial moisture. The measured results from Stokes are shown in Figure 4-6.

Figure 4-6: Thermal Expansion Measured by Stokes (Stokes, 1990)

Figure 4-7: Moisture-Induced Thermal Expansion vs. Temperature (Stokes, 1990)

88
 Corrosion Tutorial

Strain response due to water is obtained by subtracting the strain response for
the 0% moisture specimen from the response for the 4% and 8% moisture specimens.
Separated strain profiles for 4% and 8% moisture levels obtained through subtraction
technique are shown in Figure 4-7 referred to as the moisture-induced thermal
expansion.

Stokes [1990] measured the swelling response of a typical carbon phenolic

composite in the three primary material directions. The data obtained suggest that at
low and high relative humidities, the incremental increase in moisture absorption can be
attributed primarily to the resin whereas at intermediate relative humidities, water is
moving largely into the carbonized fibers.

Figure 4-8 (A) shows the mean equilibrium moisture content of each set of
specimens from each conditioning chamber as a function of the relative humidity of the
conditioning environment. A sigmoidal (shape of the alphabet S) relationship was found
between the two variables.

Figures 4-8 (B), (C) and (D) show the equilibrium linear swelling of each
specimen of FM 5055 in the three primary orthogonal directions (warp, fill, and across
ply) as a function of equilibrium moisture content of the material. Using regression
analysis, a fourth-degree polynomial was fit to each of the equilibrated data sets as
shown in Figures 4-8 (B), (C) and (D). The larger swelling in the across-ply direction, as
opposed to the two fiber directions, is evident.

89
 Corrosion Tutorial

Figure 4-8: (A) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen as a function on the
humidity of conditioning environment (Stokes, 1990)

90
 Corrosion Tutorial

Figure 4-8: (B) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in the Across Ply
Direction (Stokes, 1990)

91
 Corrosion Tutorial

Figure 4-8: (C) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in the Fill Direction
(Stokes, 1990)

92
 Corrosion Tutorial

Figure 4-8: D) Moisture Absorption/Swelling Response of Carbon Phenolic Specimen in the Wrap Direction
(Stokes, 1990)

From the work as shown in figures 4-8 (A) to 4-8 (D), Stokes concluded that large
increases in moisture content at intermediate moisture levels resulted in negligible
increases in volume of the composite. Moreover, less than 20% of the water absorbed
by the composite can be accounted for by the swelling of the material, which indicates a
large free volume within the composite. The unaccounted volume of water absorbed by
the fully saturated composite indicates that dry FM 5055 has a free volume of
approximately 11.5% and an apparent density of approximately 1.61 g/cm3. It was
proposed that the phenolic network polymer is responsible for the majority of the
absorption of water at low and high moisture levels, whereas the fibers absorb most of
the intermediate moisture content. These findings appear to indicate that there are
multiple sites for the absorption of water in the cured resin and that these sites vary in
their affinity for water.

93
 Corrosion Tutorial

4.3.2.2.3 Effect of Temperature and Polymer Structural Variables on

Sorption of Water

Temperature
Temperature increases the rate of sorption. The diffusion coefficient has been
found to increase with temperature according to the Arrhenius relationship [1981]

D = D0 exp(− E / RT ) ….(4.7)

where E is the activation energy for diffusion. Bonniau & Bunsell (1981)
calculated E to be of the order of 11000 cal/mol for (Diglycidyl ether of bisphenol A)
DGEBA epoxy cured with different hardeners. Marsh et al. (1984) in their experiments
calculated E for neat resins and composites to be 9500 cal/mol and 9940 cal/mol,
respectively. The two values seem to be consistent. In addition, the value of activation
energy does not seem to vary too much between neat resins and epoxies glass fiber
composites. Verghese et al. (1999) too found that the diffusion coefficient follows an
Arrhenius relation with E/R= 4650 K.

At higher temperatures (close to Tg), the sorption approaches that of the Fickian
response. However, under extreme conditions (i.e. temperatures close to boiling)
irreversible damage to the resin and composites was observed. Ishai [1975] found
significant damage to the resin (shown by Scanning Electron Microscopic (SEM) studies
of cut samples) and glass fibers at temperatures close to boiling. Significant damages
included extensive cracking, debonding and degradation of the glass fibers. Bunsell
and Dewimille [1983] studied sorption in DGEBA composites and found similar results.
Significant damage was found to reduce fiber regions, which was attributed to
imbalance of stress distribution. However, damage at lower temperatures was
negligible. Samples immersed in distilled water at room temperature for over 3 years
showed no damage to their structure. An important conclusion of their study was that
accelerated aging could not be simulated by subjecting the resin to higher temperatures
because under these conditions other phenomena (such as permanent damage to

94
 Corrosion Tutorial

resin) take place. This study also led to the conclusion that at higher temperatures,
other factors controlled the sorption process, i.e., cracking/crazing of the resin and
degradation of the interfacial layer.

Presence of --OH group in Polymer

Interactions of water with polar groups within the polymer chain of vinyl ester
resins have been confirmed through FTIR (Fourier Transform Infrared Spectroscopy)
studies on saturated samples. FTIR studies made on vinyl ester resins before and after
aging showed changes in the shape of the peak at 1450 cm-1, which was attributed to a
stretching vibration of the carbon monoxide and the bonding of the primary alcohol OH
bond. Verghese et al. demonstrated the influence of polar OH groups [1999]. Specific
interactions through hydrogen bonding were observed in Derakane 441-400 vinyl ester
resin composites (which had an OH group in its structure) as against their model resin
in which the OH groups was substituted for a CH3 group. The model resin did not exhibit
the thermal spiking phenomenon, while the saturation level of the resin was lower as
compared to the Derakane 441-400 vinyl ester resin.

Nature of Water
Water may exist as either “bound” or “unbound” within the system. The
existence was confirmed by 2H – NMR studies by Klotz et al. [1996] on diglycidyl ether
bisphenol A resin cured with dicyandiamide, and/or diamino-diphenyl sulfone. Woo and
Piggott [1987] observed that the effective dielectric constant of water is only 55-77%
that of free water. Hence, the mobility of water within the polymer is between that of ice
and free water. It was believed that water might cluster within a polymer, and water
molecules from hydrogen bonds may become bound with polymer groups. However,
contrary theories were postulated [Netravalli et al., 1984].

Changes in the Resin Structure

95
 Corrosion Tutorial

Changes taking place within the polymer due to the sorption of water may be
reversible or irreversible. Weitsmen [1988] and Wong et al. [1985] showed that slow
rearrangement of the polymer chains takes place due to the ingress of the water
molecule. This rearrangement of polymer chains causes changes in the free volume
and hence the second and subsequent sorption is comparatively faster.

Wong and Broutman [Part I and II, 1985] studied the sorption of water into EPON
828 resin (DGEBA cured with m-phenyldiamine/aniline) and concluded that Fickian
sorption was taking place although the diffusion coefficient was concentration
dependent. They proposed that the water molecules caused polymer chains to
rearrange and did not cause any damage to the epoxy. However, this rearrangement
was not permanent and the polymer collapsed to its original form when annealed or
heated to temperatures greater than its Tg. When this sample was subjected to the
sorption experiment after annealing, the behavior was found to be the same as the
original sample. The researchers also observed that the post-cured sample did absorb
more water.

Due to additional cure, the resin had more fractional free volume and more–OH
Groups, which caused increased water absorption. McMaster and Soane [1989] also
found the second and third sorption to be faster than the first. The diffusion coefficient
for one such result was first sorption, 3.5 x 10-9 cm2/sec and second sorption 4.2 x 10-9
cm2/sec. Hence the history of the polymer has a definite bearing on subsequent
sorption. Marsh et al. [1984] reported that the resins retained some moisture on drying.
The irreversible changes that may take place are cracking/crazing, and degradation of
the matrix/fiber interface are shown by Ishai [1975], and Dewimille and Bunsell [1983].
They took SEM photographs, which clearly show extensive cracking attributed mainly
due to imbalance in stress and degradation of the interface. In some cases, cracks
developed in the fiber rich zones. This is because the water plasticized the resin and
rendered the resin rich zones more resistant to damage.

Netravalli et al. [1984] used (Differential Scanning Calorimetry) DSC technique to

obtain the glass transition temperatures and curing energies of wet and dry samples.
They concluded that the absorbed water can act as a plasticizer, but the effect was

96
 Corrosion Tutorial

reversible. They also found that the curing energies progressively decreased as the
amount of water taken in increased. The water was found to cause the unreacted
epoxide groups to react, thereby causing some permanent changes in the resin
structure.

Cure
The effect of curing temperature and time of cure has been reported by a number
of researchers. In all cases, the amount of water sorbed has been found to increase
with the curing. Wong and Boutman [1985] found this in their study of DGEBA/m-
phenyldiamine/aniline epoxy resin. Sahlin and Peppas [1991] found the post cured
TGDDM/DDS resin to consistently sorb more water than the one without the post cure.

The extent of cure of a resin can be found using Torsional Braid Analysis (TBA),
Torsion Pendulum and FTIR (Fourier Transform Infrared Spectroscopy). The Tg of a
sample increased as the time of an isothermal cure was increased and hence the extent
of cure increased. Enns and Gillham [1983] cured DGEBA with stoichiometric amount of
DDS at 175°C for four different times: 50, 100, 180 and 600 minutes. Six hundred
minutes was not enough to fully cure the sample, as the Tg was below the Tg∞ (approx.
215 °C) of the fully cured sample. The samples were then subjected to a humid
environment at 25 °C. Four different humidities were used, 31%, 51%, 79.3% and 93%.
The result of the sorption experiments was that the sample with the highest percent of
cure absorbed more water at all the conditions. More cured resins exhibit higher
sorption because the highly cross-linked specimen has a lower density and
consequently a greater free volume. Similarly, a greater cure leads to the formation of
more –OH groups. A typical result is shown in Table 4-2.

97
 Corrosion Tutorial

Table 4-2: Variation of Equilibrium Moisture Content with Degree of Cure

Cure time
Tg °C Density (g/ml) M∞ D x 109 cm2/s
(minutes)

50 135 1.237 1.074 1.69

100 160 1.2357 1.136 1.7707

180 185 1.2339 1.65 1.58885

600 195 1.2334 1.737 1.7170

From the viewpoint of mechanical properties, it is desirable to have a fully cured

polymer. This is because a partially cured resin has a lower modulus compared to a
fully cured resin, and it displays more creep. The most common method of determining
the extent of cure is with the help of a differential scanning calorimeter (DSC). During
the course of a curing reaction, heat is liberated, and the instantaneous rate of energy
evolution can be measured using a DSC. The extent of reaction, α , then is simply the
ratio of the total heat evolved to the heat of reaction. When dα dt is plotted as a function
of time, t, it is found (Gupta, 2000) that data can be described by the following equation.

dα
dt
( )
= k1 + k 2 αm (1 − α )
n
…..(4.8)

in which the ks are temperature-dependent rate constants while m and n are

temperature independent constants.

White and Mather [1991] used an ultrasonic cure monitor technique to assess the
simultaneous extent of cure and mechanical property development during the cure on
an epoxy resin EPON 815/V 140 and compared the results with DSC monitoring. The
modulus extent was derived and presented as a characterization parameter similar to
the degree of cure in thermal cure characterization. The results have shown that the
degree of cure does not accurately reflect the mechanical property development during
cure. In comparison to the thermal degree of cure, the modulus extent shows that

98
 Corrosion Tutorial

significant mechanical property development is still occurring in the later stages of cure
when the degree of cure is fully developed. In other words, if the goal is to determine
how close a sample is to being fully cured, the ultrasonic method is likely to provide the
needed information while the thermal method may not provide such information. The
former method is a non-destructive method.

Hardener
A hardener is used in the cure of an epoxy resin to cross-link the epoxy chains,
thus giving structural rigidity. The commonly used hardeners are Diamino Diphenyl
Sulphone (DDS), diphenyl diamine, dicyandiamine (DICY), anhydride and Lewis acid
hardeners.

Due to their polarity, hardeners influence the sorption of water. Sahlin and
Peppas [1991] cured TGDDM resin with different amounts (5, 15, 25, 35, 45 wt %) of
DDS. The sorption increased as the amount of the hardener was increased. Within a
reasonable deviation, the increase was linear with the amount of water. The polarity of
the hardener also had an effect.

Diamant et al. [1981] attempted to keep the polarity of the resin a constant by
replacing the diamine hardener with aniline in DGEBA (Figure 4-9). By keeping the
polarity a constant, morphology of the polymer has changed as the length of the matrix
between cross-linking increased, thus reducing the density of cross-links in the resin
without affecting the polarity and increased chain mobility.

99
 Corrosion Tutorial

Figure 4-9: Difference Between (a) Diamine and (b) Aniline Hardener
Contrary to expectations, the resin cured with only diamine hardener was
observed to have the maximum sorption, which is attributed to (and confirmed by
etching experiments) regions that had a greater cross-linking density, which surrounded
areas of lower density. Higher cross-linking density caused hindrance to the movement
of the water molecules and effectively reduced the sorption. However, the inherent
polarity of diamine and aniline was not taken into account. Diamine is more polar than
aniline and hence could have accounted for the increased uptake. In addition to polarity
of individual hardeners, the presence of excess hardener increases the affinity of the
resin towards water. A residual hardener, for example, DICY means greater affinity for
water. DGEBA was cured with 5, 15 and 25 phr (parts per hundred parts of resin) of
triethylene tetramine (TETA) at 100 °C. The results are tabulated in Table 4-3 [1982].

Table 4-3: Effect of Hardener on Equilibrium Moisture Content

%TETA
Tg (dry) °C Tg (Wet) °C M∞ % (70 °C) M∞ % (20 °C)
in DGEBA

5 109 105 1.92 1.5

15 142 109 3.3 2.7

100
 Corrosion Tutorial

25 95 52 8.6 10.8

It is clear that the amount of water absorbed increased with the amount of the
hardener and temperature. However there was a discrepancy from expected Tg. Thus,
important parameters that influence sorption of water are:

• Extent of cure, like curing temperature and time of cure.

• Type of hardener used to cure the resin as well as the amount used.
• Amount of free volume present in the resin.
• Sizing agent (whether it forms a good bond or not between the matrix and
fiber).
• Environment like pH, temperature, etc.
• Effect of Glass Reinforcement

Influence of glass fibers in polymers on the sorption of water can be determined

by sorption experiments on neat samples as well as composites. The polymer resin
used should be cured with the same hardener/catalyst as well as under the same
conditions.

Contradictory results have been obtained on the above subject. Marsh et al.
[1984] studied the sorption of water in bisphenol A and cresol novolac epoxy cured with
dicyandiamide. Neat resins and composites with 40% E-type glass were studied at
75°C /100% RH. The sorption of water in the glass composite was the same as that of
the neat resin. Both the neat resin as well as the glass composite showed an
intermediate saturation before the onset of residual moisture. These similarities led the
authors (Marsh et al., 1984) to the conclusion that water did not enter the interface
between the matrix and the fiber; hence, there was no difference in the sorption of neat
resin and composites. On the other hand, Ishai [1975] showed that the behavior of neat
resins was quite different from composites. In the case of diffusion of moisture into
Epon 828 resin with E-glass fibers, significant damage was found not only to the

101
 Corrosion Tutorial

interface but also to the glass fiber (confirmed by SEM pictures). The degradation was
signaled by a drastic change in the sorption curve. Plotting the Relative Weight Change
(RWC) Vs. Relative Length Changes (RLC) also showed the onset of degradation. The
extent of degradation was more for samples exposed to extreme environments, i.e.,
temperatures of 80°C. Also the degradation of the interface was considerably less at
lower temperatures i.e. 20°C. Similar results were obtained by Dewimille and Bunsell
[1983], who found that composites (DGEB/Anhydride with E-Glass) degrade when
exposed to water at high temperatures (80°C and above).

Similar sorption studies were also made on vinyl ester glass fiber reinforced
composites. Pai et al. studied the effect of glass fiber lay-up sequencing in various
acidic environments [Parts I and II, 1997], using six different types of resins including
vinyl esters. They found that the composite with the Chopped Strand Matrix exhibited
least resistance to all liquids (water, 15%, 25% and 35% Sulfuric acid). Although the
diffusion process became sluggish as the concentration of sulfuric acid increased, the
saturation levels were much higher. They also studied the extent of degradation on the
composite. They assessed the fiber/matrix interface by performing an interlaminar
shear strength Test. The loss of the shear strength increased as the concentration of
sulfuric acid increased, showing an increased rate of degradation with increased acidic
pH.

In order for a composite to function properly, there must be a chemical bond

between the matrix and the reinforcing fibers so that the applied load (applied to the
matrix) can be transferred to the fibers. In 'fiber glass' the fiber is inorganic while the
matrix is organic, and these two do not bond readily unless the fibers are treated to
modify their surface. Silica (SiO2) is hygroscopic, i.e., however slow it absorbs water
onto its surface where the water breaks down into hydroxyl (-OH) groups. The coupling
agent takes the form of a silane (R-SiX3), where R is an organic radical that is
compatible with the polymer matrix and X is a hydrolisable organic group such as an
alcohol. The most common silane couplant is tri-ethoxy-silane. Heat will force the
elimination of water between the -OH pairs at the hydrated silica surface and the silane

102
 Corrosion Tutorial

as well as between the adjacent silane molecules forming a strong bond between the
matrix and the fibers as shown in Figure 4-10.

Figure 4-10: Bonds Between Glass Fiber and Coupling Agent.

If the bonds are chemical, then the presence of the glass will have a negligible
effect. If, however, the bonds are weak and can be displaced by the hydrogen bonding
due to water, debonding and degradation of the glass fiber can be pronounced. This
was studied by Ritter et al. [1998]. They studied the propagation of a crack in
monolithic glass (soda-lime and fused silica) untreated glass-epoxy interface and glass-
epoxy interface sized with 2-amino propyl triethoxy silane (3-AMPS) using a double
cleavage drilled compression test.

The increase in resistance of the silane bonded epoxy interface is attributed to

chemical bonding of epoxy to the glass via the coupling agent. The rupture or
debonding will take place only by breaking of the Si-O-Si bonds formed between the
glass and the silane-coupling agent. However, the highest threshold energy release
rate, Gth for the soda-lime glass is lowered as the alkali molecules can bond with water
and hence prevent the silane molecules from properly bonding to the glass surface.
The Gth calculated is given in the Table 4-4.

Table 4-4: Calculated Values of Gth

103
 Corrosion Tutorial

Specimen Gth Jm-2

Soda-Lime glass (SLG) 1.69

Fused Silica (FS) 2.76

Untreated SLG-Epoxy 0.25

Untreated FS-Epoxy 0.25

Silane treated SLG-Epoxy 1.32

Silane treated FS-Epoxy 3.31

4.3.3 Long term Mechanical and Hygrothermal Behavior (Aging)

Polymers and composites used for the renewal of civil infrastructure will be
exposed to complex infrastructure service environment conditions like range of
combinations of stress, time, temperature, moisture, radiation, chemical, and gaseous
environments and are expected to perform more than forty years. These materials
should be required to go through a series of specifications based on inherent, and
residual mechanical, physical, and thermal properties after accelerated service
environment exposure conditions. The lack of understanding of the fundamental
parameters controlling long-term materials performance necessarily leads to over-
design and in-service prototype evaluations and, furthermore, inhibits greater utilization.
The determination of long term mechanical and hygro-thermal behavior of these
materials and the understanding of the phenomena in relation to civil infrastructure
renewal are critical to the further use of FRP composites in civil infrastructure.

4.3.3.1 Creep Theory

Creep is defined as the continuous deformation (strain increase) over a
prolonged period under constant load. i.e., when a polymeric material is subjected to a
constant, sustained load, it deforms instantly, but then the deformation continues over a

104
 Corrosion Tutorial

long period. This phenomenon of increasing strain is known as creep. It is a very slow
plastic deformation process that occurs at stress levels below the yield point.
Conversely, if a constant strain is imposed on a polymeric material, it exhibits
instantaneous stress, but then the stress increases with increase in time; this is known
as stress relaxation. It is a universal phenomenon and is exhibited by most materials,
including metals.

Polymers behave viscoelastically, and exhibit creep and stress relaxation to a

high extent. Viscoelasticity arises because polymers are long-chain molecules, and
under stress, parts of a molecule or even entire molecules can rearrange and slide past
each other. This is especially easy above the polymer glass transition temperature Tg.
Furthermore, creep and stress relaxation are more pronounced in thermoplastics than in
thermosets; cross linking in thermosets restrict polymer chain mobility. The presence of
fillers and reinforcements can further restrict creep. If the deformations are large
enough, chain rupture may occur, particularly in thermosets where the chains are cross-
linked into a network.

Environmental factors such as temperature, moisture, and irradiation can all

exercise their effects on molecular activity in the polymer, thus altering the macroscopic
(creep) behavior. At high stress levels, this leads to relative slip between fiber and
matrix. Rupture of fibers may also occur, resulting in higher fiber stresses in surrounding
intact fibers, thus increasing elongation and rate of creep over time.

Constant
Constant
Strain
dε/dt

Primar Secondar Teritiray

y y II III

Time, t tf

105
 Corrosion Tutorial

Figure 4-11: Typical creep behavior of plastics

The properties of viscoelasatic materials are dependent on time, temperature,

and rate of loading; instantaneous test results cannot be obtained to define material
response under sustained stress or deformation. Consequently, a sustained load is
applied to a specimen in one of several standard configurations (such as tension,
compression, or flexure) at constant temperature and the corresponding deformation is
measured as a function of time. Since the deformations are small, strain gages are
generally employed. In principle, the creep deformation should be linked to an applied
stress. Thus, as the specimen elongates the cross sectional area decreases and the
load need to be decreased to maintain a constant stress.

In practice, it simpler to maintain a constant load. When reporting creep test

results the initial applied stress is used. The effect of constant load and constant stress
is shown in Figure 4-11. For FRP, a four-stage response is generally observed: 1. rapid
initial elongation (ε0) of the specimen; 2. Rapid reduction in response rate (primary
creep, stage I); 3. Steady state (secondary creep, stage II); and 4. A rapid increase in
response and fracture (tertiary creep, stage III). In general this effect (dashed line for
constant stress) only really manifests itself in the tertiary region, which is beyond the
region of interest in the secondary region.

Creep and Relaxation

FRP with glass fibers is expected to have very limited creep in the longitudinal
direction, as compared to the substantial creep in the transverse direction and under
shear stress. The load in FRP composite materials is carried primarily by the fibers,
which behave elastically. Thus creep and stress relaxation are not as significant in
composites as in the bulk polymer matrix itself, particularly along the direction of fibers,
which is typically designed to be the primary load path. For a purely elastic
material, the stress-strain behavior is not dependent on time, even if it exhibits a
nonlinear stress-strain relationship. This is because stress is a unique function of strain.

106
 Corrosion Tutorial

σ = Е0ε ……. (4.9)

ε = J0σ …… (4.10)

This resembles the behavior of a spring. E0 is the elastic modulus and J0 is the
elastic compliance. When a sinusoidal strain is applied, the strain and stress are in
phase, meaning that they follow each other and related only by proportionality constant.
For a purely viscous material, such as a Newtonian fluid, the stress is proportional to the
rate of strain.

dε
σ(t) = η ……(4.11)
dt

When a sinusoidal strain is applied, the stress and strain are out-of-phase, i.e.,
when the strain is maximum, the stress is zero, and when the strain goes through zero,
the stress is maximum. This resembles the behavior of dashpot. Polymers, as well as
most real materials exhibit a combination of elastic and viscous responses. They can
therefore be represented as combination of springs and dashpots (Maxwell’s model).
From equations 4.10 and 4.11

σ (t ) 1
t

η ∫0
εt = + σ (r )dr …..(4.12)
E0

For a creep test, where a constant stress is applied at t=0, the compliance is
found by integrating the above equation as

1 t ………………………....(4.13)
J (t ) = +
E0 η

and creep increases passively with time. If the elastic and viscous parts are
subjected to the same strain, the applied stress is the sum of the first part of Equations
4.10 and 4.11. This is a parallel combination of a spring and dashpot attributed to Kelvin

107
 Corrosion Tutorial

model. For a creep test under constant stress, integrating for the strain, we get the
compliance as:
E 0t
1 −
J (t ) = [1 − e η ] ….. (4.14)
E0

and creep is predicted to attain a constant value with increasing time. Clearly the
creep behavior shown in the Figure 4-11 is more complex than what can be predicted
based on the above equations.

Overview of Creep Models

Maxwell and Kelvin Models are used for representing the creep of thermoplastic
and thermoset resins. If the deformations and stresses are small and the time
dependence is weak, creep and stress-relaxation tests are essentially the inverse of
one another. Therefore, to a first approximation stress relaxation data can be converted
into creep by the following equation.

⎛ ε (t ) ⎞ ⎛ σ ⎞
⎜⎜ ⎟⎟creep = ⎜⎜ 0 ⎟⎟relax … (4.15)
⎝ ε0 ⎠ ⎝ σ (t ) ⎠

where, ε0 = initial strain in a creep test

ε(t) = creep strain after time t

σ0 = intial stress measured at the beginning of a stress-relaxation test

σ = stress after time t

Maxwell’s Model
Maxwell’s model consists of a spring (Hookean) and a dashpot (Newtonian) in
series as shown in Figure 4-12.

108
 Corrosion Tutorial

Figure 4-12: Maxwell’s Model

(Ref: http://www.matter.org.uk/matscicdrom/manual/pm.html)

The modulus of the spring is E, and the viscosity of the dash pot is η. In a stress-
relaxation experiment, the model is given a fixed strain ε while the stress σ is measured
as a function of time as shown in equation 4.16.

dε 1 dσ σ
= + =0 ….(4.16)
dt E dt η

Since, ε = σ/E for the spring and σ/η=dε/dt for the dashpot, the solution of the
equation is

⎛E⎞ ⎛ −t ⎞
σ −⎜⎜ ⎟⎟ ⎜ ⎟
= e ⎝ η ⎠ = e⎝ τ ⎠
…(4.17)
σ0

where ‫ = ح‬η/E is known as the relaxation time.

Since a dashpot deforms instantly, all the initial deformation takes place in the
spring; later the dashpot starts to relax and allows the spring to contract. Most of the
relaxation takes place when t is close to .‫ح‬

Mathematically, the stress relaxation can be written as

⎛ −t ⎞
σ (t ) σ ⎜⎝ τ ⎟
Er = = e ⎠
…..(4.18)
ε σ0

109
 Corrosion Tutorial

Kelvin Model
Kelvin Model consists of a spring and dashpot connected in parallel as shown. In
thiis the elastic and viscous parts are subjected to same strain, and hence the applied
stress is the sum of the first part of (4.15) and (4.16). For a creep test under constant
stress

Figure 4-13: Kelvin’s Model

E 0t
1 −
E(t ) = [1 − e η ]
E0

…… (4.19)

Neither the Maxwell nor the Kelvin model can describe the creep of thermosets.
A more realistic model is the four-element model. Maxwell’s model does not describe
the creep behavior completely. According to Maxwell model, as t goes to infinity the
stress ratio becomes zero, which indicates that all creep and corresponding creep
stress are recoverable. Whereas, in the four element described later, fraction if creep is
not recoverable for the flow that occurred in the dashpot with viscosity η3, which models
the actual behavior of polymers. Therefore, the Four Element Model accounts for the
actual creep behavior.

Four Element Model

110
 Corrosion Tutorial

Figure 4-14: Four Element Model

A four-element is shown in Figure 4-14. When a constant load is applied, the

spring with modulus E1 deforms first. Later, the dashpot with the viscosity η1 deforms.
Finally, it is the spring E2 and dashpot η2 that deform. The total elongation is the sum of
the individual elongation of the three parts.

σ0 σ0 σ0
E 2t
−
η2
ε= [1 − e ]+ + t
E2 E1 η1

….. (4.20)

If at time t1, the load is removed, the spring with modulus E1 retracts instantly.

The equation for subsequent creep recovery is:

σ 0 t1
ε = ε 2 e ( − ( t −t ) / τ +
1

η3 ……… … (4.21)

where

σ0
ε= (1 − e (−t1 / τ ) )
E2
……. (4.22)

As tÆ ∞, it is found that the creep of dashpot with viscosity η1 cannot be

recovered. Equation 4.22 is shown in the Figure 4-15:

111
 Corrosion Tutorial

Figure 4-15: Behavior of Creep and Stress Relaxation in Four Element Model

Master Curves
In order to compute the spectrum of relaxation or retardation times, experimental
data covering about 10-15 decades of time are needed. This is a very fine consuming
proposition. In practice, the data can be obtained in short intervals but over a series of
constant temperatures, and then they can be superimposed to extend the time scale of
measurement. In this task, Boltzman superposition principle and the principle of time-
temperature superposition are employed.

According to the Boltzman superposition principle, the response of a material to a

given load is linear and additive. For the case of creep, if there are several stresses σ0,
σ1, σ2, σ3, σ4,……… σi applied at times 0,t1, t2, t3, t4,…. ti, the total creep is

ε (τ ) = J (t )σ 0 + J (t − t1 )(σ 1 − σ 2 ) + .... + J (t − t i )(σ i − σ i −1 ) …..(4.23)

where the creep ε(t) at time t depends on the compliance function J(t), which
depends on temperature. Figure 4-16 illustrates the behavior for a polymer that obeys
the following equation 4.21.

ε (τ ) = Kσt n ….(4.24)

112
 Corrosion Tutorial

Figure 4-16: Behavior of Creep when subjected to series of stresses

where K and n are temperature dependent constants. It describes a system
when subjected to a series of stresses σi and ti, creep is given by the sum of identical
responses.

It has also been found that the creep curves made at different temperatures can
be superposed by horizontal shifts along a logarithmic time scale to give a single creep
curve. This procedure was originally suggested by William, Landel and Ferry (WLF),
and the result is called a master curve. The extent of shifting is given numerically by an
equation called the WLF equation, which holds between Tg or Tg+10K and about 100K
above Tg. Above the upper limit of applicability of the WLF equation, one may use an
Arrhenius equation with a low activation energy. Note that master curves can be made
from stress relaxation data, dynamic mechanical data, or creep data. Sometimes a
vertical shift may be needed in addition to the horizontal shift and the vertical shift may
be needed in addition to the horizontal shift and the vertical shift may depend on
temperature. Aging and heat treatments may also affect the shift factors. For these
reasons the vertical shift factors are largely empirical.

113
 Corrosion Tutorial

Creep and Relaxation in Composite Laminates

Correspondence Principle: To find the relaxation corresponding to the
compliance of the Maxwell model, the correspondence principle is used. The
correspondence principle is valid for a linearly viscoelastic material, i.e., non-linearity is
in time, not on stress. Stress only magnifies the deformations in a linear, proportional
way.

According to the correspondence principle, any viscoelastic problem in the time

domain can be solved as an elastic problem in the Laplace domain. By transforming all
the equations to the Laplace domain, it reads

J(s) s =1/ ( E(s) s) …(4.25)

where s is the Laplace variable. Taking the Laplaces of the Maxwell model
equation, multiplying by s2 and inverting we get the Laplace transform of the relaxation

E(s) = E/ ((E/η) + s) …(4.26)

Taking the inverse Laplace transform, the relaxation time domain is

E (t) = E0e-(E0/η) t …..(4.27)

If the material follows a Maxwell model, this equation should model well the data
of relaxation test. The Kelvin model does not have a simple relaxation equation because
the stiffness at t=0 is infinity, and because the stress is applied suddenly to the viscous
component. Increasingly complex equations can be used in order to fit the experimental
data better, but the number of parameters and the complexity increases accordingly.
The concept and methods of analysis remain the same.

Unidirectional Composites
To predict the creep behavior of unidirectional lamina micromechanics is used.
Since all the micromechanics models are formulated for elastic fiber and matrix, they

114
 Corrosion Tutorial

must be used in Laplace domain. Models that include empirical adjustable parameters
cannot be used because the time dependence of the adjustable parameters is not
known, so it is not possible to take the Laplace transform of them. Luciano and Barbero
[1995] used micromechanics of periodic microstructure to find analytical, complicated
expressions for the creep and relaxation tensors of unidirectional composites. From
these, they obtained all the creep compliances and relaxation functions in all directions
for the composite, such as E1, E2, G12, G23 and all the Poisson components. All that is
needed are the elastic properties of the fibers, the fiber volume fraction, and
representation of the creep behavior of the matrix.

Simple micro-mechanics formulas such Halpin -Tsai cannot be used because

they contain adjustable parameters. Since the properties of the matrix often differ from
the bulk properties, Harris and Barbero [1998] suggested that creep tests be performed
on the composite to back-calculate the creep behavior of the matrix. This has not been
done to present. On the contrary, Harris and Barbero, as well as many others, struggled
to perform creep tests on bulk matrix.

Laminated Composites
The approach for prediction of laminate creep is to use classical lamination
theory in the Laplace domain. Harris and Barbero [1998] used such a method to predict
composite behavior of various laminates. Although the concept is simple, the equations
are too complicated for hand calculations. Instead, a simple program or spreadsheet
can be used.

4.3.3.1.1 Effect of moisture and temperature on Creep

Moisture and time, like temperature and time, often have an interchangeable
effect on the creep behavior of polymers. Moisture absorption in polymer-matrix
composites will result in the development of residual stresses and will plasticize the
resin. Both of these effects can accelerate the time-dependent behavior of material. The
effects of time, temperature and moisture on the creep compliance are illustrated

115
 Corrosion Tutorial

schematically in the Figure 4-17. Usually, creep compliance is increased with an

increase in moisture content and temperature over time. Although there are some
studies on creep-rupture for pultruded FRP in fluids, data on viscoelastic behavior of the
materials under the influence of fluid absorption are scarce. Moreover, the moisture
absorption level is history-dependent, and therefore sorption behavior under
temperature and/or humidity cycling is not the same as under a constant humidity and
temperature level.

Figure 4-17: Schematic representation of effects of time, temperature, and moisture on creep compliance.
(Liao,1998)
When moisture is absorbed in a polymer-matrix composite the resin is
plasticized. If the resin swells, stress will be generated. The first of these effects will
soften the polymer and increase creep.

Parasyuk et al. [1987] investigated the effect of water immersion on compressive

creep of uni-directional glass-reinforced composites. In the dry-condition, creep ceased
after sometime when the applied stress was low. However, when the applied stress
exceeded 85% of the ultimate strength, a steady state creep rate (dε/dt=constant) was
reached. In liquid media, similar behavior was observed but considerably lower stress
levels compared to tests conducted in air. Furthermore, at a given stress level, the rate
of creep increased with immersion in water. This was attributed to the redistribution of

116
 Corrosion Tutorial

stresses between glass fibers and the polymer matrix, and between damaged and
undamaged reinforcing elements. These general conclusions remained unchanged
when data were obtained at higher temperatures.

Wang and Wang [1980] have investigated the influence of moisture, temperature
and stress on the tensile creep behavior of Scotchply 1002 glass/epoxy composites.
Unidirectional laminates were loaded at angles 00, 450, and 900 with respect to the fiber
direction. At from temperature with low stress 6.2 MPa and moisture content (mass
fractions from 0.5% to 0.94%), 00 laminates exhibit minimal creep compared to the 900
and 450 laminates, but exhibited a significant increase in creep deformation when the
temperature was increased to 1020C. Creep of the 450 and 900 laminates was also
strongly influenced by moisture and temperature, even at low stress levels.

Figure 4-18: Moisture Absorption Behavior (adapted from Weitsman [116])

117
 Corrosion Tutorial

Moisture absorption behavior of composite materials can be categorized into

several types, as shown in Figure 4-18. Curve LF represents linear Fickian behavior,
where after a rapid initial take-off the moisture weight gain gradually attains equilibrium.
Glass fiber reinforced plastics (GFRP) exhibit such behavior under specified conditions.
For instance, E-glass/vinyl ester with acryl-silane or epoxy silane surface treatment
follows linear Fickian behavior for water absorption up to 80°C. Curve A represents
pseudo-Fickian behavior where the moisture weight gain never reaches equilibrium
after the initial take-off. Curve B is two-stage diffusion with an abrupt jump in moisture
weight gain after initial take-off. The cause for the jump is attributed to a change of
environment such as temperature, applied load, or relative humidity. This is due to the
fact that there are some periodic changes in the aforementioned environments. Curves
C and D represents the most adverse situation pertained to the material performance.
The rapid moisture weight gain depicted by curve C results from large deformation or
damage of the material, for example, fiber/matrix debonding and matrix cracking, which
are often irreversible. For curve D, moisture weight gain follows a decreasing trend after
the initial take-off, also an irreversible process as a result of leaching out of the material
from the bulk following chemical or physical break-down. Sorption process involving
severe circumstances such as elevated temperatures, external load, and high solvent
concentration will often result in behavior described by curves C or D. For instance,
glass/polyester at 40°C and under an applied load of 50% ultimate tensile stress
displayed type D behavior; S-glass/epoxy followed curve C in water at above 80°C. In
general, the moisture absorption behavior depends on temperature, applied load, type
of media, time, and material system, and is inseparable from other performance aspects
concerning durability.

The rate of fluid sorption and the quantity absorbed are governed for the most
part by the chemical structure of the resin, the degree of cross-linking, the type of cross-
linking, and presence of voids. As a consequence, the diffusion process can be actively
controlled by using a matrix with lower uptake or lower permeability, a hybrid matrix
composite.

118
 Corrosion Tutorial

4.3.3.1.2 Effect of Physical Aging on Creep

Physical aging is a process, occurring below the glass transition temperature Tg,
where the macromolecules gradually change their packing in order to approach the
equilibrium free volume state. The gradual approach towards equilibrium affects the
mechanical properties of the polymer, often resulting in a material that is stiffer and
more brittle, so that the compliance is decreased (or the modulus increased) than
expected in a viscoelastic material without aging. In terms of free volume theory, it can
be visualized that as the free volume decreases towards its equilibrium values; the
mobility of chain segments is hindered, giving rise to a stiffer response. Aging is a
characteristic of the glassy state and is found in all polymer glasses. The effects of
physical aging continue until the material reaches volume equilibrium. The time required
to reach volume equilibrium depends on the aging temperature. During this time the
mechanical properties may change significantly.

Effects of physical aging on long-term performance of FRP could be substantial,

especially when the material is subjected to an aging time as long as 50 or more years,
typical for infrastructure. In general, as polymeric materials physically age, they become
stiffer and more brittle, show less stress relaxation, or delayed increases in creep
compliance. In some cases this may be “desirable” if the changes are understood and
predictable.

119
 Corrosion Tutorial

Figure 4-19: Effect of physical again on creep behavior.

Physical aging can lead to changes in the short-term as well as long-term
mechanical properties. Effects of physical aging on long-term performance of FRP can
be substantial, especially on aging the material for 50 years or more. This is because
the materials become glassier. In general, as polymeric materials physically age, they
become stiffer and more brittle, show less stress relaxation, or delayed increases in
creep compliance. In some cases this may be “desirable” if the changes are understood
and predictable. It is found that the short-term creep compliance curves shift to longer
times with increasing initial aging time, and then the long-term compliance decreases
relative to simple extrapolation of the short-term compliance. In addition, the process of
physical aging is found to be both temperature and load dependent. This phenomenon
has been investigated extensively in the recent past, and it is well understood.

4.3.3.1.3 Effect of Ultraviolet (UV) Radiation on Creep

Ultraviolet radiation that reaches the earth’s surface comprises about 6% of the
total solar radiant flux and has wavelengths between 290 nm and 400 nm. Radiation
below approximately 290 nm is effectively eliminated by stratospheric ozone. The
remainder of the solar radiation is composed of visible (52%) and infrared (42%)
radiation. Since most polymers have bond dissociation energies on the order of the 290

120
 Corrosion Tutorial

nm to 400 nm wavelengths in the ultraviolet region, they are greatly affected by

exposure to this portion of the solar spectrum.

Chemical changes induced by UV exposure are the result of a complex set of

processes involving the combined effect of UV and oxygen. Bond dissociation is
initiated by the absorption of UV radiation, resulting in chain scission and/or cross
linking; subsequent reactions with oxygen result in the formation of functional groups
such as carbonyl (C=O), carboxyl (COOH), or peroxide (O-O). The effects of UV
exposure, or photo degradation, are usually confined to the top few microns of the
surface. However, in some cases, degradation at the surface of a polymeric component
has been shown to affect mechanical properties disproportionately, as flaws that result
from surface photo degradation can serve as stress concentrators and initiate fracture
at stress levels much lower than those for unexposed specimens. The effect of
ultraviolet radiation is also compounded by the action of temperature, moisture, wind-
borne abrasives, freeze-thaw and other environmental components.

The effect of UV radiation on the creep behavior of different polymeric materials

was investigated by Regel et al. [1967]. By irradiating a loaded specimen in the
wavelength interval from 248.3 to 300.0 nm, they found that during the time that the UV
radiation was turned on, creep strain increased sharply. On turning off UV radiation, the
creep rate returned to the original value, showing that the creep-rate change was
reversible. This increase occurs at each and all steps of creep and is fairly general, as it
is exhibited by a large number of polymers.

Regel et al. (1967) suggested that the increase in creep of exposure to UV

radiation was the result of increased stress relaxation or easier relative movement of
polymer chains.

4.3.3.2 Fatigue and Fracture

Fatigue is defined as the failure or rupture of a plastic article under repeated
cyclic stresses, at a point below the normal static breaking strength. Fatigue failure
occurs when a specimen has completely fractured into two parts, has softened or has

121
 Corrosion Tutorial

otherwise significantly reduced in stiffness by thermal heating or cracking. It can also be

arbitrarily defined as having occurred when the specimen can no longer support the
applied load within the deflection limits of the apparatus.

Fiber Reinforced composites have a rather good rating regards to life time in
fatigue. The same does not apply to the number of cycles to initial damage nor to the
evolution of damage. Composite materials are inhomogeneous and anisotropic, and
their behavior is more complicated than that of homogeneous and isotropic materials
such as metals. The main reasons for this are the different types of damage that can
occur (eg. Fiber fracture, matrix cracking, matrix crazing, fiber buckling, fiber matrix
interface failure, delaminations,…), their interactions and their different growth rates.

The following are the parameters that influence the fatigue performance of
composites

• Fiber type
• Matrix type
• Type of reinforcement structure (unidirectional, mat, fabric, braiding..)
• Laminate Stacking Sequence
• Environmental conditions (mainly temperature and moisture absorption)
• Loading conditions (stress ratio R, cycling frequency …) and boundary
conditions

There are a number of differences between the fatigue behavior of metals and
fiber reinforced composites. In metals, the stage of gradual and invisible deterioration
spans nearly the complete lifetime. No significant reduction of stiffness is observed
during the fatigue process. The final stage of the process starts with the formation of
small cracks, which are the only form of macroscopically observable damage. Gradual
growth and coalescence of these cracks quickly produce a large crack and final failure
of the structural component. As the stiffness of a metal remains quasi unaffected, the
linear relation between stress and strain remains valid, and the fatigue process can be
simulate d in most of the cases by a linear analysis and linear fracture mechanics.

122
 Corrosion Tutorial

In fiber-reinforced composite damage starts very early and the extent of the
damage zones grows steadily, while the damage type in these zones can change (e.g.,
small matrix cracks leading to large size delaminations). The gradual deterioration of a
fiber reinforced composite-with a loss of stiffness in the damaged zones – leads to a
continuous redistribution of stress and reduction of stress concentrations inside a
structural component. As a consequence an appraisal of the actual state or a prediction
of the final state (when and where final failure is to be expected) requires the simulation
of the complete path of successive damage stress.

Studies comparing glass and carbon fibers suggest carbon fiber composites are
superior in fatigue performance in terms of fatigue life and rate of damage development.
The matrix also influences fatigue performance at a low number of cycles. It was found
that the influence of the matrix on the quasi-static properties is on the position of the
knee point in the stress-strain curve. It is a quantity defined by the intersection of two
linear parts on the stress strain curves. Fatigue loading above the knee point results in
degradation of stiffness followed by sudden drop in stiffness leading to the death of the
composite material and loading below knee point is the no-failure situation. Low
deflection fatigue is matrix and interface dominated while high deflection levels include
matrix cracking, fiber matrix debonding, glass fiber fracture at the tensile surface, and
plane fiber buckling and delamination on the compressive side. Fatigue behavior of
composite laminates is both frequency and temperature dependent. Higher frequencies
and higher temperatures tend to reduce the fatigue life of the composite material.

The effects of elevated temperatures, humidity, and other corrosive fluids (such
as acids) on FRP are to shorten their fatigue life, compared to those fatigued without
imposed environment. Jones et al. (1983) noted that the fatigue degradation rate of
GFRP preconditioned in boiling water is slower compared to dry specimens. The
authors attribute this phenomenon to several factors; first, Plasticization of the resin
may result in an increase in the long life fatigue strain in the resin. Second,
preconditioning in boiling water permitted relaxation of the thermal strains introduced
during processing. Third, stress transfer capacity of the resin-fiber interface will be
reduced by boiling, which in turn will reduce the stress concentration in the vicinity of the
broken fibers or resin micro-cracks.

123
 Corrosion Tutorial

Romans et al. (1971) have shown that the susceptibility of different epoxies to
water is different, which suggests that the effect is matrix and/or interface controlled and
there is a close relationship between chemical structure and environmental
susceptibility. Specimens exposed to water have reduced fatigue life and is attributed
to the combined effects of mechanical fatigue and localized pressure exerted by water
trapped in the micro cracks.

The fiber matrix interface region has a controlling effect on the environmental
fatigue of composites. The rate of reduction on the off-axis specimens in water is higher
than the unidirectional specimens, implying direct impact of water on the interphase
region. It has been indicated that fluid absorption during fatigue is faster than under
static condition, and there is a dynamic interaction of fatigue behavior and the
environment.

4.3.3.2.1 Fatigue Process

Unlike homogeneous materials, FRP composites accumulate damage in general
rather than developing localized damage, and fracture does not always occur by
propagation of a single macroscopic crack. The damage accumulation in these
materials is micro structural, which includes fiber/matrix debonding, matrix cracking,
delamination and fiber fracture [Mathews, 2000]. Fatigue damage mechanism in
unidirectional composites primarily depends on loading mode (e.g., tensile,
compressive, bending, torsion or combinations) and on the loading direction i.e., parallel
or inclined to the fiber direction. In unidirectional fiber reinforced composites, fractures
in fibers occur but the accumulation is slower and the life of the composite is not
dependent on fatigue fractures in fibers. But matrix micro cracks transverse to the
loading axis develops and propagates, thus breaking fibers or causing interfacial failure,
leading to the failure of the composite. In uni-directional composites, fatigue damage is
initiated by debonding between fiber and matrix. Typically, the damage mechanism in
tensile fatigue is of three stages as shown in Figure 4-20 [Talreja, 1987] namely:

Fiber breakage

Matrix cracking

124
 Corrosion Tutorial

Interfacial shear failure

Figure 4-20: Fatigue Damage Mechanism in Unidirectional Composites Under Loading Parallel to Fibers: (a)
Fiber Breakage, Interfacial Debonding; (b) Matrix Cracking; (c) Interfacial Shear Failure [Talreja, 1987]

Mechanical fatigue is the most common type of failure of structures in service.

The fatigue behavior of composite materials is conventionally characterized by a Wöhler
or S-N curve. For every new material with a new lay-up, altered constituents or different
processing procedure, a whole new set of fatigue life tests has to be repeated for such a
characterization. If the active fatigue damage micromechanisms and the influence of the
constituent properties and interface were known, it would be possible, at least
qualitatively, to predict the macroscopic fatigue behavior. A study of the fatigue damage
mechanisms would also give indications of the weakest microstructural element, which
is useful information in materials selection for improvement in service properties. In
tensile fatigue of a multidirectional laminate, the critical elements are the longitudinal
plies, which are the last to fail.

Fiber breakage is due to the failure of the weakest fiber in the laminate due to
excess stress, which causes shear-stress concentration at the interface i.e., close to the
tip of the broken fiber, leading to debonding of the fiber from surrounding matrix. The
debonded area leads to matrix cracking when the stresses exceed the fatigue limit.
Under low strains, approximately 50% of ultimate tensile strain of matrix, a matrix crack
stops at the interface. However, at high strains, the stresses at crack tips exceed the
fracture stress leading to fiber pullout or breakage of adjoining fibers due to higher
stresses. Strength degradation is assumed also to take place in these two stages
reflecting the development of the underlying damage process.

125
 Corrosion Tutorial

In the first stage, a general weakening of the material is assumed and is

considered dependent on damage parameters representing the stage of damage. A
power law is assumed for the rate of increase of the damage parameter [Talreja, 1987],
taking it as a function of an effective stress. A relationship between the residual
strength (R) and the initial strength (R0) is then given as:
m'
⎛ N ⎞
R = R c + (R 0 − R c )⎜⎜ 1 − ⎟⎟ …(4.28)
⎝ Nc ⎠

1
m' = …(4.29)
(1 + m)
1
Nc = …(4.30)
k (1 + m )S m

where Rc, Nc - residual stresses and number of cycles at the CDS, respectively;

m’, m, k - material constants, and S- maximum applied stress, respectively.

In the second stage, strength degradation is assumed to result from the localized
zones of damage which are conceptually replaced by a single crack capable of
releasing the same amount of elastic energy as that released collectively by the various
crack growth mechanisms. Residual strength (R) is related to a characteristic
dimension of the "equivalent” crack C through a fracture mechanics type relationship

R = αC −1 / 2 …(4.31)

where α is the material constant characterizing material toughness [Talreja,

1987].

The evolution of damage is expressed by the rate of growth of the crack

dimension, which is assumed to depend on the current state of damage given by the
current crack dimension. Assuming a power law for the crack growth, a relationship
between residual strength and the applied maximum stress is derived. This relationship
forms the basis for determining the probability distribution of the residual strength and
the probability distribution of the number of cycles to attain the Characteristic Damage
State. The complete two-stage strength degradation model for fatigue reliability

126
 Corrosion Tutorial

analysis of composites is illustrated in Figure 4-21 where R is the initial strength, Rc and
Nc are the residual strength and the number of cycles corresponding to CDS, S is the
maximum applied stress and Nf is the number of cycles to failure.

Figure 4-21: Two-Stage Strength Degradation Model for Fatigue Reliability of Composites [Talreja, 1987]

4.3.3.2.2 Fatigue in Unidirectional Composites

The S-N curve for carbon fiber, glass fiber and aramid fiber in the same standard
epoxy matrix is shown in Figure 4-22. The use of stiff fibers such as carbon fibers
results in low strains (1.0 - 1.8%) to failure and less stiff fibers like glass lead to
relatively higher strains (2.5 – 3.5 %) to failure. Hence, the curve is steep for glass fibers
while it is shallow for carbon fibers in Figure 4-22. The slope of the curve (Figure 4-21)
is a function of the strain in the matrix [Curtis and Dorey 1986]. The S-N curve for
carbon fibers with different stiffness in the same standard epoxy resin is shown in
Figure 4-21.

127
 Corrosion Tutorial

Figure 4-22: Comparison of S-N Curve for Three Different Unidirectional Composite Materials [Curtis and
Dorey, 1986]
It can be seen that there is little improvement in the fatigue behavior with change
in fiber stiffness. This is because the fatigue behavior of composites is dependent on
the strain in the matrix and interfacial characteristics rather than fiber strength. Due to
this reason, plots of mean strain rather than stress versus log cycles to failure are
commonly used for composite materials (Figures 4-22 and 4-23).

128
 Corrosion Tutorial

Figure 4-23: Comparison of S-N curve for Four Different Materials with Different Carbon Fibers in Same
Epoxy Resin [Curtis and Dorey, 1986]

A typical fatigue life diagram (Figure 4-24a) for a unidirectional composite under
loading parallel to fibers is shown. In Figure 4-24a, fatigue limit of the matrix is defined
as the maximum strain below which no cracks or only non-propagating cracks maybe
initiated in the matrix material. This matrix material property is taken as the lower limit
of the progressive matrix damage. It can be seen that as the fiber stiffness reduces,
distinct progressive damage band (matrix cracking) is observed before fiber breakage.

129
 Corrosion Tutorial

Figure 4-24: Fatigue Life Diagram of Unidirectional Composites Under (a) Loading Parallel to Fibers, (b)
Off-Axis Loading (Dotted line correspond to on-axis loading) [ Talreja, 1987]

For off-axis loading angles between 0o and 90o, the tip of crack initiated in the
matrix will be subjected to two displacement components, i.e., an opening normal to the
fibers and a sliding parallel to the fibers. This leads to a mixed mode crack growth
parallel to the fibers. The limiting values of crack tip displacement will depend on the
off-axis angle; with crack tip displacement increasing with an increase in off -axis angle.
The fatigue life diagram for off-axis loading is shown in Figure 4-24 (b). It was found
that for off-axis angles more than a few degrees, the fiber breakage bond would be lost,
as matrix and/or interfacial cracking will become the predominant damage mechanism
for strain up to fracture strain. [Talreja, 1987]

4.3.3.2.3 Fatigue in Multidirectional Composites

The damage mechanism in multidirectional composites is similar to off-axis
loading in unidirectional composites except that delamintion is found to occur in these
laminates [Talreja, 1987]. In multidirectional composites, the first event of failure is
debonding of transverse fibers. The debonded crack then grows towards the ply
interface causing stress concentration in the interfacial layers. This leads to
delamination and hence overstressing of the 0o ply; thus, the increase in the number of
non-axial plies in a laminate reduces the strength and stiffness since only fewer fibers

130
 Corrosion Tutorial

are available to support the mean applied stress in the axial direction [Mathews, 2000].
For a multidirectional laminate, Figure 4-25 gives the comparison of S-N curve for
varying percentage of 0o plies

Angled ply layers with fibers typically at ±450 can also develop intraply damage,
which causes a small reduction in strength and stiffness [Curtis and Dorey, 1986]. Also
stress concentration is developed at the ends of intraply cracks, which causes
delamination between the layers. Multidirectional laminates also develop edge-induced
stresses because of different elastic properties of the layers, often giving rise to
delamination between layers.

Figure 4-25: Normalized S-N Curves for (0/±45) CFRP Laminates with Varying Percentage of 0o Fibers
[Curtis and Dorey, 1986]

4.3.3.3 Aging Due to Environmental Factors

Several researchers have investigated the changes in properties and
performance of composites under various environments, when they are manufactured
with different constituent materials. In the following sections, an extensive review of the

131
 Corrosion Tutorial

literature dealing with durability/aging of composites is carried out. Special attention is

paid to understanding the existing experimental and analytical methods to qualify and
predict the effects of constituent materials and environmental conditions on composites.

4.3.3.3.1 Environmental Factors Influencing the Durability of

Composites
Environmental factors such as moisture (water, humid air or liquid), temperature
(free-thaw cycling, elevated temperature, fire) and other weathering conditions
(physical, chemical, and UV rays exposure) affect the performance of both neat resin
and composite materials. The physical weathering condition occurs when either the
neat resin or a composite material is subjected to mechanical loadings such as static
load, fatigue and creep. The chemical weathering condition occurs when either the neat
resin or composite materials is exposed to chemical solutions such as alkaline, acid or
aqueous. When composite materials are subjected to these environmental factors,
mechanical and chemical properties such as strength, stiffness, creep, fatigue life, glass
transition temperature, and interfacial bond strength of the composite material change
with exposure time. Degradation of mechanical properties depends mainly on: 1)
chemical and physical structure of the polymer, 2) physical state of the material, 3)
additives, 4) time and temperature, 5) moisture and pressure, and 6) nature of stress
[Kilen, 1983]. Composite material property changes over a long service life (» 50 years)
can be predicted by experimental methods simulating the environmental conditions in
the laboratory. The moisture and temperature distribution inside the composite
materials, commonly known as “moisture problem,” can be predicted by analytical
methods such as Fick’s diffusion law [Springer, 1981].

4.3.3.3.1.1 Effect of Moisture

The effect of moisture on composite materials occurs when the composite
materials are exposed to humid air, water or any liquid. Depending on the
environmental conditions and the condition of the material, the material either absorbs

132
 Corrosion Tutorial

or loses moisture as manifested by weight gain or weight loss [Springer, 1981].

Moisture absorption and desorption in a composite material eventually leads to the
degradation in its properties. Moisture affects the composite materials at the matrix or
the fiber level, and even at the interface of fiber/matrix level.

Effect of moisture in resins

Moisture content in resins depends on various factors such as type of resins,
fillers, additives, nanomers, type of liquid to which the resin is exposed to, temperature,
etc. First, moisture penetrates through the resin and later moisture is transferred
through the cracks [Springer, 1981]. Neat resins show higher moisture absorption than
the composites show, because in the resins the matrix swells when exposed to
moisture. The swelling of the matrix causes stress within the material, which eventually
tends to decrease the strength and stiffness. However, many resin systems tend to
recover their properties upon drying. Further, the percentage of moisture absorption
varies from resin to resin based on their chemical structures. Chin [1999] observed the
moisture uptake for vinyl ester and isopolyester resin exposed to distilled water, salt
water and concrete pore solution at 22oC and 60oC. For vinyl ester (at both ambient
temperature and 60oC), salt-water uptake was higher than pure aqueous or alkali
solution uptake. Similar results were observed in the case of isopolyester at ambient
temperature, but at 60oC, mass loss occurred after a certain period in alkaline solution
and salt water. This is attributed to the fact that in a polyester resin, ester groups are
distributed along the main chain, making them more available to hydrolysis reactions at
higher temperatures. The structure and morphology of a resin affect the moisture
uptake. In general, a high concentration of polar functional groups can promote
increased sorption of polar penetrants [Apicella et al., 1982]. Among epoxy, vinlyester,
and isopolyester resins, the sorption was greater for epoxy compared to the other two
resins because more hydroxyl groups are present in epoxy matrix. Most of the resins or
composites follow the Fickian process, and a non-Fickian behavior occurs when the
resins or composites undergo damages such as cracks. Diffusion in all three liquids
(water, salt, alkaline) and in three resins (epoxy, vinyl ester and isopolyester) followed
the Fickian process [Chin, 1996].

133
 Corrosion Tutorial

Effect of moisture in glass fibers

Studies conducted by Ehrestein and Spaude [1984] showed that both glass fiber
and glass fiber-resin bond are susceptible to degradation through moisture content.
Glass fibers can lose up to 10% of their bending strength when exposed to moisture.
While resins recover their lost properties while drying, glass fibers do not recover their
properties but tend to corrode, eventually leading to loss of effective cross-section.
Results from a companion study of Karbhari et al. [1998] show that water accelerates
the rate of crack growth in glass with the degradation being more severe and following
different mechanisms with higher temperature exposures. Acceleration is thought to be
the result of two factors: 1) reduction in surface energy of glass fibers after exposure to
moisture that reduces the energy required for interfacial crack formation, or debonding
and 2) reduction in energy required to break the Si-O bonds. The strength of E-Glass is
time dependent in the presence of moisture and is susceptible to stress corrosion.
Stress corrosion in turn is dependent on the type of attacking fluid, wherein more
concentration of corrosive fluid leads to greater detriment to glass fibers.

Effect of moisture in composites

Moisture content in composites depends on the type of composites and
environmental conditions that the composite is exposed to over a certain period and
range of temperature. When composites with polymer matrix are placed in a wet
environment, the matrix begins to absorb moisture. The moisture absorption of most
fibers used in practice is negligible; however aramid fibers alone absorb significant
amount of moisture when exposed to high humidity [MIL-HDBK-17, 1997]. The effect of
temperature and moisture on Kevlar/epoxy laminates was studied by Allred [1984], who
showed that in the saturated state, the room temperature flexural strength of the
laminates decreased by 40% over the dry state. Similarly, at an elevated temperature,
the strength drop was found to be in the range of 60 – 70%.

When composites are exposed to humid air, the moisture content depends on
the relative humidity in the air. When composites are exposed to acidic or alkaline
liquids, the moisture content depends on the type of the attacking liquid. The maximum

134
 Corrosion Tutorial

moisture content in the Graphite/epoxy composite was found to be lower in salt solution
(1.25%) than in distilled water [Springer, 1981]. A similar trend was noted in the E-
glass/vinyl ester composite with maximum moisture content of 0.18 ~ 0.29% in the salt
solution compared to the moisture content of 0.22 ~ 0.33% in the tap water [Vijay,
1998]. The maximum moisture content was nearly twice in the alkaline solution
compared to tap or salt water. This hypothesizes that the degradation of the material
has started at the interface of the fiber/matrix level. In the case of E-glass /polyester
composites, the interface tends to become more hydrophilic when exposed to moisture
and the following is noted: 1) The fibers weaken due to crack growth that is accelerated
by water in the resin; 2) The resin swelling produces radial stresses at interface that is
reinforced by water pressure, and leads to fiber debonding and consequent weakening
of composite; 3) plasticization of resin by water results in increase in viscoelasticity.
When a composite absorbs moisture, the swelling coefficient of fiber is lower than the
matrix. Free swelling of layers does not take place and, consequently, internal stresses
are developed. These internal stresses can be calculated as in MIL-HDBK-17 [1997].

4.3.3.3.1.2 Effect of Temperature

Temperature plays a vital role in the durability of composites. Temperature
affects the rate of moisture absorption and chemical and mechanical properties of the
composites. The magnitude of these temperature effects depends on the type of liquid
to which the composite is exposed. The mechanical and visoelastic behavior of
composites could degrade dramatically at elevated temperatures and under freeze-thaw
cycles, which is discussed below.

Elevated temperature
When the fiber reinforced composite materials are exposed to elevated
temperature, mechanical properties such as modulus, tensile and flexural strength,
fatigue strength and creep resistance and adhesive strength may decrease [Kelen,
1983]. Composite materials generally degrade when exposed to moisture, but the

135
 Corrosion Tutorial

degradation is further enhanced at elevated temperatures mainly due to matrix

degradation. An increase in temperatures may also cause time-dependent effects such
as creep and stress relaxation [Janas and McCullough, 1987], whereas low
temperatures may result in brittle failures. Vinyl ester composites aged at high
temperatures in an aqueous environment showed an overall decrease in strength with
an increase in the duration of conditioning at a given condition, particularly at higher
temperatures [Buck, 1998]. At an elevated temperature, alkaline solution will be the
most damaging solution to glass composites and also to the neat resins in terms of
tensile strength. The alkali affects the fiber/matrix debonding as well as the fibers. As
the temperature increases, the pH value of an alkaline system also increases, thereby
increasing the corrosiveness inhibited by the alkaline solution. At 99oC the alkaline
solution was found to be more corrosive and weight losses found to be about two to five
times greater at temperatures higher than at 66oC.

Freeze-thaw cycles
The excess moisture in composites generally expands upon freezing and causes
internal stresses, which initiate cracks or delaminations. Due to the formation of cracks,
the mechanical properties of a composite degrade largely under freeze-thaw cycling.
For example, the ultimate tensile strength of Kevlar laminates was found to decrease by
23% after 360 cycles and by 63% after 1170 cycles when subjected to two hour
temperature cycles from –20oF to 125oF [Allred, 1995]. Similarly, there was significant
strength and stiffness loss of GFRP composites in alkaline solution under freeze-thaw
cycling (0 – 70 oF) [Vijay and GangaRao, 2000]. An average strength reduction of
about 10% was observed for glass reinforced isopolyeser and vinyl ester structural
plates when treated in 4% salt solution and exposed at both room temperature and
cyclic temperature of 0 – 70oF [Ajjarapu, 1994]. The durability of pultruded vinyl ester
composites was investigated by means of freeze-thaw tests. Samples were subjected
to three levels of exposure, 100, 300 and 500 cycles. The strength and strain to failure
were found to be approximately 50% lower for E-Glass/vinyl ester and E-Glass/epoxy
samples when subjected to 4.4oC to –17.8oC freeze-thaw cycling temperature [Lesko,
2000]. In the work done by Vergheese, et al. [1999], differential scanning calorimetry

136
 Corrosion Tutorial

(DSC) was used to identify the nature and presence of freezable water for each
constituent material within an E-glass/vinyl ester composite, i.e., matrix and interface.
Heat flow measurements during thawing taken for a single cycle (-150oC to +50oC) on
saturated, unreinforced vinyl ester resin samples indicated no melt endotherm and thus
the absence of freezable water. This was attributed to the fact that water resides in the
free volume of the resin. Since this free volume size is in the order of about 4.20 A,
these voids are thermodynamically too small for water to freeze. It is highly unlikely to
freeze water in highly cross-linked amorphous polymers. This is due in part to
geometric space constraints in addition to hydrogen bonding, which further impede the
freezing process. However, the crack dimensions in composite systems are large
enough to facilitate the freezability of water. The freezability of water leads to
accumulation of damage due to the growth of cracks. In one other study, Dutta, [1994],
concluded that low temperatures stiffen the polymer composites. The flexural behavior
of composites is matrix-dominated and the increase of bending and shear modulus at
lower temperature controls the composite’s flexural properties. Thus, polymer matrix
and its type play a crucial role in the composite’s behavior at subfreezing temperatures.
Low temperature thermal cycling has shown that both bending and shear moduli
degrade in case of plain weave glass composites.

4.3.3.3.1.3 Effect of Solutions with Different pH Levels

Effect of salt solution

The effect of salt solution on a composite is very low compared to the effect of
other environmental aging conditions. This is because salt molecules are larger than
other liquid molecules; hence the diffusion rate is slower. The slow diffusion rate
prevents early damage of fiber/matrix interface and the glass fibers. In fact, several
researchers have observed a strength gain in composites when exposed to salt
solution. Strength gain is mainly due to post curing which improves the properties of
matrices in the composites. Strength gain (less than 10%) and stiffness loss (less
than10%) were observed for a glass/vinyl ester composite when conditioned in salt

137
 Corrosion Tutorial

water at room temperature [Vijay, 1998]. The reduction in strength and stiffness is
greater when composites in salt solution are exposed at elevated temperature because
the rate of diffusion increases at elevated temperatures. The tensile strength loss of
about 19% was observed in a glass/epoxy composite conditioned in salt solution at
60oC. From the SEM micrographs, it was concluded that the failure of composites was
due to matrix degradation; i.e., cohesive failure [Kajorncheappunngam, 1999]. The
degradation in tensile strength (when exposed to salt solution) can be reduced to some
extent by adding chopped strand mats in the composites. The ester linkages in the
outer layers of the continuous strand mat bind the free water through hydrogen bonds in
the surface layers, hence reducing its effect through the thickness. In general, the
degradation in strength and stiffness of composites exposed to salt solution is
insignificant compared to other aging liquids.

Effect of aqueous solution\acid solution

Acid affects on the composite in terms of reduction of strength and stiffness at
room temperature. When composites are exposed to acids, the acid diffuses through
the matrix and subsequently reaches the surface of glass fibers. Once the acid
contacts the glass fibers, the ion exchange takes place between glass fibers and acid,
eventually leading to surface shrinkage. The surface shrinkage causes internal stress
within the fibers and initiates cracks in the fibers. Sometimes, the ions in the matrix
cause fracturing of matrix, thereby increasing the rate of diffusion and leading to
debonding of fibers. The reduction in tensile strength of a glass/epoxy composite
exposed to acid solution over a 5-month period was 73% at room temperature, but it
was only 48% at elevated temperature [Kajorncheappunngam, 1999]. At elevated
temperatures, the effect of acid on strength reduction is low because the ion exchange
reaction reduces at elevated temperature, and hence the damage to glass fibers is low
compared to room temperature damage.

Durability of composites in an aqueous solution greatly depends on the type of

fiber that reinforces the composite. For example, boron free glass fiber shows improved
performance over traditional E-glass fiber because the former has improved corrosion

138
 Corrosion Tutorial

resistance. ECRGLAS (boron-free glass) laminates were found to have 30% higher
flexural strength than E-glass laminates. The aqueous solutions cause dramatic
increase in hydrolysis of Kevlar 49 yarn, especially in the combination of temperature
and stress. The degradation in such glass fibers can be protected to some extent by
choosing the appropriate resin system, application of gel coats and providing
appropriate protective coatings. The efficacy of application of gel coats and protective
coating has been shown by the marine industry to prevent blistering, jackstraw, matrix
degradation and fiber attack [Altizer et al., 1996].

Effect of alkaline solution

Significant loss in strength and stiffness occurs when the composites or neat
resins are exposed to alkaline conditions. This loss is attributed to the fact that the rate
of moisture absorption in composites is more when exposed to alkaline solution than
other liquids. The rate of strength and stiffness loss was about twice in alkaline
environment for E-glass/vinyl ester composite over that for glass composite exposed to
salt environment [Vijay, 1998]. The alkaline solution mainly attacks at the interface of
fiber/matrix debonding. The hydroxide ions in an alkaline environment attack the
primary component of glass (silica) and cause the breaking of Si-O-Si bonds in glass
fiber. This results in fiber corrosion and reduction in strength. At an elevated
temperature alkali has a greater effect on the strength and stiffness of the composites.
This is attributed to better matrix cross-linking reaction and becomes brittle. The
brittleness leads to matrix cracking, thus reducing the strength and stiffness of the
composite. A reduction of about 70% in tensile strength and ultimate strain to failure
was observed in a glass/polyester composite (Vijay and GangaRao, 1999). The effect of
alkali can be anywhere in the composites, i.e., fibers, matrix or at the interface of
fiber/matrix. Hence, durability of composites in alkaline solution can be improved by
selecting proper fiber and/or resin. For example, corrosive resistant glass fibers and
alkali resistant resins can be used to make composites. Boron free glass fibers (ECR)
show improved performance over traditional E-glass fibers because of their improved
corrosion resistance. Composite with Advantex glass fibers (boron free glass) had

139
 Corrosion Tutorial

about 95% tensile strength retention, while those with E-glass had only about 85%
retention in the tensile strength Devalpura [1998].

Glass fibers are more sensitive to alkali environment when compared to aramid
or carbon fibers. The penetration of alkali into such fibers is mostly time dependent. For
GFRP bars, the penetration of alkali increases with time. The glass fibers deteriorate in
the area where alkali has penetrated, which reduces strength of the bars. The strength
of GFRP bars decreased with time when immersed in alkali solution, whereas those of
AFRP and CFRP bars were not decreased [Katsuki, 1995]. Higher alkali concentration
increases the degradation on composites. GFRP bars immersed in 5gm/L of sodium
hydroxide (over a 4 month period) had about 20% reduction in strength while those in
20 gm/L of sodium hydroxide had about 30% reduction in strength [Alsayed, 1998].

With respect to performance of resin in the alkaline solution, vinyl ester has
better alkaline resistance compared to other resins and exhibits excellent strength and
stiffness properties. The increased distance between cross-linkages in vinyl ester
implies that it does not completely polymerize. Performance characteristics of vinyl
ester changes with cure time. The ultimate tensile strength of vinyl ester samples after
1300 hours of immersion in alkaline solution was about 70 MPa while that of
isopolyester was only about 50 MPa. The pH level of an alkaline solution is another
important factor, which acts as a catalyst in degrading the glass fibers. Cementitious
extract with pH 10 buffer and water had the greatest degradation in composite strength.
This is hypothesized due to greater concentration of Ca ions available for formation of
calcium hydroxide crystals at the surface of glass fibers. The effect of alkali solution on
composite materials can be potentially reduced by fiber sizings (to promote fiber/resin
debonding) and by selecting alkali resistant resins and corrosive resistant fibers [Altizer
et al., 1996].

140
 Corrosion Tutorial

4.3.3.3.1.4 Effect of Environmental Aging on Glass Transition

Temperature (Tg)
The glass transition temperature (Tg) generally indicates the thermal stability of a
composite material. The Tg varies depending on the type of aging environment and the
exposure temperature of composites. The aging solutions (depending on moisture
absorption) lower the glass transition temperature (Tg) and enhance the apparent
phase separation in composites due to the effect of polymer plasticization. The effect of
plasticization was greater in glass/epoxy composites than it was in epoxy neat resin
samples. This was probably due to exposed edges that allowed solution to diffuse
easily into the composite than the neat resin [Kajorncheappunngam, 1999]. In contrast
to neat resins, the reinforcing fibers in a composite and the resulting interface regions
actually enhance resin plasticization and hydrolysis, slowing down Tg kinetics. When
the composites are exposed to acidic environment, Tg increases rapidly due to the
hydrogen bonding, and then remains constant, once the hydrogen bond formation
reaches its maximum state due to the finite number of accessible active sites available
for H+ ions. The performance of composite material in terms of Tg varies with
temperature. At ambient temperature, no significant changes were observed in Tg for
vinyl ester and isopolyester resins following 1300 hour immersion in water, salt solution,
and concrete pore solution [Chin, 1985]. As the cure temperature increases, the glass
transition temperature also increases. This is because, at elevated temperature,
additional cross-linking reactions take place and there is continued resin curing process.
At temperatures above glass transition, polymer molecules have sufficient
instantaneous mobility to get back towards equilibrium during temperature changes.
When a polymer is quenched from above-to-below glass transition temperature, the lack
of instantaneous mobility results in free volume in the system. This change in free
volume during the movement towards equilibrium results in altering mechanical
properties of the bulk polymer [GangaRao et al., 1995].

141
 Corrosion Tutorial

4.3.3.3.1.5 Effect of Ultraviolet (UV) Rays

The UV radiation affects polymeric composites, especially at and near the
surface [Ashbee, 1989]. However, no significant damage in terms of composite material
properties has been found [Ashbee, 1989]. In addition, accelerated UV exposure tests
under wet/dry cycles on marine fabrics with polyesters or nylon fibers were found to
have significant reductions in tensile strength and elongation [Moore and Epps, 1992].
Based on the above data, it is clear that the resins and fibers made of polymers have
significant property changes. On the other hand, FRP composites primarily driven by
glass or carbon fibers do not vary significantly.

4.3.3.3.1.6 Structural and Manufacturing Factors Influencing

Durability of Composites
Durability of composites not only depends on environmental factors such as
moisture, temperature, physical and chemical exposure, but also to some extent on
structural factors. The factors that influence structural properties are: 1) type of fibers
(glass, aramid, carbon etc.), 2) type of resins (epoxy, vinyl ester, polyester etc.), 3) type
of composites (epoxy/glass, vinyl ester/glass etc), 4) fiber orientations, 5) fiber volume
fractions, 6) thickness of the composites, 7) interfacial bond, 8) manufacturing
techniques 9) others. Performance of a composite as function of some of the structural
factors is addressed, herein.

Fibers
The performance of composites under aging conditions depends on the type of
fiber reinforcement. Since the fibers are the main load resisting constituents of
composites, the early degradation of the fiber should be avoided. The fiber should be
selected in such a way that they are alkali resistance, because alkali solution breaks the
glass bonds in the fiber leading to fiber breakage. Generally, boron free glass fibers are
corrosion resistant and perform well when compared to the traditional E-glass fibers. As
mentioned earlier, the penetration of alkali occurs more in glass fibers than in aramid or
carbon fibers. Although carbon fibers do not absorb moisture and are resistant to many

142
 Corrosion Tutorial

chemical solutions, carbon composites do absorb moisture, when formulated with

polymer matrices. Although the degradation of carbon fibers may not occur by itself, the
oxidation reaction at the carbon cathode degrades the matrix material in that location
causing degradation of the composites. Similarly, ECR-glass has an enhanced
chemical resistance, especially in acid environment [EUROCODE, 1996].

A chopped strand mat is used for a smooth finish of a composite. The chopped
strand mats are actually resin rich surfaces and increase the moisture absorption and
diffusion coefficient. Diffusion coefficient for laminates with chopped strand mats at the
surface was found to be considerably higher than with continuous fabrics. The fiber
volume content is one of the factors responsible for the durability of composites.
Interlaminar shear strength and impact strength of the laminates were measured and
found to have the properties of the composites with higher fiber content degraded faster
than those with lower fiber content [Singh, 1991]. The fiber orientation plays a vital role
in the moisture absorption. In one study, Karbhari et al. [1998] found higher moisture
absorption but lower strength degradation in triaxial fabrics compared to the uniaxial
fabrics. The extra moisture absorption effects in specimens with triaxial fabrics were
hypothesized due to absorption along the fiber-resin interfaces with increased
directionality resulting in increased crossover or contact points.

Resins
The durability of composites varies with the type of resin used in the composites.
Failure in the composites primarily initiates at the resin level. Since resins have more
void contents, they are easily attacked by the aging solutions. Most of the aging
solutions penetrate the resin and reach the core, thus degrading the fibers or the
interface of fiber/matrix. Hence, one should be careful in selecting the type of resins. In
one study, bisphenol polyster was found to perform much better as compared to the
isophthalic polyester, because the former was more corrosion resistant. Also several
studies have proven that vinyl ester has good stability against harsh environments
compared to the polyester. This is mainly attributed to the chemical structure of vinyl
ester resins. Polyesters have double bonds at about 250g/mol level while vinyl esters

143
 Corrosion Tutorial

have reactive double bonds at about every 500-1000 g/mol. In addition, performance
characteristics of composites with vinyl ester change with cure time.

Manufacturing Techniques
Manufacturing techniques play a partial role in the durability of composites.
Possibility of high void content exists in a composite during manufacturing. The
presence of voids in the components increases the moisture absorption and diffusion
coefficient, which eventually leads to degradation in strength and stiffness on a long-
term basis. Controlling the line speeds can reduce the void fractions during pultrusion.
Pultruded samples made at different line speeds (4, 8, and 12 ipm) were aged, then
different conditions and mechanical properties were evaluated [Garland, 2000]. Based
on the microscopy results, no difference was observed in the void fraction due to the
effect of line speeds; hence, no difference was observed in the rate of moisture
absorption. Pull speeds at higher line speeds may provide some differences in void
fractions, fiber wet-out and degree of cure, which may then show the rate of degradation
in the strength and stiffness when exposed to environmental conditions. Hence, the
void contents in the composites should be kept as low as possible during manufacturing
process, i.e. less than 0.5% if possible and certainly no more than 1%.

4.3.3.4 Knockdown Factors

The mechanical properties of a composite material, such as strength in tension,
bending, shear etc. can be obtained by conducting experiments at coupon, component
or system level on non-aged specimens or by using the analytical formulae given in
section 1.4.1. In order to calculate the nominal strength and stiffness values for design,
the base values obtained should be multiplied with modification factors for actual field
and environmental conditions. These modification factors are called knockdown factors.
Equations 4.32 and 4.33 are equations used to calculate nominal strength and stiffness.
(AASHTO LFRD Bridge Design Specifications)

F=F0CfCmCcCaCst …(4.32)

144
 Corrosion Tutorial

E=EoCm …..(4.33)

where

F= Nominal resistance in bending (b), or torsion (t), or compression (c), or shear

(s)

F0 =Base resistance of b,t,c, or v

E = Nominal modulus for b,t,c,or v

Eo = Base modulus for b,t,c,or v

Cf = Size effect factor for dimensions of width, depth, span etc.

Cm = Moisture content factor and/or humidity factor with pH variation

Cc = Environmental factor, which varies with the FRP material exposure to

different temperature levels

Ca = Physical aging factor that varies with number of years of service

Cst = Sustained load factor

These knockdown factors or reduction factors are established through different

tests and field evaluations. These factors can be used when no test data are available.
For example, if the tensile strength of a bigger diameter bar is required and the data are
not available then the size effect factor can be used to establish these values. Vijay,
(1998) has given a table to account for various knock down factors by conducting tests
on 3 GFRP bars each, weathered under natural atmospheric exposure for 3, 7 and 10
years and tested in tension for this research.

145
 Corrosion Tutorial

Table 4-5: Knockdown Factors (Vijay,1998)

Notation Knockdown Factor

Factor Parameter
(Reduction Coeff.)
Eqn.1.1 & 1.2

1.00-#4

0.85-#5

Size effect Factor Cf Diameter 0.70-#6

0.65-#7

0.60-#8

Moisture Content Salt (Ph ≈ 7) 0.9-0.75

Cm
Factor
Alkaline (Ph ≈ 13) 0.8-0.65

Sustained Load Salt/Water 0.85-0.70

Factor (20%-40% Cst
on GFRP bar) Alkaline 0.70-0.40

Mean Annual 1(T ≤ 52.5 0 F )

Temperature Temperature (T0F)
(T − 52.5)
Factor to be used Cc (In combination 1− for
with (Cm and Cst) 100
with alkalinity and
stress) (52.5 ≤ T ≤ 92.5 0 F )

Physical Aging
Ca 0.90
Factor

Notes:
size effect factor can be used only for interpolating bigger bar diameter strengths
when smaller diameter bar (in this table #4 is chosen as reference) is tested.

values in this investigation were correlated for a mean annual temperature of

52.50F and hence knock-down factor of 1 is chosen at that temperature.

If mean annual temperature is more than 52.50F then a minimum reduction of

0.1 is applied for every 100F increase in the mean annual temperature. This is an
empirical approach purely based on strength reductions in GFRP bars under
accelerated aging at 69.80F, 93.680F and 1500F in addition to natural weathering

146
 Corrosion Tutorial

results of Litherland et al., 1981. Mean annual temperatures above 900F are not
expected in any part of the globe.

A limit of 0.4 is provided as the reduction factor for combined effects (Vimala,
2002). This factor is given considering that all the environmental factors that cause
aging do not act at the same time and place.

4.3.3.5 Durability Models

Various analytical models used to predict the effect of environmental factors on
the durability of the composite materials is collected and cited in the paragraphs, which
follow.

4.3.3.5.1 Analytical Methods to Predict the Effects of Environment

on Composite Materials

4.3.3.5.1.1 Effect of Moisture

Following parameters are necessary to describe the behavior of composite
material exposed to an environment with temperature ‘Ta’ and moisture content ‘ca’ as a
function of time ‘t’ [Springer, 1981].

The temperature distribution inside the material as a function of position and time
T (x, t)

The moisture concentration inside the material as a function of position and time
c (x,t)

The total amount (mass) of moisture inside the material as function of time m(t)

Changes in “performance (e.g., physical, chemical or mechanical property)” of

the material as a function of time P(t)

147
 Corrosion Tutorial

When changes in temperature and moisture inside the material are to be

determined and not the performance, analytical methods can be employed if the
diffusion process is “Ficikian”

Fickian Diffusion
The diffusion process is said to be “Ficikian” if the following conditions are met
[Springer, 1981].

Heat transfer through the material is by conduction only and can be described by
Fourier’s law

The moisture diffusion can be expressed by a concentration-dependent form of

Fick’s law

Energy (Fourier) and mass transfer (Fick) equations are decoupled

Thermal conductivity and mass diffusivity depend only on temperature and are
independent of moisture concentration or the stress levels in the core.

Analytical predictions based on Fickian diffusion are a function of geometry,

boundary conditions, initial conditions and material properties such as density (ρ),
specific heat C, thermal conductivity K, maximum moisture content Mm and a
relationship between the maximum moisture content and the ambient conditions [Shen
and Springer, 1981].

Fourier’s Equation of Heat Transfer

Fourier’s equation of heat transfer is given by:

∂T ∂ ∂T
ρC = Kx …(4.34)
∂t ∂x ∂x

where ρ = density, C = specific heat, T= temperature, t= time, x = distance, and

K x = thermal conductivity.

148
 Corrosion Tutorial

Fick’s Equation of Mass Transfer

Fick’s equation of mass transfer is given by:

∂c ∂ ∂c
= Dx …(4.35)
∂t ∂x ∂x

where c = moisture concentration, Dx= diffusion coefficient, x = distance, t = time

Diffusion is said to be non-Fickian [Shen and Springer, 1981], if:

Cracks develop in the material or delamination occurs leading to an altered

structural representation

Moisture propagation is dominated by fiber-matrix interface

Many composites under ambient conditions follow Fickian diffusion and this
process is extensively modeled, whereas the non-Fickian diffusion models are sparsely
used because excessively cracked specimens are removed from service well before the
non-Fickian phenomenon sets in, leading to lack of experimental data on specimens
under service.

Moisture Content (M)

In practice, the percent of moisture content M of a composite is defined on weight
gain

Weight of the Moist FRP ( w ) − Weight of the dry FRP ( w d )

M= x100 …(4.36)
Weight of the dry FRP ( w d )

Mm is the maximum moisture content that can be attained under given

environment and is found to be insensitive to the temperature but dependent upon the
moisture content in the environment. For a composite material exposed to humid air,
Mm depends upon the relative humidity (φ) , and is given by:

149
 Corrosion Tutorial

Mm=aφb (for humid air exposure) …(4.37)

where a and b are constants. For a composite material immersed in a liquid, Mm

is a constant with time after the material reaches saturation level.

Mm=constant (for liquid immersion) …(4.38)

Diffusion Coefficient (Dc)

The diffusion coefficient characterizes the speed at which moisture is transported
through the material. The temperature dependence of diffusion coefficient for a
rectangular composite exposed to moisture is characterized by Arrhenius relationship
[Rao et al., 1981].

Dc = D0 exp −Ed / RT …(4.39)

where Do = diffusion coefficient with respect to reference temperature, Ed =

activation energy for diffusion, R = universal gas constant, T = absolute temperature.

Diffusion coefficients (Dc) can be calculated by using [Rao et.al, 1981]

⎡⎛ ⎞
2
⎛ M2 − M1 ⎞ ⎤
2
h
D c = π ⎢⎜⎜ ⎟ ⎜ ⎟ ⎥ …(4.40)
⎢⎝ 4Mm ⎟⎠ ⎜⎝ t 2 − t 1 ⎟⎠ ⎥
⎣ ⎦

where

h = thickness of the composite, Mm= maximum moisture content, t1 and t2 = time

taken to reach the moisture contents M1 and M2.

Diffusion Coefficient for Alkaline or Salt Solution (k)

For FRP circular sections such as bars immersed in an alkaline or salt solution,
the diffusion coefficient is a function of the depth of liquid penetration, concentration of

150
 Corrosion Tutorial

the liquid, exposure duration and the bar diameter [Katsuki, 1995] as given in the
following eqn.

x = s ⋅k ⋅C⋅ t …(4.41)

where

x = depth from surface of rod

C = alkali or salt concentration (mol/l)

t = curing time (hrs)

k = diffusion coefficient of alkali or salt in rod.

Effect of Temperature
Empirical relations for predicting hygrothermal degradation effects have been
studied at Lewis Research Center of NASA and given by [Chamis, 1984].
0.5
PmD ⎡ TGW − T ⎤
= …(4.42)
Pmo ⎢⎣ TGD − T0 ⎥⎦

where

PmD = degraded mechanical property, Pmo = mechanical property at reference

condition, TGW = glass transition temperature of wet resin, TGD = glass transition
temperature of dry resin, To = reference temperature at which PmD is determined

The manufacturer supplies TGD, whereas TGW is given by empirical relation:

TGW = (0.005M2 – 0.1M + 1) TGD (M≤ 10%) …..(4.43)

where M = weight % moisture in the resin

It is clear that the matrix with the higher TGD will yield a composite with better
resistance to hygrothermal degradation.

151
 Corrosion Tutorial

4.3.3.5.1.2 Prediction of Residual Stresses Due to Moisture and

Temperature
Moisture absorption at low temperatures results in matrix swelling and reduction
in strength and stiffness. If uniform strain in longitudinal direction and uniform stress in
transverse direction are assumed, residual stresses in the matrix and fiber along the
longitudinal direction due to matrix swelling and thermal shrinkage is given by [Hahn,
1976]:

where

Vf E f Em
σmL = [(α f − αm )(T − T0 ) + (β f c f − βm − c m )] …(4.44)
VmEm + Vf E f

Vm
σ fL = σmL …(4.45)
Vf

where

E= elastic modulus, V= Volume ratio, α = coefficient of thermal expansion, β =

coefficient of moisture swelling, c = specific moisture content, T = temperature σ L =

longitudinal stress, To = stress-free temperature (usually cure temperature), Subscript m

and f correspond to matrix and fiber respectively.

4.3.3.5.1.3 Prediction of Rate of Degradation in Composite Strength

under Harsh Environment
Ajjarapu (1994) suggested the rate of degradation of the composite materials
under harsh environmental conditions using the following relationship:

σ t = σ 0 e − λt …(4.46)

where t < 450 days, λ = 0.0015, σ o = initial tensile strength, σ t = tensile

strength at time t,

σ t > 450 days =σ o /2 …..(4.47)

152
 Corrosion Tutorial

From the experiments, it was concluded that the maximum reduction was 50% in
450 days. However, beyond 450 days, the strength did not change considerably.
However, for the design purposes, the strength of the material due to long-term aging
should to be taken a minimum of 50% of the initial ultimate strength.

4.3.3.5.1.4 Fatigue Damage Models

This section deals with damage models and fracture energy absorption in
composites.

Fatigue Damage Model

The fatigue damage can be measured by the variable D, which is a function of
the number of cycles applied on a composite. Cyclic loading causes the damage to
increase from Di to Df after N cycles at which point catastrophic failure of the composite
laminate occurs. (Di is zero for undamaged material.) Assuming that the damage
accumulation rate depends on the cyclic rate amplitude, Δσ, the load ratio, R, and on
the current level of D, then:

dD
= f (Δσ,R, D) …(4.48)
dN

Above eqn. is valid when temperature, frequency, etc., are constant or have
negligible effects (Beaumont). The lifetime, Nf, (the number of cycles to increase D from
Di to Df) is therefore:
Df
dD
Nf = ∫ f (Δσ , R, D )
Di
…(4.49)

Relation between the axial Young’s modulus, E, of the composite laminate and
the accumulated damage, D is given by:

E = E0 g(D ) …(4.50)

where Eo is the initial or undamaged modulus. Therefore:

153
 Corrosion Tutorial

1 dE
= g' (D ) …(4.51)
E0 dN

where g’ stands for the derivative of g with respect to D. Differentiating and

substituting into Eq (4.49), we get:

1 dE ⎡ ⎛ E ⎞⎤ ⎡ ⎛ E ⎞⎤
= g' ⎢g−1 ⎜⎜ ⎟⎟⎥ f ⎢ Δσ,R, g−1 ⎜⎜ ⎟⎟⎥ …(4.52)
E0 dN ⎣ ⎝ E0 ⎠ ⎦ ⎣ ⎝ E0 ⎠ ⎦

where g-1 is the inverse of g:

⎛E⎞
D = g' ⎜⎜ ⎟⎟ …(4.53)
⎝ E0 ⎠

The function g(D) has to be established either experimentally or theoretically

before determining function f. Function g(D) depends on the properties and the lay-up of
the composite laminate, and not on how the damage, D, was introduced. Data of (E/Eo)
is obtained as a function of N and, knowing g(D), the function of f (Δσ, R, D) is
determined experimentally using :

1 1 ⎛ dE ⎞
f (Δσ,R, D) = ⎜ ⎟ …(4.54)
⎡ −1 E ⎤ E0 ⎝ dN ⎠
g' ⎢g ⎥
⎣ E0 ⎦

The right hand side of the equation is evaluated for different values of Δσ at a
constant (E/Eo) and R, for different values of R at constant Δσ and R. The function f is
determined from the plot of these results.

The mechanical and hygrothermal properties of a composite material have been

elaborated upon in the earlier subheadings. The aging of composites with relation to
various environmental factors and analytical models used to predict the effects of
environment on composite materials have also been discussed.

Following this subdivision we will discuss the applications of composite materials

in various fields. The reader can thus appreciate the variability of the use of composites
in various fields and application of composites especially in the field of defense.

154
 Corrosion Tutorial

4.4 Summary and Concluding Remarks

Technical issues concerning the long-term and short-term response of composite
materials are dealt with in this chapter. Issues include mechanical properties, fluid
sorption and damage, thermal coefficient, creep, fatigue, and aging due to
environmental effects. The mechanical and hygrothermal properties of the composite
are established first in terms of short-term response. The aging of the composite
material due to physical and chemical factors are elaborated upon. This chapter brings
to light to the reader that composite material also age under corrosive environments.
But the rate of aging is slower than in the case of metals.

An important point worth mentioning is the effect of size on performance. Most of

these results obtained from the tests conducted, are from coupon level specimens. The
size of FRP structural elements for an actual application is much larger. A proper
correlation between these two parameters in size should be done to implement these
results in the field. At the present systematic studies on the size effect is not available,
and there is no clear conclusion on whether or not a size effect exists.

155
 Corrosion Tutorial

5 APPLICATIONS OF COMPOSITES

This chapter deals with the applications of metal and composites. Special
emphasis is given to the application of these materials in the manufacture of defense
equipment. Composites are vastly used in defense applications and also in other
industries such as construction, automotive, recreational, etc. The cost factor of
composite material makes it suitable for manufacture of weapons in the field of defense.
Thus the applications of composites can be broadly classified as those used in defense
industry and in various other civilian purposes.

5.1 Applications of Composites for Defense Purposes

The use of composites in the field of defense is multipurpose. The application of
composites for defense equipment is elaborated in the following paragraphs.

5.1.1 Aircraft Systems

Composites are widely used in the manufacture of aircrafts. The need for
improved materials to withstand varied environments is leading to the demand of
composites in various fields of defense. The F-22 Raptor aircraft (Figure 5-1) is the
next-generation air superiority fighter for the Air Force to counter emerging worldwide
threats. It is designed to penetrate enemy airspace and achieve a first-look, first-kill
capability against multiple targets. The F-22 is characterized by a low-observable, highly
maneuverable airframe; advanced integrated avionics; and aerodynamic performance
allowing supersonic cruise without afterburner.

The Raptor was built with a requirement for a fighter to replace the earlier
fighters, with emphasis on agility, stealth and range. The F/A-22 raptor construction is
39% titanium, 24% composite, 16% aluminum and 1% thermoplastic by weight.
Titanium is used for its high strength-to-weight ratio in critical stress areas, including
some of the bulkheads, and also for its heat-resistant qualities in the hot sections of an

156
 Corrosion Tutorial

aircraft. Carbon fiber composites have been used for the fuselage frame, the doors,
intermediate spars on the wings, and for the honeycomb sandwich construction skin
panels.

Figure 5-1: F-22 Raptor Aircraft -Tactical Fighter Aircraft

Reference: http://www.airforce-technology.com/projects/f22/
The RAH-66 Comanche is a helicopter designed for armed reconnaissance,
attack and air combat missions.

Figure 5-2: RAH-66 Comanche

Reference: http://www.gdatp.com/Products/2002/arm_systems/rh66_comanche/RAH66.html

Externally mountable aircraft guns are also manufactured using composite

materials. The GAU-19A (Figure 5-3a) is an externally mounting 12mm gatling gun and
the F18C/D is a 20mm gatling gun system. The F18C/D system (Figure 5-3b) is
lightweight and the compact design is mounted on a common pallet structure.
Lightweight components include a fiber reinforced plastic inner drum and rotating scoop
disc assemblies. The GAU-19/A gun is especially effective in high clutter environments
and for engagements that are inside missile envelopes.

157
 Corrosion Tutorial

Figure 5-3: a.GAU –19A b. F18C/D

Reference: http://www.gdatp.com/Products/2002/aircraft.htm

5.1.2 Ground Systems

The use of composites in armor systems enables the manufactures to decrease
the weight of the armor thus enabling capability of further increasing the protection
without increasing self-weight. Composites are resistant to the harsh environments and
the impact loads. The ammunition the armor utilizes is a very insensitive high energy
explosive with reduced weight. This promotes for carrying a larger quantity of
ammunition for attack purposes.

Figure 5-4: Reactive Armor and XM-301 Gun

Reference: http://www.gdatp.com/Products/2002/ground.htm

5.1.3 Individual and Crew Served Systems

The Objective Crew Served Weapon (OCSW) is the next generation replacement
for current heavy and grenade machine guns. It is truly a lightweight, two-man portable

158
 Corrosion Tutorial

system that incorporates the most modern technology advancements in fire control,
materials and munitions. The use of lightweight composite material made it feasible for
the manufacturer to develop a crew system to be handled by two men.

Figure 5-5: Objective Crew Served Weapon

Reference: http://www.generaldynamics.com/

5.1.4 Rocket and Missile Systems

One of the rockets made of composite component parts is the DELTA II rocket
(Figure 6-4). It makes use of the lightness and durability of composites to bring about
the added features required for the increased serviceability and service life of the
rocket. Delta II can launch single, dual, or multiple payloads on the same mission. To
accommodate these varying requirements, one of the companies designed a variety of
payload attach fittings. The company also builds several fairing types to enclose and
protect payloads on the launch pad and during ascent. Fairing is the front end of the
rocket that serves to protect the satellite being launched from the external
environmental factors.

Some factors affecting the fairing are aerodynamic loads, vibration, noise,
temperature extremes, dirt, dust, rain, snow, and micrometeorites that may be
encountered as the satellite is launched and accelerates through the atmosphere into
space. A composite fairing is offered in a 3-m diameter (10-ft) size. An aluminum 2.9-m
(9.5-ft) diameter fairing is available, as is a 3-m diameter stretch composite fairing for
certain payloads. The fairing being made of composite reduces the weight of the entire
system.

159
 Corrosion Tutorial

Figure 5-6: Delta II

Reference: http://www.boeing.com/defense-space/space/delta/delta2/delta2.htm

Figure 5-7: Missiles from the Hydra 70 Family

Reference: http://www.fas.org/man/dod-101/sys/missile/hydra-70.htm

5.1.5 Shipboard Systems

Ships such as the carriers, battleships that are used in warfare need to carry
heavy loads and need to resist high wear and tear. Ships are also prone to high rate of
corrosion due to the environment, in which they operate, which is highly corrosive. The
need to design and manufacture better battleships and cruisers for combat is the high
priority in the defense. This brings about the use of composites that have better

160
 Corrosion Tutorial

corrosion resistance and higher fatigue lives. The weapon systems mounted on ships
for battle are also built using composites making the weapons lighter and increasing
their service life.

Figure 5-8: Destroyers

Reference: http://www.chinfo.navy.mil/navpalib/factfile/ships/ship-dd.html

Figure 5-9 Goalkeeper: In-Ship Defense System

Reference: http://www.gdatp.com/Products/2002/arm_systems/goalkeeper/goalkeeper.html

5.2 Applications of Composites for Civilian Purposes

5.2.1 Automotive
Automotive body parts, body panels, structural components, and under hood
parts, especially made of steel, are subjected to severe corrosion under high

161
 Corrosion Tutorial

temperature. Steel is prone to high corrosion under harsh environments. The design
and manufacturing versatility of composites along with high endurance to corrosion
allows replacement of steel with composites in automotive parts.

Figure 5-10: Composite Fire Truck Panels

Reference: http://www.pultrude.com/automotive.html

5.2.2 Infrastructure
Aging bridges, highways, buildings, weapons, machinery etc. in infrastructure are
subjected to corrosion and high internal stresses. Repair, rehabilitation and retrofit of
these infrastructures have set a stage for composites. In order to bring about this
rehabilitation, FRP laminates, wraps and jacketing systems are used. The retrofitting of
columns using FRP wraps is a fast developing technique to increase the service life of a
bridge.

Figure 5-11: All Composite Bridge, Laurel Lick, CFC-WVU

5.2.3 Construction
Pultruded profiles play a dominant role in composite construction applications.
They are used in a number of construction purposes such as bridge decks, support
systems for bridge decks, corrosion resistant walkways, and railings. They are also

162
 Corrosion Tutorial

used as reinforcing material in concrete as steel bars corrode at a rapid rate and FRP
bars have higher corrosion resistance. A number of panels made of FRP material are
used together in infrastructure development i.e., energy plant towers, cooling towers,
pedestrian bridges and many other structures.

Figure 5-12: Energy Plant Towers

Reference: http://www.pultrude.com/construct.html

5.2.4 Transportation
Composites are used in various transportation vehicles such as aircrafts, rockets
and heavy-duty vehicles. They have replaced aluminum, steel and other traditional
materials due to their high resistance to corrosion and their ability to withstand high
temperatures. In transportation systems such as pedestrian walkways they are used as
handrails etc. They are used, also in railways in order to wrap the existing wooden
crossties.

Figure 5-13: Third Rail Protection in Monorail System

Reference: http://www.pultrude.com/construct.html

163
 Corrosion Tutorial

5.2.5 Biomedical
Composites are being applied today to medical devices ranging from artificial
limbs to light weight tubing used in invasive surgery. Magnetic resonance imaging units
and electromagnetic shielding application units are built using composites.

Figure 5-14: MRI Units

Reference: http://www.gemedicalsystemseurope.com/euen/rad/mri/products/vhi/vhi.html

5.2.6 Computer products

Composites are used to manufacture computer-housing products, computer
boards, outer frame and even the microprocessors and chips. The high factor of
corrosion inhibition of composites enhances its use in the building of component parts of
the computer

Figure 5-15: Composite Computer Chip

Reference: http://news.bbc.co.uk/1/hi/sci/tech/2053539.stm

164
 Corrosion Tutorial

5.2.7 Corrosion Resistant products

Composites are used to manufacture various corrosion resistant products. They
are used to manufacture pipes in sewer systems, which lasts longer then the traditional
pipes. Corrosion resistant composite tanks, scrubbers and pressure vessels have
expanded further into the industrial sector. Equipment used in wastewater treatment
plants must withstand sustained exposure to highly corrosive chemicals and composites
are proving the best materials to be used in such environments.

Figure 5-16: Waste Water Plant

Reference: http://www.pultrude.com/ww.html

5.2.8 Electrical
Electrical cables, optic fibers, cable supports, telecommunication towers, power
transformers, power transmission lines etc. are manufactured using composites. They
have various advantages over conventional material. They are corrosion resistant, fire,
smoke and toxic safe and have high ranges of electrical and thermal insulation. They
also boast of minimum maintenance, minimum initial cost and ease of installation.

165
 Corrosion Tutorial

Figure 5-17: Telecommunication Towers

Reference: http://www.pultrude.com/elec.html

5.2.9 Recreational
Composites have successfully replaced wood and conventional materials such
as steel in various consumer recreational products such as fishing rods, tennis
racquets, golf club, Paddles, windsurfing masts, kites, bicycle handlebars and various
other fastenings. Composites are found in most of the outdoor sports and recreational
activity equipments.

Figure 5-18: Recreational Products

Reference: http://www.pultrude.com/consumer.html

5.2.10 Marine
Corrosion in marine environments has led to opportunities for composites in
waterfront applications such as marine fenders and pilings. Some of the composite

166
 Corrosion Tutorial

pilings used are pilings made with vacuum-assisted technology, filament wound
composite piling jackets filled with cement, and extruded thermoplastic pilings reinforced
with extruded thermoset composite rebar.

Figure 5-19: Sheet Piling and Fender Applications

Reference: http://www.pultrude.com/mar.html

167
 Corrosion Tutorial

6 RETARDATION METHODS FOR CORROSION

There are four main methods used for retardation of corrosion process. They
are:

ƒ Cathodic Protection

ƒ Coatings

ƒ Inhibitors

ƒ Anodic Protection

These methods can be employed individually or in combination with each other.

6.1 Cathodic Protection

A metal in contact with corrosive environment starts to corrode due to
electrochemical reactions. This effect results in metal dissolution and oxygen reduction
reactions when the oxidizing reagent is oxygen. Cathodic Protection reduces the
corrosion rate by supplying electrons to the metal structure. There are two main
techniques employed in cathodic protection. They are:

• Sacrificial Anode System

• Impressed Current Cathodic Protection

6.1.1 Sacrificial Anode System

The sacrificial anode is a more active metal than the metal structure to be
protected (Figure 6-1). The metal to be protected and the sacrificial anode is a coupling
for galvanic corrosion. The dissolution of sacrificial anode “takes over” for the
dissolution reaction of the metal to be protected. This mechanism is shown in Figure 6-
2. The sacrificial anode makes the metal to be protected as cathode. This sacrificial
anode method cannot be used on acid because the consumption of sacrificial anode is

168
 Corrosion Tutorial

very high. Thus, this method is rather suitable to protect the metal structure exposed to
oxygen environment in neutral solution. Sacrificial anodes are installed at every 10 feet
to protect the structure (e.g., pipeline). So, this system cannot be implemented for very
long structures (pipelines). This system is economical and suitable to a pipeline that
runs through short distance, such as 0.5 miles.

Figure 6-1: Steel Tank Protected by Sacrificial Anode System

169
 Corrosion Tutorial

H2O O2 OH-

e- e-
Zn Zn2+
Fe

Figure 6-2: Mechanism of Anodic Protection System

6.1.1.1 Advantages of Sacrificial Anode Systems

• Simple and easy to design.
• Low maintenance requirements.

6.1.1.2 Disadvantages of Sacrificial Anode Systems

• Used only where small current requirements are needed.
• Soil resistance should be low.

6.1.2 Impressed Current Cathodic Protection

In this method current is provided to the structure by some means such as AC
supply, which is converted to DC by means of a rectifier and supplied, to the ground
beds of usually graphite, silicon cast iron or precious material surrounded with
carbonaceous backfill. The system is shown in Figure 6-3. The current drains from
there and reaches the structure to be protected. To complete the circuit the negative
terminal of the DC power supply is connected to the structure to be protected and the
positive terminal is connected to the ground bed system.

The mechanism is seen in Figure 6-4. In this method, electrons are supplied to
the metal structure, reducing the corrosion rate. The applied voltage is Eapp as shown in
Figure 6-4. Thus, the corrosion rate is reduced from icorr to i’corr. This method is not
suitable to acid environment because current requirement will be too high. This method
is only suitable to oxygen corrosion in neutral environments like the sacrificial anode
method. Unlike the sacrificial anode method, this method can be applied to pipelines,
which run long distances.

170
 Corrosion Tutorial

Figure 6-3: Steel Tank Protected by Impressed Current System

MÆ M++e-

Eap

O2+2H2O+2e-

i’corr icorr
Log i

Figure 6-4: Mechanism of Impressed Current Systems Explained Using Anodic Polarization Curves

171
 Corrosion Tutorial

6.1.2.1 Advantages of Impressed Current Cathodic Protection

• High output capacity.
• Single installation can protect a large structure.

6.1.2.2 Disadvantages of Impressed Current Cathodic Protection

• Greater maintenance requirements.
• Depends on availability of power supply.

6.2 Coatings
Coatings are used to cover or spread the material to be protected against
corrosion with a finishing, protecting or enclosing surface. There are mainly three types
of coatings. They are

• Metallic
• Organic
• Inorganic

6.2.1 Metallic
Metallic coatings are with more active metals than the substrate metal. Metallic
coatings are further classified as follows:

6.2.1.1 Hot Dipping

The process of hot dipping is carried out by immersing a pre-treated substrate in
a bath of molten metal or alloy. Hot dipping is used to increase corrosion and wear
resistance. Coatings of all low melting-point metals and alloys such as zinc and
aluminum are deposited. The steels coated with such metals are called galvanized
steels. The coating of 55% zinc and 45% aluminum is used because the addition of

172
 Corrosion Tutorial

aluminum suppresses the transport of iron into the coating; thus reinforcing the physical
property of the coating.

6.2.1.2 Chemical Vapor Deposition (CVD)

Chemical vapor deposition is a process in which gaseous molecules of a metal,
alloy or polymer is deposited on the surface of the substrate in the form of thin film or
powder. Gaseous compounds of materials to be deposited are transported to a
substrate surface where a thermal reaction/deposition occurs at temperatures around
1000 °C. CVD offers many advantages over other processes. It can deposit any
element or compound and it can also produce high purity and high density coatings
economically. The disadvantages are high process temperature, loss of hardness and
significant dimensional changes and geometric distortions. The disadvantage of high
temperature CVD process can be overcome by using plasma enhanced CVD process,
which usually requires a temperature range of 200-300 °C.

6.2.1.3 Ion Vapor Deposition (IVD)

Ion Vapor Deposition is a process by which aluminum is vaporized at high
temperatures and adheres to metal substrate. The process requires a vacuum chamber
and a vaporizing source. IVD coatings can be applied to a wide variety of metallic
substrates, aluminum alloys, carbon steels and stainless steels. The advantages of IVD
coatings are uniformity of thickness, applicability to complex shapes and prevention of
hydrogen embrittlement. The disadvantages are unable to coat deep holes and simpler
methods are not available to repair the coatings.

6.2.1.4 Spraying
Spraying is the deposition of the metallic coating by dispersing it on the metallic
substrate to be protected. All spraying processes feed the material into the heating
device where it is heated, melted and sprayed on the surface. The molten particles
strike the surface and form a thin coating on the substrate. As they cool, they form a
lamellar structure to form the desired coating. Some common spraying process include
flame spraying, plasma arc spraying, electric arc spraying, high velocity oxy-fuel etc.

173
 Corrosion Tutorial

The thermal sprayings are capable of competing with paintings and plating for
atmospheric corrosion.

6.2.1.5 Electroplating
Electroplating is a deposition of metal ions onto the metallic substrate by passing
current. A schematic is shown in Figure 6-5 for electroplating zinc ions on steel. Zinc
chloride is added to the cathode compartment. Zinc ions are attracted to the cathode
where they are reduced to elemental zinc and are deposited on the cathode surface.
The cathodic reaction is:

Zn2+ + 2e- = Zn …(6.1)

e-
e-

H+ cl-
O2
Zn2+
cl-
Anode Cathode
(Inert (Steel)
alloy)

Anionic
membrane

Figure 6-5: Mechanism of Electroplating

Chloride ions are transported through the anionic membrane to the anode
compartment in order to maintain the electrolytic neutrality. At the anode, water is
dissociated by the reaction:

2H2O = 4H+ + O2 + 4e- …(6.2)

At the anode, the electrolytic neutrality is maintained by producing hydrogen ions

against the influx of chloride ions from the cathode compartment. Some of the

174
 Corrosion Tutorial

advantages are plating samples having complex shapes, cheap, rapid technique and no
sophisticated instrument is needed for the process. Another advantage is that the
coating properties of strength, uniformity and grain size can be improved by adding
various additives. However the disadvantage is that the electrode position requires
higher energy.

6.2.2 Inorganic
Inorganic coatings perform conversion coatings, Portland cement, ceramics, and
glass on surface of the materials. They are further described below.

6.2.2.1 Portland Cement Coatings

Portland cement coatings are used to protect the pipes made of cast iron or steel
on both water and soil environments. The coatings can be applied by centrifugal
casting for interior surfaces of pipes and spraying for exterior surfaces. The advantages
are low cost and easy to repair. The disadvantage is that coatings can be easily
damaged by mechanical or thermal shock and also easily attacked by sulfate-rich water.

6.2.2.2 Ceramics
Ceramic coatings are used to improve the wear and corrosion resistance to
withstand high temperature applications such as internal combustion engines, rocket
nozzles and exhaust passages of hot gases. These coatings can also be applied to
steel to provide acid and heat resistance.

6.2.2.3 Chromate Filming

Chromate conversion coatings or chromate filming is a process by which the
material is protected by applying chromate using immersion. The most suitable method
for the formation of film will be the treatment with chromic acid. These films are about
5mm thick and form a color depending on the base alloy.

175
 Corrosion Tutorial

6.2.2.4 Phosphate Coatings

Phosphate coating is a type of chemical conversion process that transforms the
surface of a base metal with a non-metallic crystalline coating. These coatings are
produced by holding the metal in a hot bath of phosphoric acid and zinc. Manganese
and zinc phosphate coatings are most commonly selected for their wear-resistant
properties. It also can retain oil such as petroleum products, which can avoid rusting.

6.2.2.5 Nitriding
Nitriding procedures are thermo-chemical processes, where the surface of the
material is enriched with nitrogen. In this process, nitrogen is diffused into the bulk
material from outside. Nitriding can be done using solid, liquid or gaseous nitrogen
media. It is typically carried out in the temperature ranges of 500-575ºC. The
advantages of Nitriding are increased fatigue strength, excellent dimensional stability
without distortion, completely non-toxic, environmentally clean, and low energy
consumption.

6.2.3 Organic
Coatings consisting of organic materials like esters, etc. are called organic
coatings. They are composed of hydrocarbon and are further classified into:

6.2.3.1 Binders
Binders are usually resins or oils, but can be inorganic compounds such as
soluble silicates. The binder is the film-forming component in the paint. The nature and
amount of binder determines the performance properties such as toughness, adhesion,
and color retention.

6.2.3.2 Pigments
Pigments are finely ground organic or inorganic powders that provide color,
opacity, film cohesion, and corrosion inhibition. The distinction between powders that

176
 Corrosion Tutorial

are pigments or dyes is based on their solubility. Pigments are usually insoluble and
dispersed in the material whereas dyes are readily soluble in a solution.

6.2.3.3 Solvents
Solvents are used to dissolve the binder and to facilitate application of the paint.
Solvents are usually organic liquids or water. A true solvent is a single liquid that can
dissolve the coating. Solvent is often used to describe terpenes, hydrocarbons, and
chlorinated solvents.

6.2.4 Nonstick Coatings

These coatings provide a polished and smooth surface. The non-stick quality of
the surface is due to the silicone, which is the non-stick, hydrophobic and lubricious
component. It offers superior surface protection in both fresh and salt-water
environments, and extends the life of steel, iron, aluminum, concrete, and a wide range
of other substrates.

6.3 Inhibitors
Corrosion inhibitors are used to reduce the corrosion rate of metallic surfaces in
a corrosive environment by adding chemical compounds. These inhibitors will reduce
the rate of anodic, cathodic or both reactions. Inhibitors are adsorbed on the metal
surface by physisorption or chemisorption. Physisorption occurs due to inter-molecular
forces between the metallic surface and inhibitor molecules. Chemisorption occurs due
to the formation of equivalent chemical bonds between the metal surface and inhibitor
molecules. After the inhibitor molecules are adsorbed, they form a protective film on the
metal surface. Inhibitors can be transported to the metal surface by various methods.
Some of them are:

1. Dispersing the inhibitor in the corrosive liquid

2. Adding the inhibitor to paints
3. Emitting vapors of volatile inhibitors onto the metal surface

177
 Corrosion Tutorial

Inhibitors are classified into three types. They are:

1. Anodic inhibitors
2. Cathodic inhibitors
3. Mixed type inhibitors

6.3.1 Anodic Inhibitors

These inhibitors protect the metal by forming a passive film on the metal surface.
This film retards the rate the anodic reaction. However, if the concentration of the
oxidizer is too low, the inhibitors are not effective. This is because cathodic polarization
curve will intersect the active region of the anodic polarization curve, giving high
corrosion rate. In this case, the anodic inhibitors are not suitable for usage. Some
examples of anodic inhibitors are sodium chromate, phosphate and molybdate.

Sodium chromate (Na2CrO4) is used for inhibiting metal corrosion, pigment

formulation, and oil well drilling. Sodium chromate is used in certain types of corrosion
control applications as well as in the formulation of pigments, where alkalinity is
required. Since sodium chromate is hygroscopic (having the characteristic of drawing
moisture from the atmosphere), the anhydrous form is better suited for areas where
high humidity could cause caking and handling problems.

Inorganic phosphates are compounds of phosphorus and oxygen that exists in

many forms and is usually combined with other elements (metals such as sodium,
potassium, calcium, and aluminum). Salt or ester of a phosphoric acid is used as non-
toxic inhibitors.

Molybdate is a salt of molybdenum containing the group of MoO4 or Mo2O7. It is

an environmentally benign inhibitor. Molybdate inhibitors have been proven effective as
demonstrated in numerous outdoor exposure studies and used for commercial
applications for more than 30 years. Molybdate inhibitors are effective in both
conventional salt-spray tests and the newer cyclic salt-spray/UV exposure tests (e.g.,
ASTM D 5894).

178
 Corrosion Tutorial

6.3.2 Cathodic Inhibitors

These inhibitors form a protective coating on the metal surface like anodic
inhibitors but retard the rate of cathodic reactions on the metal surface. Some common
examples of cathodic inhibitors are zinc salts (e.g., ZnSO4), sodium sulfonates
(NaRSO3) and phosphonates (H2PO3).

Sodium sulfonates are used as additives to oils and lubricants used in functional
objects to extend the maintenance period of the object in oily, waxy or greasy coatings.
Phosphonates are extensively used in scale/corrosion inhibition, metal finishing, ore
recovery, oil drilling, industrial cleansing, pulp, paper, textile dyeing, and crop
production. Phosphonates are derivatives of phosphates.

6.3.3 Mixed Inhibitors

These inhibitors influence both the anodic and cathodic reactions. Many organic
compounds are of this type. Some examples are aliphatic, cycloaliphatic, aromatic and
heterocyclic amines, organic esters, etc.

6.3.4 Applications
They are used in open water-cooling systems, closed cooling systems of motor
vehicles, in primer of the anti-rust paint, and in closed containers.

6.4 Anodic Protection

This technique is used for tanks in which strong acids are stored. The tank metal
should exhibit active-passive behavior in order to be applied by this technique. The
idea is to increase the potential, which is in the middle of the passive zone. In this
situation corrosion rate will be much reduced.

Consider Figure 6-6 in which the anodic polarization curve intersects with the
cathodic polarization curve at the active region having the corrosion rate icorr under
normal conditions. A device called potentiostat is needed to increase the potential. As
the potential increases from Ecorr to E’corr the applied current density decreases from icorr

179
 Corrosion Tutorial

to i’corr. The optimum range for this applied current density would be in the middle of the
passive region for the system to be more effective.

Anodic protection can be implemented using a potentiostat. It has three

terminals. One is connected to the structure to be protected which is anode; another to
the auxiliary electrode which is a cathode and third to the reference electrode. The
potentiostat maintains constant potential between the structure and the reference
electrode. The optimum potential can be determined by the anodic polarization curve.
Many reference electrodes are used in the anodic protection systems along with the
conventional reference electrodes such as glass and calomel electrodes.

The primary advantage of anodic protection is its applicability in extremely

corrosive environment whereas cathodic protection can be utilized only in weak to
moderate corrosive environments. The current requirements are very low in anodic
protection whereas they are very high in cathodic protection and increases as the
corrosivity of the environment increases. Thus, the operating costs in anodic protection
systems are lower than those of cathodic protection systems.

The limitation of anodic protection systems is that it is only applicable to active-

passive alloys. The installation costs are high due to complex instruments including
potentiostats and electrodes.

180
 Corrosion Tutorial

Transpassive

iapp

E’corr Passive

Active

Ecorr

i’corr icorr
Log i

Figure 6-6: Effects of Applied Anodic Current on the Behavior of Active-Passive Alloy

181
 Corrosion Tutorial

7 METALS AND COMPOSITES DICTIONARY

7.1 Metal Alloys

7.1.1 Cast Iron

Cast iron is a common term that applies to high carbon iron alloys containing
silicon. The common alloys include gray cast iron, white cast iron, malleable cast iron
and ductile/nodular cast iron. Most cast irons contain carbon content between 3.0 to 4.5
wt%. The melting points of cast iron ranges from 1150 to 1300 °C, which is
considerably lower than that of steels. Thus, they are easily melted and amenable to
casting. Furthermore most cast irons are very brittle because of the high carbon
content.

The cementite (Fe3C) is a metastable phase and is dissociated into ferrite

(almost pure iron) and graphite under some conditions. For most cast irons, the carbon
exists as graphite and both microstructure and mechanical properties depend on
composition and heat treatment. The important structural constituents of cast iron are
graphite, ferrite, and cementite. These are the least expensive of the engineering
metals. They can be alloyed for improvement of corrosion resistance and strength.
These materials are brittle and exhibit practically no ductility.

7.1.1.1 White Cast Iron

When silicon content is less than 1% and the cooling rate is rapid, most carbon
exists as cementite instead of graphite. This is called white cast iron. These irons are
extremely hard and brittle because of the cementite inclusion. Thus it is used for
applications that necessitate a very hard and wear resistant surface such as rollers,
crushers, and grinding mills.

182
 Corrosion Tutorial

7.1.1.2 Malleable Iron

Heating white cast iron between 800 to 900 °C decomposes the cementite
forming graphite into clusters. It has high strength and appreciable ductility or
malleability. It is used in numerous applications in automobiles (such as connecting
rods and transmission gears), locomotives, road machinery, pipefittings, valves, etc.

7.1.1.3 Ductile Iron

Ductile iron is also called nodular cast iron. Adding magnesium to the gray cast
iron before casting produces a distinctly different microstructure and mechanical
properties. The mechanical properties of ductile irons can be improved by heat
treatments. It is used in applications such as automobile crankshafts, main shafts and
rotors for machinery drive etc.

7.1.1.4 Gray Cast Iron

The carbon and silicon contents of gray cast irons lie between 2.5 to 4 wt% and
1.0 to 3.0 wt%, respectively. Because of the high silicon content, cementite
decomposes into ferrite and graphite. The graphite exists in the form of flakes.

Gray cast iron is weak and brittle in tension. However its strength and ductility
are much higher under compressive loads. They are very effective in damping
vibrational energy. It is used as base structures for machines and heavy equipment that
are exposed to vibrations.

7.1.1.5 High Silicon Cast Iron

High silicon cast iron is produced by increasing the silicon content in gray cast
iron to about 14%. It is usually corrosion resistant in many environments. The notable
exception is hydrofluoric acid. Their inherent hardness makes them corrosion resistant
to erosion corrosion. A straight high silicon iron such as Duriron contains about 14.5%
silicon and 0.95% carbon. This composition is suited to provide the best combination of

183
 Corrosion Tutorial

corrosion resistance and mechanical strength. The excellent corrosion resistance of

high silicon irons is due to the formation of passive SiO2 surface layer, which forms
during exposure to the environment. The high silicon cast iron has a major application
in pipelines and fittings.

7.1.2 Steels
Steels are basically iron-carbon alloys in which the carbon content is usually less
than 1.0 wt%, along with the addition of other alloying elements. The mechanical
properties of steels depend on its carbon content. Steels are classified into different
types depending on their carbon content. They are plain carbon steels, low alloy steels
and high alloy steels.

7.1.2.1 Plain Carbon Steels

Plain carbon steel contains carbon as the only alloying element. As the carbon
content increases, brittleness increases. The mechanical properties of this steel are
controlled by the carbon content. The plain carbon steels are further classified as low-
carbon (0.3%), medium-carbon (0.3 to 0.6%) and high-carbon (0.6 to 1.0%). Low
carbon steels are used in automobile body panels, tin plate, and wire products. Medium
carbon steels are used in shafts, axles, gears, crankshafts, couplings, and forgings.
High carbon steels are used in spring materials and high strength wires.

7.1.2.2 Low Alloy Steels

Low alloy steels contain alloy content less than 8%. Carbon steel is usually
alloyed individually or in combination with small quantities of chromium, nickel, copper,
molybdenum, phosphorus, and vanadium to produce low alloy steels. Better
mechanical properties can be obtained by increasing the alloy content, but the most
important advantage is better corrosion resistance to atmospheric corrosion. Strengths
are higher than ordinary carbon steel. These materials can be used for stampings,
forgings and boiler plates.

184
 Corrosion Tutorial

7.1.2.3 Stainless Steels

The most important advantage of stainless steels is their resistance to corrosion
and good mechanical properties at atmospheric and elevated temperatures. Chromium
is the main alloying element and the steel should contain at least 11%. Chromium
tends to form passive film and exhibit excellent resistance to many environments.
Stainless steels form pits when exposed to chloride environments. The stainless steels
are classified into three groups based on their structure, composition, and
characteristics. They are austenitic stainless steels, ferritic stainless steels, and
martensitic stainless steels. Austenitic stainless steels are also called as work
hardening steels. The strength and hardness of this steel can be improved by cold
working. The most predominant alloying elements are chromium and nickel, which is
usually in the range of 16 to 26% and 6 to 22%, respectively. Austenitic stainless steels
are the most corrosion resistant because of the high chromium contents and the nickel
addition. They are produced in the largest quantities. The applications include chemical
processing equipment. Ferritic stainless steels contain 11.5 to 27% chromium and the
carbon content is usually low. These stainless steels are also called non-hardening
steels because they cannot be hardened by heat treatment. These steels find
applications in automotive industry. Martensitic stainless steels are also known as
hardened alloy steels. Chromium content will be usually in the range of 11.5 to 18%.
The mechanical properties can be improved by quenching. These steels find major
applications in oil and gas industry.

7.1.3 Aluminum and its Alloys

Aluminum alloys are a mixture of base metal aluminum with one or more alloying
elements, which can be metallic or non-metallic (such as silicon). The aim of alloying is
to enhance the properties of the base metal, (e.g. its strength and corrosion resistance,
etc). Aluminum has a specific gravity of 2.7. Aluminum alloys have a strong resistance
to corrosion because of an oxide skin that forms as a result of reactions with the
atmosphere. This corrosive skin protects aluminum from most chemicals, weathering
conditions, and even many acids. However alkaline substances are known to penetrate

185
 Corrosion Tutorial

the protective skin and corrode the metal. Aluminum has high conductivity for heat and
electricity. It finds applications in aerospace and automotive industries.

7.1.4 Magnesium and its Alloys

Magnesium is the lightest metal having specific gravity of 1.74. Magnesium is a
silvery-white metal that is used as an alloy element for aluminum, lead, zinc, and other
nonferrous alloys. Magnesium is ductile and suitable for all metal working processes.
Magnesium forms a film to protect against corrosion. However, it is easily corroded by
chlorides, sulfates, and other chemicals. Magnesium is easily susceptible to corrosion
in marine environments. Hence magnesium is usually anodized to improve its corrosion
resistance. Magnesium is non-toxic and non-magnetic. Magnesium finds various
applications in the aerospace parts such as fuselage, engine parts and other
accessories. Magnesium is extensively used in printing and textile industries.

7.1.4.1 Lead and its Alloys

Lead is one of the oldest metals used. It is used for water piping. Lead has
excellent atmospheric and sea-water corrosion resistance. Lead also possesses
excellent corrosion resistance against sulfuric acid. Lead and its alloys are used in
piping, sheet linings, solders, storage batteries, radiation shields, cable sheath,
bearings, roofing, and ammunition. Lead is soft, easily formed and has a low melting
point.

In the process industry, lead is alloyed with 0.06% copper to improve corrosion
resistance. It is rapidly attacked by acetic acid and generally not used in nitric,
hydrochloric, and organic acids. The strength of the lead can be improved by addition
of antimony or calcium.

7.1.5 Copper and its Alloys

Copper is a base material alloyed with tin, zinc, nickel, etc. to enhance its
strength. The mechanical properties can be improved by cold working. When copper is
alloyed with tin, it forms bronze. Similarly, copper alloyed with zinc forms brass. The

186
 Corrosion Tutorial

most popular brasses or bronzes are cold heading brass, naval bronze, and leaded
brass. Copper possesses higher electrical conductivity, thermal conductivity, corrosion
resistance, and ductility. The major applications of copper alloys are power utilities,
lighting and wiring devices, electronics, appliances, electric cords, etc.

7.1.6 Nickel and its Alloys

Nickel has low corrosion rates in acid solutions in the active state. Alloying
additions of copper, molybdenum, and tungsten lowers the corrosion rate further.
Nickel is one of the major alloying elements in the stainless steels, corrosion resistant
steels, and high temperature steels. Nickel alloys possess high strength, toughness,
and ductility. Some of the important nickel alloys are Monel, Constantan, German
silver, Hastelloy D, Iconel, etc. The nickel alloys are used extensively for vessels,
piping, pumps, and in the production of most minerals and organic acids.

7.1.7 Zinc and its Alloys

Zinc is not a corrosion resistant metal but it is utilized as a sacrificial anode for
cathodic protection of steel. Its use is in galvanized steel for piping, fencing, nails, etc.
It is also utilized in the form of bars or slabs as anodes to protect ship hulls, pipelines,
and other structures.

Zinc alloy parts are made by die casting because of their low melting points.
Many automobile components such as grilles and door handles are die cast but are
usually plated with corrosion resistant metals.

7.1.8 Cadmium
Cadmium is used exclusively as an electroplated coating. Cadmium is soluble in
hydrochloric acid, sulfuric acid and nitric acid. Cadmium can be used to protect steel,
but it is not as effective as zinc. Cadmium is more expensive than zinc and its salts are
toxic.

187
 Corrosion Tutorial

Cadmium plating is utilized on high strength steels in aircraft because of

improved resistance to corrosion fatigue. It can be soldered and hence it finds
applications in radio and television industries.

7.1.9 Titanium and its Alloys

Titanium is highly reactive forming a continuous, stable, protective, and adherent
oxide film on the surface in presence of oxygen and moisture. Titanium alloys are often
unsuitable for hot, concentrated, reducing acids in which the oxide film cannot form.
Titanium finds wide spread application in the aircraft industry.

7.1.10 Coated Alloys

Alloy materials, which have a coating material on it, are called coated alloys.
They have more resistance to corrosion. The coatings used should be compatible with
the underlying alloy materials.

7.1.11 Molybdenum
Molybdenum shows good resistance to hydrofluoric, hydrochloric, and sulfuric
acids, but oxidizing agents such as nitric acid cause rapid attack. It is used as an
alloying element for steel to increase its hardness, toughness, strength, and abrasion
resistance. Molybdenum is lighter in weight, easier for fabrication, and possesses high
ductility. Molybdenum finds applications in electronic tubes and in pressure applications
where galling is a problem.

7.1.12 Tantalum
Tantalum is widely used in handling chemically pure solutions such as
hydrochloric acid. Tantalum possesses high thermal conductivity and corrosion
resistance. But tantalum is easily attacked by alkalies. Tantalum is used for surgical
implants.

188
 Corrosion Tutorial

7.1.13 Tungsten
Tungsten has the highest melting point temperature. Its chief use involves
strength at high temperatures. A common example is filament in bulbs. Tungsten
shows good resistance to acids and alkalies except nitric acid.

7.1.14 Zirconium
Zirconium finds extensive application in the ceramic industry. Moreover,
zirconium is an important structural metal in atomic energy plants. Zirconium has
excellent corrosion resistance due to its protective oxide film. This metal exhibits good
corrosion resistance to alkalies and acids except for hydrofluoric acid, hot concentrated
hydrochloric, and sulfuric acids. Zirconium has found some applications in hydrochloric
acid service. Its corrosion resistance is affected by impurities in the metal such as
nitrogen, aluminum, iron, and carbon.

7.1.15 Gold
Gold is one of the oldest metals used. Gold and its alloys are used in jewelry,
dental inlays, electrical contacts, plating, tableware and decorative purposes. Gold is
not attacked by dilute nitric acid and sulfuric acid. But gold is attacked by concentrated
nitric acid, chlorine, and bromine, mercury and alkaline cyanides. The color, stability
and luster made this metal useful in jewelry and coinage.

7.1.16 Platinum
Platinum exhibits good mechanical properties such as high temperatures and
wear resistance. The inertness of platinum is attested by its extensive service as a
catalyst. It is very expensive and hence it is used for limited applications. Platinum has
excellent corrosion resistance and oxidation resistance in hot oxidizing gases. Platinum
is attacked by aqua regia, hydroiodic, hydrobromic acids, ferric chloride, chlorine and
bromine. It is used in spark plugs, electrical resistors, burner nozzles, and as anodes or
cathodes in electrolytic cells.

189
 Corrosion Tutorial

7.1.17 Silver
Silver is best known for its use as coinage, jewelry and tableware. Silver
possesses high electrical and thermal conductivity, stability, and luster. Silver finds
extensive applications in the photography industry. Silver is also widely used in the
chemical industry as solid silver and also as loose, clad, or brazed linings. Silver
tarnishes in the presence of hydrogen sulfide and sulfur bearing environments. It is
highly resistant to organic acids. Silver is attacked by nitric acid, hot hydrochloric acid,
mercury, and alkaline cyanides and may be corroded by reducing acids if oxidizing
agents are present.

7.2 Plastics
A plastic is a material that contains organic substance of larger molecular weight,
is solid in its finished state. Plastics are classified into two types thermoplastics and
thermosets. Thermoplastic materials soften when heated and return to the original
hardness when cooled. Some common examples of thermoplastic materials are nylon,
acrylic and cellulose. On the other hand thermosets harden when heated and retains
the hardness after cooling. Some common examples of thermosets are epoxies,
phenolics and polyesters. Plastics are generally much weaker, softer, and more
resistant to chloride ions and hydrochloric acid, less resistant to concentrated sulfuric
and oxidizing acids such as nitric, less resistant to solvents.

7.2.1 Thermosets
A thermoset is a resin in liquid form before curing (eg. epoxy or polyester), which
undergoes a chemical reaction by the action of heat, catalyst, ultraviolet light, etc., to
become a relatively insoluble substance. Upon the application of heat or catalysis the
liquid resin becomes rigid due to curing process. The resultant product is less sensitive
to temperature and it is nonrecyclable. The chemical bonds are formed through cross-
linking of molecules and this provides thermal stability without any flow of resin upon

190
 Corrosion Tutorial

heating. A thermoset composite is a material containing a thermosetting polymeric

matrix.

7.2.2 Thermoplastics
Thermoplastics are those materials whose change upon heating is substantially
physical rather than chemical. They are largely one-dimensional or two-dimensional
molecular structures such as nylons, polycarbonates, acetals, and polysulfones. These
are linear or branched structures and they are recyclable. The polymer melts and flows
upon heating and has a number of heat sensitive properties. Individual polymer
molecules are held together by weak forces, such as Van der Waal forces, hydrogen
bonds and dipole- dipole interactions. Thermoplastic matrices reinforced with carbon,
glass or aramide fibers are called thermoplastic composites.

7.3 Ceramics
A ceramic material consists of compounds of metallic and non-metallic elements.
Ceramic materials find extensive applications in jet engines and atomic reactors.
Ceramics include brick, stone, fused silica, stoneware, glass, clay tile, porcelain,
concrete, abrasives etc. Ceramic materials have low tensile strength and high
compressive strength. The strength of the material depends on cross-sectional area,
composition and surface conditions. Most ceramic materials exhibit good resistance to
chemicals with exception to hydrofluoric acid and alkalies. Ceramic parts are usually
formed by pressing, extrusion or slip casting.

7.4 Composite Materials

A composite material is made by combining two or more materials to give a
unique combination of properties. Composites maintain an interface between
components and act in concert to provide improved specific or synergistic
characteristics not obtainable by any of the components acting alone. Composites

191
 Corrosion Tutorial

include: (1) fibrous (composed of fibers usually in a matrix), (2) laminar (layers of
materials), (3) particulate (composed of particles or flakes, usually in a matrix), and (4)
hybrid (combinations of any of the above).

7.4.1 Organic Matrix Composites (OMCs)

The matrix in the composite is a chemical compound containing carbon
molecules with the exception of CO2, which is considered inorganic. These composites
in which fibers are embedded in an organic matrix are called OMCs. They are primarily
used in aerospace structures as they have high resistance to corrosion and fatigue
damage.

OMCs are further subdivided as:

Polymer Matrix Composites (PMCs)

A polymer is an organic compound, natural or synthetic, whose structure can be

represented by a repeated small unit (mer). These long molecular chains consist of
repeating chemical units held together by covalent bonds formed by a polymerization
reaction. PMCs consist of polymer resin as the matrix. When the matrix material is
such a polymeric chain, then it is called a PMC. PMCs are typically used in low-
temperature structural applications such as in civil-structures, biomedical implants,
automobiles, and airframe structures. The fibers typically provide the stiffness and
strength to the composite and can be made from a wide variety of materials including
glass, graphite, kevlar, and boron. The fibers can be arranged in almost any fashion,
ranging from totally random to highly structured and organized.

Carbon Matrix Composites (CMCs)

Extra steps of carbonizing and densifying the original polymer matrix typically
form carbon matrix composites. They are commonly refered to as carbon-carbon
composites.

192
 Corrosion Tutorial

7.4.2 Metal Matrix Composites (MMCs)

MMCs include metallic matrix materials reinforced with continuous fibers such as
boron, silicon carbide, graphite or alumina, wires including tungsten, beryllium, titanium
and molybdenum and discontinuous materials such as fibers, whiskers and particulates.
The reinforcements are chosen to increase stiffness, strength, as well as heat, and wear
resistance. The principal motive of using metal matrix composites was to dramatically
extend the structural efficiency of the metallic materials while retaining their advantages
including high chemical inertness, high shear strength and good property retention at
high temperatures.

7.4.3 Ceramic Matrix Composites (CMCs)

Materials consisting of a ceramic or carbon fiber surrounded by a ceramic matrix,
primarily silicon carbide. Ceramic materials are inherently resilient to oxidation and
deterioration at elevated temperatures. Ceramic matrix composite focuses on achieving
useful structural and environmental properties at high operating temperatures.

7.4.4 Particulate Reinforcements

Particulate reinforced composites include those reinforced by spheres, rods,
flakes and many other shapes of roughly equal axes. These can be classified as
discontinuous reinforcements.

Figure 7-1: Particulate Reinforcement

Reference: http://www.asm-intl.org/pdf/spotlights/IntroToComposites.pdf

193
 Corrosion Tutorial

7.4.5 Whisker Reinforcements

Whisker reinforcements are short, discontinuous fibers of polygonal cross-
sections, made of a large number of materials such as graphite, aluminum oxide, silicon
carbide, silicon oxide, boron carbide and beryllium oxide.

Figure 7-2: Whisker Reinforcement

Reference: http://www.asm-intl.org/pdf/spotlights/IntroToComposites.pdf

7.4.6 Continuous Fiber Reinforced Composites

Continuous fiber reinforced composites contain reinforcements whose lengths
are much greater than their cross sectional dimensions. If any increase in length of the
fiber does not provide further increase in elastic modulus or strength of the composite,
then the composite is considered to be continuous fiber reinforced.

Figure 7-3: Continuous Fiber Reinforcement

Reference: http://www.asm-intl.org/pdf/spotlights/IntroToComposites.pdf

7.4.7 Braided Fabrics

Braided fabrics are fabrics in which two sets of continuous fibers are interwoven
symmetrically about an axis. Braided fabrics are engineered with a system of two or
more yarns intertwined in such a way that all of the yarns are interlocked for optimum
load distribution. Biaxial braids provide reinforcement in the bias direction only with fiber
angles ranging from ± 15o to ± 90o. Triaxial braids provide reinforcement in the bias
direction with fiber angles ranging from ± 10o to ± 80o and axial (0o) direction.

194
 Corrosion Tutorial

Figure 7-4: Braided Fabrics

Reference: http://www.asm-intl.org/pdf/spotlights/IntroToComposites.pdf

7.4.8 Hybrid Fabrics

The term hybrid refers to a fabric that has more than one type of structural fiber
in its construction. If low weight or extremely thin laminates are required, a hybrid fabric
will allow the two fibers to be presented in just one layer of fabric. Typically, the
available fiber orientations include the 0o direction (warp), 90o direction (weft or fill). It
would be possible in a woven hybrid to have one fiber running in the weft direction and
the second fiber running in the warp direction, but it is more common to find alternating
threads of each fiber in each warp direction. There are several types of hybrid
composites characterized as: (1) interply or tow-by-tow, in which tows of the two or
more constituent types of fiber are mixed in a regular or random manner; (2) sandwich
hybrids, also known as core-shell, in which one material is sandwiched between two
layers of another; (3) interply or laminated, where alternate layers of the two (or more)
materials are stacked in a regular manner; (4) intimately mixed hybrids, where the
constituent fibers are made to mix as randomly as possible so that no over-
concentration of any one type is present in the material; (5) other kinds, such as those
reinforced with ribs, pultruded wires, thin veils of fiber or combinations of the above.

Figure 7-5: Hybrid Fabrics

Reference: http://www.netcomposites.com/education.asp

195
 Corrosion Tutorial

7.4.9 Knitted or Stitched Fabrics

Stitched fabrics are produced by assembling successive layers of aligned fibers.
Typically, the available fiber orientations include the 0o direction (warp), 90o direction
(weft or fill), and +45o direction (bias). The assembly of each layer is then sewn
together. This type of construction allows for load sharing between fibers so that a
higher modulus, both tensile and flexural, is typically observed. This allows for
maximum resin flow when composites are manufactured.

Figure 7-6: Knitted or Stitched Fabrics

Reference: http://www.enae.umd.edu/ASC/abstracts/abs102.pdf

7.4.10 Woven Composites

A planar woven fabric composite is a fabric produced by interlacing two or more
sets of yarns, fibers, rovings, or filaments where the elements pass each other
essentially at right angles and one set of elements is parallel to the fabric axis.

Figure 7-7: Woven Fabric

Reference: http://www-mech.eng.cam.ac.uk/ccm/projects/mpfs/departabs2.pdf

196
 Corrosion Tutorial

7.4.11 Carbon Fiber Reinforced Plastics

A composite material composed of carbon fiber as filler reinforcement and
plastics as matrix. The most important feature of it is that it has excellent mechanical
properties though it has low density. They have high stiffness to weight ratios and
provide better fatigue characteristics to the composite by reducing the amount of strain
in the polymer matrix.

7.4.12 Glass Fiber Reinforced Plastics

In this type of FRP the reinforcement is provided by glass fibers. Glass fibers
exhibit the typical glass properties of hardness, corrosion resistance, and inertness.
Tensile strength of glass fibers reduces with increases in temperature and with chemical
corrosion.

7.4.13 Aramid Fiber Reinforced Plastics

The trade name of this type of fiber is Kevlar. Aramid fibers have high-energy
absorption during failure, which make them suitable for impact and ballistic protection.
They have low compressive strength, they creep absorb moisture and are sensitive to
UV radiation.

7.5 Manufacturing Processes of Composites

7.5.1 Open-Mold Processes

Open mold processes make use of a single cavity mould and requires little or no
external pressure. The mold is waxed and sprayed with gel coat. After the gel coat
cures, catalyzed resin is sprayed along with fibers. The fibers are chopped directly into
the resin stream. The laminate is then compacted by hand with rollers. The composite
is then cured, cooled and removed from the reusable mold. The open mold technique
produces emission of volatile organic compounds. Types of open mold spray up are
hand lay up and tube rolling.

197
 Corrosion Tutorial

7.5.1.1 Hand Lay Up

An open mold process in which the reinforcements are applied to the mold and
the composite is built by hand. Resins are impregnated by hand into fibers, which are in
the form of woven, knitted, stitched or bonded fabrics. This is usually accomplished by
using rollers or brushes, with an increasing use of nip-roller type impregnators for
forcing resin into the fabrics by means of rotating rollers and a bath of resin. Laminates
are left to cure under standard atmospheric conditions. Curing is normal at ambient
temperature but if heating is done the curing process is accelerated.

Figure 7-8: Hand Lay Up

Reference. http://www.netcomposites.com/education.asp?sequence=55

7.5.1.2 Tube Rolling

Tube rolling is the manufacturing process used to produce finite length tube and
rod. The material is precut in particular patterns to achieve the required ply schedule
and the fiber architecture. The pieces are laid and the mandrel is rolled over under
pressure. Fibers must be continuously realigned to impart bending strength. This
technique is more environmentally friendly.

198
 Corrosion Tutorial

Figure 7-9: Tube Rolling

Reference: http://www.harrisonrods.co.uk/production.htm

7.5.2 Closed-Mold Processes

A technique used in composite fabrication that utilizes a two-piece mold (male
and female). The processes are usually largely automated. Various methods are used
to transfer liquid resin from an external source into the dry preform that will be placed in
a two-sided matched closed mold. Closed mold processes include RTM, VARTM, resin
Injection molding, compression molding, pultrusion, extrusion, and filament winding
process.

7.5.2.1 Resin Transfer Molding (RTM)

A closed-mold pressure injection system that allows for faster cure times as
compared to contact molded parts. The process uses polyester matrix material systems
in association with cold-molding and reinforcement material types such as continuous
strand, cloth, woven roving, long fiber and chopped strand. In RTM, resins and catalyst
are metered and mixed in the dispenser equipment before they are injected/infused into
the mold.

199
 Corrosion Tutorial

Figure 7-10: Resin Transfer Molding Machine (CFC-WVU)

7.5.2.2 Vacuum Assisted Resin Transfer Molding (VARTM)

Figure 7-11: VARTM –Tabletop Model of VARTM and Schematic Process of Manufacture

Reference: http://www.ncat.edu/~sasmith/C2.pdf

7.5.2.3 Resin Injection Molding Process

Resin injection molding is similar to the resin transfer molding process except
that it injects a resin/catalyst into the mold in two streams, so that mixing and the
resultant chemical reaction occur in the mold instead in the dispensing head. The
material is forced from an external heated chamber through a runner or gate into a
cavity of a closed mold by means of a pressure gradient, independent of the mold's
clamping force.

200
 Corrosion Tutorial

Figure 7-12: Injection Molding Machine (CFC-WVU)

7.5.2.4 Compression Molding

Compression molding is a method of molding in which the molding material,
generally preheated, is first placed in an open, heated mold cavity. The mold is closed
with a top force or plug member, and pressure is applied to force the material into
contact with all mold areas. Heat and pressure are maintained until the molding
material has cured. Compression molding is a high-volume, high-pressure method
suitable for molding complex, high-strength fiberglass reinforcements. Advanced
composite thermoplastics can also be compression molded with unidirectional tapes,
woven fabrics, randomly orientated fiber mat or chopped strand. The advantage of
compression molding is its ability to mold intricate parts of large dimensions.

201
 Corrosion Tutorial

Figure 7-13: Compression Molding Machine (CFC-WVU)

7.5.2.5 Pultrusion
Pultrusion is a continuous automated closed molding process that is cost
effective for high volume production of constant cross section parts. This process relies
on relies on reciprocating or puller/clamping systems to pull the fiber and resin
continuously from a resin impregnating bath through a heated steel die. Excess resin is
squeezed out by the shaped bushings. The compacted part then enters the die where it
cures.

Figure 7-14: Schematic Representation of Pultrusion Process (Bedford Plastics)

202
 Corrosion Tutorial

7.5.2.6 Extrusion
Extrusion is a process used for forming composite preformed materials from
mixtures of a matrix powder and short fibers suitable for MMCs. It is a thermoplastic
process whereby pellets, granules, or powder are melted and forced through a die
under pressure to form a given, continuous shape.

Figure 7-15: Basic Extruder

Reference: http://www.reliance.com/prodserv/standriv/appnotes/d7741.pdf

7.5.2.7 Filament Winding Process

"Filament Winding" is a highly automated process in which fiber yarn (Carbon
Fiber, Fiberglass, Kevlar, etc.) is pulled from a large spool, pulled through a bath of
resinous polymeric material (epoxy, etc.), and "wound" upon a tool, or mandrel. A
release agent is applied to the mandrel before winding which enables the composite
part to be removed later. The mandrel is then placed under tension in the winding
machine, which rotates the mandrel while moving a carriage that applies the composite
material. A computer controls these motions, and ensures that the composite material
will be applied accurately. Once the composite material is applied, a special non-stick
plastic film is wrapped under tension around the part. This film is applied to provide
compaction to the composite, and is removed later. The mandrel is then placed in a
computer-controlled oven, and special heating profiles harden the polymeric resin,
solidifying the composite material. The mandrel is then removed by placing the mandrel

203
 Corrosion Tutorial

/ part into an extraction machine which pulls the mandrel out of the part. The part can
then be machined, finished, and painted into a final form.

Figure 7-16 a: Winding Machine Showing Carriage and Mandrel b: Filament Winding

Reference a: http://www.advancedcomposites.com/winding.htm

Reference b: http://www.netcomposites.com/education.asp?sequence=57

7.6 Terms Related to Composites

Abraded – Make the surface rough by mechanical means such as wirebrushing.

Accelerated Aging - Any set of conditions designed to produce in a short time

the results obtained under normal conditions of aging.

Additives – This material modifies and enhances the final FRP product.

Adherent – A member of a bonded joint.

Adhesive – A substance capable of holding two materials together by surface

treatment.

Adhesive Failure – Failure caused due to the rupture of the adhesive bond

leading to the separation of the adhesive - adherend interface.

Aging - The effect of environmental factors, like moisture, temperature, etc. on

the composite material when exposed for a period of time.

204
 Corrosion Tutorial

Aging Factor – Aging Effects due to physical and chemical exposure are

accounted for using aging factors in design methodology.

Anisotropic Material – Elastic properties are different in all the directions.

Aramid Fibers - A manufactured fiber in which the fiber forming substance

consists of a long chain synthetic aromatic polyamide in which at least 85% of the

amide linkages are attached directly to two aromatic rings.

Axial Strength – The strength of the material in tension or compression when

the load is applied length wise along the axis. It may be tensile or compressive

strength.

Bending Strength - The strength of a material in bending, expressed as the

stress on the outermost fibers of a bent test specimen, at the instant of failure.

Bending Modulus - The ratio, within the elastic limit, of the applied stress on a

test specimen in bending, to the corresponding strain in the outermost fibers of the

specimen.

Bending Rigidity - Stiffness due to bending forces.

Bi-directional Fibers/Fabrics (2-D) – Continuous rovings placed in a plane in

any two directions.

Block Shear Failure - Combination of tension failure along one plane and shear

failure along another plane of the same component.

Bolt Shear Failure – Is caused by high shear stress in the fastener.

Bond – The adhesion of one surface to another, with the use of an adhesive or

bonding agent.

205
 Corrosion Tutorial

Carbon Fibers – Fibers produced by the pyrolysis of organic precursor fibers

such as rayon. PAN or pitch in an inert atmosphere.

Chemical degradation – The degradation or the deterioration of a material due

to chemical attack.

Cleavage Failure – Characterized by a single-plane cleavage failure where the

apparent laminate transverse tensile strength is less than the corresponding in plane

shear strength.

Coefficient of Thermal Expansion - The coefficient of thermal expansion

(linear) is the change in length per unit length of material, for a one degree Centigrade

change in temperature.

Cohesive Failure – Is caused due to the failure of the adhesive/adherend when

subjected to loads exceeding the adhesive/adherend strength.

Composite - Composites are a combination of a reinforcement fiber in a polymer

resin matrix, where the reinforcement has an aspect ratio that enables the transfer of

loads between fibers, and the fibers are chemically bonded to the resin matrix.

Composite Moment of Inertia - Moment of inertia due to joint action between

the composite deck and girder.

Crazing – Fine cracks at or near the surface of a plastic material.

Creep – Time dependent deformation of a material (or structure) under constant

load.

Debonding – Separation of fiber from the matrix.

Delamination – The separation of the layers of material in a laminate.

Delams – Delamination in the FRP deck.

206
 Corrosion Tutorial

Ductility – Ability of material to undergo large deformations before fracturing.

Ductility Factor – The ratio between the difference of total impact energy and

energy to peak impact force to energy to peak impact force.

Durability – The ability of a structure to maintain strength and stiffness

throughout the service life of the structure.

ECR Glass – ECR glass fibers are boron free, very resistant to chemical attack

and have similar properties to E glass.

Effective Flange width - In an FRP composite deck system, the shear

deformations tend to reduce the longitudinal stresses as they progress transversely

from the web of the girder (shear lag effect). In engineering practice, this problem is

accounted for assuming only a portion of the flange to the effective. This reduced flange

width is referred to as the effective flange width.

Elastic Deformation - Nonpermanent deformation, after which body returns to

original shape or volume when deforming force is removed.

Epoxy Resin – Resins, which may be of widely different structures but which are

characterized by the reaction of the epoxy group to form a cross-linked hard resin.

Extensional Bending Coupling Stiffness – Stiffness due to coupling of in-plane

and bending forces.

Factored Resistance – Product of nominal resistance and the resistance factor,

which is provided to account for variability in material properties of FRP.

Failure strain – The ultimate strain at which the FRP material fails.

Fatigue - The failure or decay of mechanical properties after repeated

applications of stress.

207
 Corrosion Tutorial

Fiber – A single homogeneous strand of material having a length of at least 5

mm, which can be spun into a yarn or roving, or made into a fabric by interlacing in a

variety of methods.

Fiber Direction - The orientation of the major axes of the fiber weave as related

to the designated zero direction.

Fiber Reinforced Polymer – Fiber reinforced polymer materials consist of fibers

of high strength and modulus embedded in or bonded to a matrix with distinct interfaces

(boundary) between them.

Fire Retardant Resins – Resins that are inflammable.

Flexural Strength - The strength of a material in bending, expressed as the

stress on the outermost fibers of a bent test specimen, at the instant of failure.

Flexural Modulus - The ratio, within the elastic limit, of the applied stress on a

test specimen in flexure, to the corresponding strain in the outermost fibers of the

specimen.

Gel Coat – A quick setting resin used in molding process to provide an improved

surface for the composite.

Glass Transition – The reversible change in an amorphous polymer or in

amorphous regions in partially crystalline polymer from a viscous or rubbery condition to

a hard and relatively brittle one.

Glass Transition Temperature – Temperature range over, which a plastic

changes from a rigid state to softened (rubber-like) state, resulting in significantly

degraded mechanical and electrical properties. This occurs in a narrow temperature

range, rather than a sharp point such as a freezing point or boiling point.

208
 Corrosion Tutorial

Global Deflection – The maximum global deflection of the girder in a typical

composite structure.

Impact Resistance – Resistance offered by the structure against impact loads.

In-Plane Shear Loading – Adherend shear loads that produce shear stresses in

the bond line in lap and strap joints.

In-Plane Stiffness - Stiffness in the in-plane direction due to in-plane forces.

Isotropic – Elastic properties are same in all the directions; hence, the material

contains an infinite number of planes of material property symmetry passing through the

same point.

Lamina – A single ply or layer in a laminate of layers.

Limit State - A condition beyond which the structure ceases to satisfy the

provisions for which it was designed.

Limit Stresses – A value of stress beyond which the structure ceases to satisfy

for provision for which it was designed.

Local Deflection – Local deflection in the top flange of FRP deck.

Matrix - Polymeric material used as binder for reinforcing fibers in FRP.

Net-tension Failure – Occurs when the specimen is narrow compared to the bolt

diameter and the crack propagates transverse to the loading.

Nominal Resistance – The resistance of a component or connection to force

effects, as indicated by the dimensions specified in the contract documents and by

maximum permissible stresses, deformations, or specified strength of materials.

Nonductile Material – A material, which is brittle, or a material that can undergo

very little plastic deformation.

209
 Corrosion Tutorial

Orthotropic Material – FRP materials containing three orthogonal planes of

material property symmetry.

Overlay – The laying of FRP material or asphalt over a composite deck in order

to prevent further corrosion or for decorative purposes.

Overloads – Loads that are heavier than the design loads of the structure.

Protective Coatings – A protective and finishing enclosure surface for the FRP

material.

Resin - Polymeric material used as binder for reinforcing fibers in FRP.

Resistance Factor – Factor, which depends on, event of rupture of the section

due to tension, flexure, shear, torsion or combination.

Rovings – A number of ends, tows, or strands collected into a parallel bundle

with little or no twist.

Rule of Mixtures - Formed sub laminates undergo the same axial strain but not

necessarily the same transverse strain, based on the linear volume fraction relationship

between the composite and its corresponding constituent properties.

Service Limit State – Limit states relating to stress, deformation and cracking

under service loads.

Shear - An action or stress resulting from applied forces that tend to cause two

contiguous parts of a body to slide relative to each other in a direction parallel to their

plane of contact.

Shear Rigidity – Stiffness due to shear forces.

210
 Corrosion Tutorial

Shear Modulus - The ratio of shearing stress τ to shearing strain γ within the

proportional limit of a material.

Shearlag – The non-uniform shear distribution within any given material.

Shear-Out Failure - Occurs as the section of the material parallel to loading

pushes past the remaining specimen. It is caused by shear stress and occurs along the

shear- out planes.

Single Lap Joint – A joint formed by overlapping one laminate over the other.

Stitched Fabrics (3-D) – Multidirectional rovings in a plane with various layers in

the direction perpendicular to the plane and stitched together (yarn, glass fiber, etc)

either in-plane or out of plane.

Temperature Gradient - Temperature gradient is the rate of change of

temperature with distance in any given direction at any point i.e, the temperature

gradient from the top to bottom of composite deck.

Tensile Shear loading – Adherend shear loads that produce shear stresses to

the bond line in lap and strap joints.

Tensile Strength – Strength of a material in tension.

Thermally Induced Loads – Loads induced due to thermal gradient in a FRP

composite Deck.

Thermoplastic – A plastic that can be repeatedly softened by heating and

hardened by cooling through a temperature range characteristic of the plastic, and when

in the softened stage can be shaped by flow into shapes by molding or extrusion.

Thermoset – A plastic that is substantially infusible and insoluble after being

cured by heat or other means.

211
 Corrosion Tutorial

Unidirectional Fibers (1-D) – Continuous long fibers in one direction for which

strength and stiffness is maximum along the direction of fibers.

Void Content - Amount of voids existing in a given material

Wearing Surface - Overlay material applied on the surface of the FRP Deck.

Young’s Modulus – The ratio stress/strain within elastic limit.

7.7 Reagents

7.7.1 Sulfuric Acid

Sulfuric acid is a very strong acid. It is a dense, colorless, and corrosive liquid. It
is used in manufacturing fertilizers, pigments, dyes, drugs, and explosives. It is also
used in petroleum refining and metallurgical processes. The commercial industrial
concentrations for sulfuric acid are 78%, 93% and oleum. Steel is the most common
material used for storage and transportation of sulfuric acid. Dilute acids attack steel
more rapidly than the strong acids. Moreover, the corrosion rate of steel increases as
the temperature of the acid increases when the concentration of the acid is up to 70%.
Above 70% concentration, there is no reliable data available to predict the corrosion
rate. Aeration of sulfuric acid in the storage tanks will lead to drastic efforts. Cast iron
shows similar effects like steel. High silicon cast iron containing 14.5% silicon has
better performance against corrosion. Usage of high silicon cast iron should be avoided
in case of fuming acids. Copper alloys are not generally used for sulfuric acid
applications.

7.7.2 Hydrochloric Acid

Hydrochloric acid is used in the manufacture of fertilizers, dyes, artificial silk, and
pigment for paints. It is used in removing scales in boilers, clean membranes in
desalination plants, and to clean other metals for coatings. Hydrochloric acid is one of
the most corrosive of the non-oxidizing acids in contact with copper alloys, and is

212
 Corrosion Tutorial

handled in dilute solutions. It is soluble in benzene, alcohol, and ether. It is insoluble in

hydrocarbons. It is incompatible/reactive with metals, hydroxides, amines, and alkalis.
Hydrochloric acid’s fumes have an acid, penetrating odor. Aqueous solutions of
hydrochloric acid attack and corrode nearly all metals except mercury, silver, gold,
platinum, tantalum, and certain alloys. It may be colored yellow by traces of iron,
chlorine, and organic matter.

7.7.3 Nitric Acid

Nitric acid is a corrosive, non-volatile and inorganic acid. It is used in the
manufacture of fertilizers, dyes, explosives, and other organic chemicals. It is a strong,
monobasic acid and an oxidizing agent. In the presence of traces of oxides, it attacks
all base metals except aluminum and special chromium steels. It is soluble in water
(cold and hot), and ether. It increases the flammability of combustible organic and
oxidizable materials and can also cause ignition of some of these materials.

7.7.4 Hydrofluoric Acid

Hydrofluoric acid is a weak acid. It finds extensive applications in various
industries such as glass industry, leather industry, textile industry, fertilizers, etc.
Magnesium shows excellent corrosion resistance to hydrofluoric acid. Steel is used in
handling the hydrofluoric acid when the concentration is between 60 and 100%. Monel
shows excellent corrosion resistance at all concentrations and temperatures. But
aeration and presence of oxidizing salts leads to increase in corrosion rate. Lead
shows good resistance to hydrofluoric acid in concentrations below 60% at room
temperature.

213
 Corrosion Tutorial

7.7.5 Phosphoric Acid

Phosphoric acid usually exists as a crystal or clear liquid. It is either an oily, thick,
colorless, and odorless liquid, or a thick, colorless, unstable crystalline solid. It is used in
the manufacturing of phosphates, fertilizers, electric lights, and soft drinks. It is used as
an acid catalyst, soil stabilizer, antioxidant in food, bonding agent for refractory bricks,
and gasoline additive. It is also used in the rust proofing and polishing of metals, cotton
dyeing, tile cleaning, extracting penicillin, hot stripping for aluminum and zinc
substrates, ceramic binding, water treatment, process engraving, electro-polishing,
coagulating of rubber latex, operating lithography, photoengraving operations, and
pickling.

Phosphoric acid is incompatible with strong caustics and most metals. It readily
reacts with metals to form flammable hydrogen gas. The liquid can solidify at
temperatures below 21oC. It is corrosive to ferrous metals and alloys. It is soluble in
alcohol and hot water. It can form three series of salts: primary phosphates, dibasic
phosphates, and tribasic phosphates. It is deliquescent and hygroscopic. It is a
chelating agent. It has a low vapor pressure at room temperature.

214
 Corrosion Tutorial

8 CORROSION KINETICS

The corrosion reaction rates can be predicted using the thermodynamic

principles only when the reactions are in equilibrium. When the corrosion reactions are
not in equilibrium, the corrosion kinetics needs to be considered. Polarization, mixed
potential theory, and experimental polarization curves are discussed in this chapter.

8.1 Polarization
The polarization is a state where current flows in a circuit, where the cathodic
and anodic reactions take place. Polarization can be divided into two types. They are
activation polarization and concentration polarization. Activation polarization is related
to chemical reaction control while concentration polarization is related to diffusion
control.

8.1.1 Activation Polarization

The activation polarization can be derived using Figure 8.1. The solid line and
the dotted line represent the status of non-polarization and polarization, respectively.
The directions of these reactions are conveniently chosen as

Anodic
⎯⎯ ⎯⎯→
H2 2 H + + 2e − …(8.1)
Cathodic
←⎯ ⎯ ⎯ ⎯

The activation energies of the forward and reverse reactions are ΔG f * and ΔGr * .

When the forward reaction is polarized by a potential E, the activation energy for the
forward reaction becomes:

ΔG f * − nFE + (1 − α )nFE = ΔG f * − α nFE and the activation energy for the reverse

reaction also becomes: ΔGr * + (1 − α )nFE

215
 Corrosion Tutorial

∆G*F –ά nFE
∆G*r ∆G*r + (1-ά)nFE
*
∆G F

nFE

nFE
(1-ά)nFE

ά (1-ά)

Figure 8-1: Activation Polarization

Then the rates of the anodic and cathodic reactions become:

ΔEa
−( )
Ra = PH 2 K a = PH 2υ e RT
…(8.2)

ΔEc
−( )
Rc = [ H ]K c = [ H ]υ e
+ + RT
…(8.3)

where ΔEa and ΔEc are the activation energies of the forward and reverse
reactions, respectively. But generally i = nFR where i is the current density (amp/cm2)
or (Coulomb/cm2-sec), F is the Faraday constant 96500 (Coulomb/equivalent) and R is
the reaction rate (moles/cm2-sec).

216
 Corrosion Tutorial

Substitution of Equation (8.2) into (8.4) yields:

r −( ΔG f * − α )nFE )
i = nFRa = PH 2 nFυ exp( ) …(8.4)
RT

ΔG f * α nFE
= PH 2 nFυ exp( − ) exp( )
RT RT

r α nFE
i = PH 2 ka exp( ) …(8.5)
RT

−ΔG f *
where ka = nf υ exp( )
RT
r r s
But when E = Erev i = i0 . Erev is equilibrium potential where i and i are same as

i0 . Here i0 is called exchange current density. Then, the equilibrium rate can be written
as:

α nFErev
i0 = PH 2 ka exp( ) …(8.6)
RT

Dividing Equation (8.5) by (8.6) yields:

r i0 α nFE
i = PH 2 ka exp( )
α nFErev RT
PH 2 ka exp( )
RT

r α nF ( E − Erev )
i = i0 exp …(8.7)
RT

But E - Erev = η . η is called overvoltage and it is a potential for driving force.

Then Equation (8.7) becomes:

r α nFη
i = i0 exp …(8.8)
RT

The rate of reverse reaction can be derived similarly as:

s −( ΔGr * + (1 − α )nFE )
i = nF R e = [ H + ]nFυ exp( )
RT

217
 Corrosion Tutorial

−ΔGr * −(1 − α )nFE

= [ H + ]nFυ exp( ) exp( )
RT RT

(1 − α )nFE
= [ H + ]kc exp( − ) …(8.9)
RT

−ΔGr *
where kc = nFυ exp( )
RT
s
But i = i0 when E = Erev

−(1 − α )nFErev
i0 = [ H + ]kc exp( ) …(8.10)
RT

Dividing Equation (8.9) by (8.10) yields:

s i0 −(1 − α )nFE
i = [ H + ]kc exp( )
−(1 − α )nFErev RT
[ H + ]kc exp( )
RT

s − (1 − α )nF ( E − E rev )
i = i0 exp( )
RT

But η = E - Erev

s −(1 − α )nFη
i = i0 exp( ) …(8.11)
RT

The net anodic current is given by:

r s
ia = i − i

α nFηa −(1 − α )nFηa

ia = i0 exp( ) − i0 exp( ) …(8.12)
RT RT

Equation (8.12) is called Butler-Volmer equation. We can see that as the

r s s
overvoltage increases i increases but i decreases. Thus when ηa >> 0, i becomes

negligible. By convention ηa takes positive values. Then Equation (8.12) becomes:

α nFηa
ia = i0 exp( ) …(8.13)
RT

218
 Corrosion Tutorial

2.303RT i
ηa = log …(8.14)
α nF i0

Equation (8.13) or (8.14) is called Tafel equation. We can see that Tafel
2.303RT
equation does not consider the reverse reaction rate, where β a = is known as
α nF
the anodic Tafel slope.

In the case of cathodic reactions, the net cathodic current is given by:
s r
ic = i − i

−(1 − α )nFηc α nFηc

ic = i0 exp( ) − i0 exp( ) …(8.15)
RT RT

Equation (8.15) is also called Butler-Volmer equation. But when ηc << 0, the

reverse reaction rate becomes negligibly small. By convention ηc takes negative

values. Then Equation (8.15) becomes:

−(1 − α )nFηc
ic = i0 exp( ) …(8.16)
RT

−2.303RT i
ηc = log c
(1 − α )nF i0

ic
ηc = β c log …(8.17)
i0

This is again called Tafel equation, more exactly the Tafel equation for cathodic
reaction.

The difference between Butler-Volmer equation and Tafel equation can be seen
from Figure 8-2. One can see that when the potential is much away from Erev, the two
equations are overlapping because the reverse reaction rates are negligible as
mentioned previously. However, when the potential approaches Erev, the two equations
differ much because the reverse reactions become significant.

219
 Corrosion Tutorial

Butler-Volmer
Anodic

Erev Tafel
E

Cathodic

i0
log i

Figure 8-2: Butler-Volmer Equation and Tafel Equation

8.1.2 Concentration Polarization

Concentration polarization is a diffusion-controlled process. The cathodic rate
increases as the overvoltage increases in the activation polarization. But the increase
of the chemical reaction rate cannot continue above a certain overvoltage because the
supply of the hydrogen ions to the surface becomes a rate controlling step. This means
that the diffusion of hydrogen ion from the bulk solution to the metal surface is slower
than the consumption rate of hydrogen ion by the chemical reaction. This state is called
concentration polarization. It is usually observed for cathodic reactions because it
usually involves diffusion of a reactant.

The concentration polarization equation can be derived as follows:

When there is no current, [H+]Surface is equal to [H+]Bulk. Then,

2.303RT P
Erev = E 0 − log + H22 …(8.18)
2F [ H ] Bulk

220
 Corrosion Tutorial

When [H+]Surface is smaller than [H+]Bulk, there would be current generated by the
diffusion of [H+] ion.

2.303RT P
E* = E 0 − log + H2 2 …(8.19)
2F [ H ] Surface

The overvoltage is:

ηconc = E * − Erev …(8.20)

Substitution of Equations (8.18) and (8.19) into Equation (8.20) yields

2.303RT [ H + ] Surface
η conc = − log …(8.21)
F [ H + ] Bulk

From the Fick’s first law,

[ H + ]Surface − [ H + ]Bulk
iconc = − FDH + …(8.22)
δ

When [ H + ]Surface is zero, iconc will be at maximum because it will give the

maximum concentration gradient. This is called limiting current density iL.

[ H + ]Bulk
iL = FDH + …(8.23)
δ

Dividing Equation (8.22) by (8.23) gives

+
iconc [ H ]Surface
= 1− …(8.24)
iL [ H + ]Bulk

Substituting Equation (8.24) into (8.21) yields

2.303RT i
ηconc = log(1 − conc ) …(8.25)
F iL

ic 2.303RT i
ηc ,total = β c log + log(1 − conc ) …(8.26)
i0 F iL

This is the equation for hydrogen electrode. However, general equation for any
metal will take the form.

221
 Corrosion Tutorial

ic 2.303RT i
ηc ,total = β c log + log(1 − conc ) …(8.27)
i0 nF iL

Equation (8.27) is plotted to show the combined polarization in Figure 8-3.

i0
Erev

Activation
Polarization
E

Concentration
Polarization

iL
Log i
Figure 8-3: Combined Polarization

8.2 Mixed Potential Theory

Mixed potential theory explains the two simple hypothesis: one is that any
electrochemical reaction can be divided into two or more oxidation and reduction
reactions. The other is that at the corrosion potential the sum of cathodic current should
be same as the sum of the anodic current. This theory can be applied to determine
corrosion rate if βa, βc, i0 and iL are known.

For example when a metal is immersed in an acid solution, the following

reactions will take place.

The cathodic reaction is:

2H+ + 2e- = H2 …(8.28)

and the anodic reaction is:

M = M2+ + 2e- …(8.29)

222
 Corrosion Tutorial

M should be an active metal, which has E0 potential less than zero, such as iron,
nickel, zinc and aluminum.

The polarization lines of these reactions can be plotted, provided that βa, βc and i0
are known (Figure 8-4). βa and βc are the slopes of the anodic and cathodic polarization
lines, respectively. i0 is the exchange current density. icorr can be determined by the
intersection point between the cathodic polarization line for acid reduction and the
anodic polarization line for the metal dissolution.

H2Æ 2H++2e-

i0

2H++2e-ÆH2
Icorr
Potential
(V vs. SHE) Ecorr

i0
MÆM2++2e-

M2++2e-ÆM

Log i
Figure 8-4: Behavior of Metal M in Acid Solution

The next example is the case where two metals M and N are immersed in an
acid solution. N is more active metal than M. If M is iron, N will be zinc, magnesium or
aluminum. Also, if M is copper, N could be iron, zinc, magnesium or aluminum. Figure
8-5 shows two sets of polarization curves: one is for the anodic dissolution of metal M
coupled with cathodic reduction of acid and the other is for the anodic dissolution of N
coupled with cathodic reduction of acid. icorr,M and icorr,N are the corrosion rates when
two metals are not coupled. However, when two metals are coupled, the anodic and

223
 Corrosion Tutorial

cathodic rates of M and N are summed and also, the cathodic rates of the acid on M
and N are summed.

i0, H2(N)
i0, H2(M) Total reduction rate

E icorr, M
icorr, N

Icorr,total

M icorr, M* icorr,N*

Total Oxidation Potential

N

Log i
Figure 8-5: Behavior of Coupled Metals in Acid Solutions

The intersection point of the dotted line represents the imaginary total corrosion
rate, icorr,total. This corrosion value is horizontally extrapolated into anodic polarization
lines of the two metals. We can see that the corrosion rate of M decreases from icorr,M
to icorr,M* while the corrosion rate of N increases from icorr,N to icorr,N*. This is particularly
the basis of a cathodic protection method with metal N as a sacrificial anode.

8.3 Experimental Polarization Curves

Mixed potential theory is used to generate theoretical polarization lines according
to Tafel equation. However, these lines are generated experimentally using an
instrument called potentiostat/galvanostat. For the generation of anodic polarization
curves, the anode of the electrochemical cell is connected to the working electrode
while the cathode is connected to the auxiliary electrode or counter electrode of the

224
 Corrosion Tutorial

instrument. A reference electrode is placed closely to the anode. Anodic polarization

curve is generated when potential with respect to the reference electrode potential
increases stepwise and current is measured at every step. Cathodic polarization curve
is similarly generated. There are two methods producing polarization curves, one is
potentiostatic, in which current is measured by varying potential and the other is
galvanostatic, in which potential is measured by varying current.

The polarization curve produced experimentally is not exactly the same as the
polarization curve as used in the mixed potential theory. When potentials are farther
away from Ecorr, the two curves are almost identical. However, in the vicinity of Ecorr, the
two curves are significantly different because of the reverse reaction as mentioned
previously with Butler-Volmer equation and Tafel equation.

Let us take the cathodic polarization curve in Figure 8-6 when the potential is
much away from Ecorr and the two curves are overlapping as mentioned previously.
However, when the potential increases, the cathodic reaction becomes less polarized,
and thus the cathodic current decreases. This means the consumption of electrons by
the cathodic reaction retards. But at the same time, as the potential increases, the
electrons are produced by the anodic reaction and its rate increases. This is a negative
effect to the cathodic reaction, decreasing the cathodic rate. Similar phenomenon
happens on the anodic polarization. This rate retardation is due to the negative effect
by its opposite half-cell reaction near Ecorr. This rate retardation is unavailable because
we cannot polarize only cathode or anode.

225
 Corrosion Tutorial

2H++2e-=H2(g)
Experimental

Ecorr icorr Tafel

equation
E

Fe=Fe2++2e-

Log i
Figure 8-6: Showing Cathodic and Anodic Polarization Curves

In order to determine the corrosion rate, the linear portion of the cathodic and
anodic polarization curves are extended, and its intersection point will be icorr. However,
if there is no linear range on the anodic polarization curve which is frequently observed,
then the determination of icorr will be more difficult and its method is available in the
literature.

226
 Corrosion Tutorial

REFERENCES

• Agarwal, B. D. and Broutman, L. J., “Analysis and Performance of Fiber

Composites”, 2nd Ed., John Wiley and Sons, New York, 1990.
• Ajjarapu, S.R., Faza, S.S. and GangaRao, H.V.S., "Strength & Stiffness
Degradation of Glass Reinforced Polyester and Vinylester Structural Plates,"
CFC 95-205 & CFC 95-206, Submitted to Naval Engineering Command, Dept. Of
Navy, Oct. 1994.
• Allred, R.E., “The Effect of Temperature and Moisture Content on the Flexural
Response of Kevlar/Epoxy Laminates: Part I [0/90] Filament Orientation,”
Environmental Effects on Composite Materials, 2, Technomic Publishing Co.,
Lancaster, 1984.
• Alsayed, S. and Alhoziamy, A., “Effect of High Temperature and Alkaline
Solutions on the Durability of GFRP bars”, CDCC’98: Durability of Fiber
Reinforced Polymer Composites for Construction, Editors: Benmokrane, B. and
Rahman, H., 1998.
• Altizer, S. D., GangaRao, H. V. S. and Vijay, P. V., “Thermoset Polymer
Performance under Harsh Environments to Evaluate Glass Composite Rebars
for Infrastructure Applications”, In Composites Institute's 51st Annual Conference
& Expo '96 Proceedings (session 3-C, pp. 1-19). Cincinnati: SPI, 1996.
• Apicella, A., Migliaresi, C., Nicholas, L., Iaccarino, L. and Rocotelli, S., “The
Water Aging of Unsaturated Polyester-based Composites: Influence of Resin
Chemical Structure”, pp. 387-392, Composites, October 1983.
• Ashbee, K. H. G. and Wyatt, R. C., “Water Damage in Glass-Fiber/Resin
Composites”, Proceedings of the Royal Society, A. 312, pp. 553-564, 1969.
• Bai, S. L. and Hu, G. K., “Simple Transverse Damage Model for Unidirectional
Composites”, Engineering Fracture Mechanics, Vol. 56, No. 1, pp. 57-64,
January 1997.
• Barbero, E. J., "Introduction to Composite Materials Design", Taylor & Francis,
Philadelphia, PA, 1999.

227
 Corrosion Tutorial

• Basic course, Appalachian Underground Corrosion Short Course, West Virginia

University, Morgantown, WV.
• Bonniau, P. and Bunsell, A. R., “A Comparative Study of Water Absorption
Theories Applied to Glass-Epoxy Composites”, Journal of Composite Material, V
15, pp. 272, May 1981.
• Bowles, D. E., Griffin, O. H. Jr., "Micromechanics Analysis of Space Simulated
Thermal Stresses in Composites. Part I: Theory and Unidirectional Laminates",
Journal of Reinforced Plastics and Composites, v 10, n 5, pp. 504-521,
September 1991.
• Buck, E., Lischer, D. W. and Nasser, N. S., “The Durability of E-Glass/Vinyl Ester
Composite Materials subjected to Environmental Conditioning and Sustained
Load”, Journal of Composite Materials, V 32 n 9, pp. 874-892, 1998
• Bullock, R. E., “Strength Ratios of Composite Materials in Flexure and in
Tension”, Journal of Composite Materials, vol. 8, pp. 200-206, 1974.
• Chamis, C. C., “Simplified Composite Micromechanics Equations For Hygral,
Thermal, and Mechanical Properties”, SAMPE Quarterly, April 14, 1984.
• Chin, J. W., Nguyen, T. and Aouadi, K., “Sorption and Diffusion of Water, Salt
Water and Concrete Pore Solution in Composite Matrices”, Journal of Applied
Polymer Science, V 71 n 3, pp. 483-492, 1999.
• Chin, J., Materials Aspects of Fiber-Reinforced Polymer Composites in
Infrastructure, NISTIR 5888, National Institute of Standards and Technology,
August 1996.
• Curtis, P. T. and Dorey, G., “Fatigue of Composite Materials", International
Conference on Fatigue of Engineering Materials and Structure, Vol. II, ImechE
Publications, 1986.
• Daniel B. Miracle, and Steven L. Donaldson, “Introduction to Composites”, ASM
Handbook, V 21, issue 49, 2002.
• Denny A. Jones, “Principles and Prevention of Corrosion”, 2nd Edition, Prentice
Hall, Upper Saddle River, NJ, 1996.
• Devalapura, R. K., Greenwood, M. E., Gauchel, J. V. and Humphrey, T. J.,
“Evaluation of GFRP Performance using Accelerated Test Methods”, Durability of

228
 Corrosion Tutorial

Fiber Reinforced Polymer (FRP) Composites for Construction, Sherbrooke,

Canada, August 1998.
• Dewimille, B. and Bunsell, A. R., “Accelerated Aging of a Glass Fiber-reinforced
Epoxy Resin in Water”, Composites, pp 35-40, Jan. 1983.
• Diamant, Y., Marom, G. and Broutman, L. J., “Effect of Network Structure on
Moisture Absorption of Epoxy Resins”, Journal of Applied Polymer Science, V 26,
pp. 3015-3025, 1981.
• Dutta, P. K., “Fatigue Evaluation of Composite Bridge Decks Under Extreme
Temperatures”, Proceedings, SAMPE Symposium, 2001.
• Ehrenstein, G. W. and Spaude, R., “A study of the Corrosion Resistance of Glass
Fibers Reinforced Polymers”, Composite Structures, Vol2, 1984, pp. 191-200,
1984.
• Enns, B. and Gillham, J. K., “Effect of the Extent of Cure on the Morphology,
Glass Transition Temperature, Water Absorption and Density of an Amine cured
Epoxy”, Journal of Applied Polymer Science, V 28, pp. 2567-2571, 1983.
• GangaRao H. V. S., P.V. Vijay, Rakesh Gupta, and Ever Barbero. “Mechanical-
Hygrothermal Responses and Predictive Models for FRP Composites.” US Army
Corps of Engineers, Engineering Research and Development Center,
Construction Engineering Research laboratory, 2001.
• GangaRao, H. V. S., Vijay, P. V. and Dutta P. K., “Durability of Composites in
Infrastructure”, CORROSION-95, Paper No. 550, The NACE International Annual
Conference and Corrosion Show, March 1995
• Garland, C.A., “Effect of Manufacturing Process Conditions on the Durability of
Pultruded Vinyl Ester/Glass Composites”, MS Thesis submitted to WVU, 2000.
• Ghorbel, I. and Valentin. D., “Hydrothermal Effect on the Physico-Chemical
Properties of Pure and Glass Fiber Reinforced Polyester and Vinyl Ester Resins”,
Polymer Composites, V 14 n4, pp. 324-334, 1993.
• Gupta, R. K., "Polymer and Composite Rheology", 2nd Edition, Marcel Dekker,
NewYork, 2000.
• Gupta, R. K., "Polymer and Composite Rheology", 2nd Edition, Marcel Dekker,
NewYork, 2000.

229
 Corrosion Tutorial

• Hahn, H. T. and Kim R. Y., “Fatigue Behavior of Composite Laminate”, Journal of

Composite Materials, Vol. 10, pp. 156-180, 1976.
• Halpin, J. C., “Primer on Composite Materials: Analysis”, Technomic Stamford,
Conn., 1984.
• Hashin, Z., “Assessment of the Self-Consistent Scheme Approximation:
Conductivity of Particulate Composites”, Journal of Composite Materials, Vol. 2,
No. 3, pp. 284-300, 1968.
• Herbert H. Uhlig, “Corrosion and Corrosion Control”, 2nd Edition, John Wiley &
Sons Inc., New York, 1971.
• Hiltz, J. A. and Keogh, I. A., “A study of the Effect of Absorbed Water on the Tg
of a Poly Amideimide using DMA and DSC”, Thermochimica Acta, 212, pp. 151-
162, 1992.
• Ishai, O., “Environmental Effects on Deformation, Strength and degradation of
unidirectional glass-fiber reinforced plastics”, Journal of Polymer Engineering
Science, V 15 n 7, pp. 486-499, 1975.
• J.R. Scully, “The Polarization Resistance Method for Determination of
Instantaneous Corrosion Rates: A Review”, Corrosion 2000, Volume 56, Pages
227-242, 2000.
• Janas, V. F. and McCullough, R. C., “The Effects of Physical Aging on the
Viscoelastic Material of a Thermoset Polyester”, Composite Science and
Technology, Elsevier Applied Science Publishers Ltd., England, pp.99-118, 1987.
• Jones F.R., Rock J.W., and Wheatley A.R., “Stress Corrosion Cracking and Its
Implications for the Long-Term Durability of E-Glass Fibre Composites”,
Composites, Vol. 14, No.3, July, 1983, pp. 262-269.
• Kajomcheappunngam, S., "The Effects of Environmental Aging on the Durability
of Glass/Epoxy Composite", Dissertation submitted to the College of Engineering
of West Virginia University, 1999.
• Karbhari, V. M., Zhao, L., Murphy, K. and Kabalnova, L., “Enivironmental
durability of glass fiber reinforced composites – short term effects”, CDCC’98:
Durability of Fiber Reinforced Polymer Composites for Construction, Edited by
Benmokrane, B. and Rahman, H., 1998.

230
 Corrosion Tutorial

• Katsuki, T., Uomoto, T., Masuda, Y. and Maruyama, K., “Experimental study on
Deterioration of Adhesion Properties of Continuous Fiber Sheet”, October/
November ACI Proceedings, 1999.
• Kelen, T., “POLYMER DEGRADATION”, Van Nostrand Reinhold Company,
1983.
• Klotz, J., Brostow, W., Hess, M. and Veeman, W. S., “Epoxy and glass
composites in water studied with 2H-NMR”, Poly. Eng. Sci., V 36 n 8, p. 1129-
1133, 1996.
• L.S. Van Delinder, “Corrosion Basics - An Introduction”, National Association of
Corrosion Engineers, 1984.
• Lesko, J. J., Verghese K. N. E. and Phifer, S. P., “Remaining strength of
hygrothermally aged pultruded vinyl ester e-glass laminates”, Advanced
Composite Materials in Bridges and Structures, Edited by Humar, J. L. and
Razaqpur, A. G., Ottawa, Ontario, Canada, August 15-18, 2000.
• Liao, K., Schultheisz, C. R., Hunston, D. L. and Brinson, L. C., “Long-Term
Durability of Fiber-Reinforced Polymer-Matrix Composite Materials for
Infrastructure Applications: A Review”, NorthWestern University, 1997.
• Mars G. Fontana and Norbert D. Greene, “Corrosion Engineering”, 2nd Edition,
McGraw-Hill Book Company, 1978.
• Marsh, L. L., Lasky, R., Seraphim, D. P. and Springer, G. S., “Moisture solubility
and diffusion in epoxy and glass epoxy composites”, IBM J. Res. Develop, V 28 n
6, p. 655-661, 1984.
• Mathews, F. L., “FEM of Composite Materials & Structures”, Woodhead
Publishing Ltd., 2000.
• McMaster, M. G. and Soane, S. D., “Water sorption in epoxy thin films”, IEEE
Transactions on components, hybrids and manufacturing technology, V 12 n 3,
pp. 373-386, 1989.
• MIL-HDBK-17-3E, “Polymer matrix composites”, Vol.3, Department of Defense
Handbook, 1997.

231
 Corrosion Tutorial

• Netravalli, A. N., Fornes, R. E., Gilbert, R. D. and Memory, J. D., “Investigations

of water & high Energy Radiation interactions in an epoxy”, Journal of Applied
Polymer Science, V 29, p. 311, 1984.
• Nielsen, L. E., “Mechanical Properties of Particulate-Filled Systems”, Journal of
Composite Materials, Vol. 1, pp. 100-119, 1967.
• P. V. Vijay, “Aging and design of concrete members reinforced with GFRP bars”,
1999.
• P.V. Vijay, and H.V.S GangaRao (1999). “Accelerated and Natural Weathering of
Glass Fiber Reinforced Plastic Bars.” American Concrete Institute (ACI), Sp 188-
53.
• P.V. Vijay, and Hota V.S GangaRao (1997). “Aging of Structural Composites
under varying Environmental Conditions.” Non-Metallic (FRP) Reinforcement for
Concrete Structures. Proceedings of the Third International Symposium, Vol.2.
• Pai, R., Kamath, M. S. and Rao, R. M. V. G. K., “Acid Resistance of Glass fiber
Composites with Different Lay-up Sequencing: Part I - Diffusion Studies”, Journal
of Reinforced Plastics Comp, V 16 n 11, pp. 1002-1012, 1997.
• Parasyuk, V. E., Delyavskii, M. V. and Berezhnitskii, L. T., “Creep of
Unidirectional Glass-Reinforced Plastics Under the Effect of Liquid Media and
Elevated Temperatures”, Mekhanika Kompozitnykh Materialov, No. 5,
September-October, pp. 910-914, 1987.
• Rao, R.M.G.K. and Balasubramanium, N and Chanda M., “Factors affecting
moisture absorption in polymer composites, Part-II: Influence of External
Factors”, Environmental Effects on Composite Materials, Vol. III, Edited by
George Springer, Technomic Publishing Company, pp. 89-95, 1981
• Regel, V. R., Chernyi, N. N., Kryzhanovskii, G. G. and Boboev, T. B., “Effect of
Ultraviolet Radiation on the Creep rate of Polymers”, Medhanika Polimerov, Vol.
3, No. 4, pp. 615-618, 1967.
• Ritter, J. E., Fox, J. R., Hutko, D. I. and Lardner, J., “Moisture Assisted Crack
Growth at Epoxy-Glass Interfaces”, Journal of Material Science, V 33 n 18, pp.
4581-4588, 1998.

232
 Corrosion Tutorial

• Romans J.B., Sands A.G., and Cowling J.E., “Fatigue Behavior of Glass-
Filament-Wound Epoxy Composites in Water”, Naval Research Labortory Report
7246, April,1971.
• S.R. White and P.T. Mather, “A Comparison of Ultrasonic and Thermal Cure
Monitoring of an Epoxy Resin,” Composite Polymers, 4, 403-422 (1991).
• Sahlin, J. J. and Peppas, N. A., “Penetrant Transport in Epoxy Resins”, Ind. Eng.
Chem. Res., V 30, p. 211-217, 1991.
• Schapery, R. A., “Thermal Expansion Coefficients of Composite Materials Based
on Energy Principles”, Journal of Composite Materials, Vol. 2, No. 3, pp. 280-
404, 1968.
• Seymour K. Coburn, “Corrosion”, American Society of Metals and National
Association of Corrosion Engineers, 1984.
• Shen, C. and Springer, G. S., in Environmental Effects on Composite Materials,
Vol. 1, G. S. Edited by Springer, Technomic Publishing, Westport, CT, pp. 34-62,
1981.
• Singh, K., Shanker, S. P. N. and Rao R. M. V. G. K., "Hygrothermal Effects on
Chopped Fiber/Woven Fabric Reinforced Epoxy Composites. Part B.
Degradation Studies", J. Reinf. Plast. and Comp., pp. 457-462, 1991.
• Springer G.S. (Editor), Environmental Effects on Composite Materials (Vol.I, II,
III), Technomac Publishing Company Inc., 1981.
• Stokes, E. H., “Across-Ply Mechanical and Thermal Characteristics of FM550
(Avtex Pre-shutdown) as a function of the Material’s moisture content”, Southern
Research Report, SRI-MME-90-1109-6526-5, Southern Research Institute,
Birmingham, AL, 1990.
• Stokes, E. H., “Anomalous swelling behavior of FM 5055 carbon phenolic
composite”, AIAA Journal, V 31 n 3, pp.584-589, 1993.
• Struik, L. C. E., “Physical Aging in Plastics and other Glassy Materials”, Polymer
Engineering and Science, Vol. 17, No. 3, pp. 165-173, March 1977.
• Talreja, R., "Fatigue of Composite Materials", Technomic Publishing Co.,
Lancaster and Basel, 1987.

233
 Corrosion Tutorial

• Verghese, K. N. E., Hayes, M. D., Garcia, K., Carrier, C., Wood, J., Riffle, J. R.
and Lesko, J. J., “Influence of Matrix Chemistry on the Short Term, Hydrothermal
Aging of Vinyl Ester Matrix Composites under Both Isothermal and Thermal
Spiking Conditions”, Journal of Composite Materials, v33, n20, pp. 1918-1938,
1999.
• Vijay, P. V. and GangaRao, H. V. S., "Development of Fiber Reinforced Plastics
for Highway Application: Aging Behavior of Concrete Beams Reinforced with
GFRP bars", CFC-WVU Report No. 99-265 (WVDOH RP #T-699-FRP1), 1999.
• Vijay, P. V., GangaRao, H. V. S. and Kalluri, R., “Hygrothermal Response of
GFRP Bars under Different Conditioning Schemes”, Durability of Fibre
Reinforced Polymer (FRP) Composites for Construction, Sherbrooke, Canada,
August 1998.
• Vimala Shekar, Hota V.S. GangaRao, Udaya Halabe, “Specifications for FRP
Highway Bridge Applications”, FHWA Contract No. DTFH61-00-C-00021, 2002
• Wang, C. S. and Wang, A. S. D., “Creep Behavior of Glass-Epoxy Composite
Laminates Under Hygrothermal Conditions”, Proceedings of the Third
International Conference on Composite Materials, Bunsell, A. R., Bathias, C.,
Martrechar, A., Menkes, D. and Verchery, G., Eds., Vol. 1, pp. 569-583, August,
1980.
• Weitsman, Y. J., "A Continuum Damage Model for Viscoelastic Materials",
Journal of Applied Mechanics, 55(4): 773-780, 1988.
• White, S. R. and Mather, P. T., “Ultrasonic and Thermal Cure Monitor of an
Epoxy Resin”, SAMPE Symposium and Exhibition, v 36, Apr. 15-18, pp.284-297,
1991.
• Wong, T. C. and Broutman, L. J., “Water in epoxy resins, Part-II-Diffusion
mechanism”, Polymer Engineering Science, V 25 n 9, p. 529-534, 1985.
• Woo, M. and Piggott, M. R., “Water Absorption of Resins and Composites: I,
Epoxy Homopolymers and Copolymers,” Journal of Comp. Tech. Res., V 9, p.
101-107, 1987.
• www.corrosion-doctors.com

234
 Corrosion Tutorial

• www.corrosion.ksc.nasa.gov
• www.edstrom.com
• www.egr.uri.edu
• www.ocean.udel.edu
• www.corrosion-club.com
• www.clihouston.com
• www.faa.gov
• www.hgtech.com
• www.alu-info.dk
• www.alspi.com
• www.corrosioncost.com
• www.nace.org
• Zheng Q., Morgan R.J., and R.E. Allred, "Low-Cost Powder Pre-Pregging
Process", Polymer Preprints, A.C.S., 36, No. 1, 777-778 (1995).

235