CORROSION

Content:
• Corrosion
– Significance of the Problem
– Fundamental of Corrosion
– Chloride Induced Corrosion
– Carbonation Induced Corrosion
– Carbonation Induced Corrosion
– Carbonation Rate
• Preventative Method
– Durability Performance
– Physical Assessment
– Chemical Assessment
– Corrosion Assessment
 CORROSION OF
REINFORCEMENT
HOW SIGNIFICANCE?

• Failure is attributed to deterioration

• Cracking and delaminating
• Not only for concrete structure
• Ultimate collapse
• Material degradation is inevitable
– Infrastructure is ageing
– Environment is aggressive, e.g. CO2

• Most severe form of deterioration

– Three forms of deterioration
– Abrasion, alkali silica reaction, rebar corrosion

• Structures built in 60s or earlier

– Maunsell report: up to 60% needs repair
• In monetary terms
– UK: £30 million p.a. for bridges only
– US: $30 billion p.a. for total maintenance
– Australia: 6.7% GDP about $30 billion
• Timely maintenance saves monies
– Appreciation of the problem
– Solution to and prevention of the problem
– Extension of service life
• US: $150 mil on research to develop
methods
 WHAT IS CORROSION?
• General corrosion
– Corrosion occurs to non-steel material as well
– Reaction of material with surrounding medium
• Metal corrosion
– Dry corrosion: direct reaction between surface metal
and atmospheric oxygen
– Wet corrosion: a series of electrochemical reactions
in the presence of aqueous electrolyte
• Steel corrosion in concrete
 CORROSION IN CONCRETE
• Protective effects of concrete cover
– Physical barrier, e.g. diffusion
– Chemical protection, e.g. reaction with Cl
– High alkaline concrete passivates steel
– Provides medium of high electrolytic resistivity
– A high alkaline passive film is formed
• Concrete was thought to be durable
– To protect steel from corrosion
– Until last 20-30 years
• For corrosion to start
– This passive film has to be destroyed
– How?

• Mechanism of Corrosion
– Chloride penetration
– Carbonation

• Corrosion initiation
– The time that the passive film is destroyed
 CORROSION IN CONCRETE
• Some examples of rebar corrosion
CORROSION IN CONCRETE
 CORROSION SCIENCE
• Dissolves steel releases free electrons
• Fe  Fe++ + 2e-
• With dissolved oxygen, hydroxyl ions
formed
• O2 + 2H2O + 4e-  4(OH)-
• Further oxidized
• Fe++ + 2(OH)-  Fe(OH)2
• 2Fe(OH)2 + O2
• Corrosion product  rust
 CORROSION SCIENCE
• Schematic illustration of corrosion process
H2O
4OH-
Fe2O2H2O 2H2O O2

2Fe(OH)2 current
Anode
cathode

2Fe2+ 4e-
 CHLORIDE INDUCED
CORROSION
• Main source of chloride
– Marine environment
– De-icing salts
CHLORIDE INDUCED
CORROSION
 • De-icing salts
• USA, 0.5 M tonnes in 50s to 12 M.t. in 80s
• UK, 0.1 M.tonnes in 50s to 2 M.t. in 80s
• Calcium chloride in admixture
• Contamination of constituent materials

• Transport mechanism
• Diffusion, via pores under concentration gradient
• Absorption, via capillary flow due to MC gradient
• Others, e.g. electrostatic fields, cracks, etc.
• Rate of Cl transport is affected by the
nature of Cl present

• States of Cl in concrete
• Chemically bound, part of hydrated compounds
• Physically absorbed, on hydrate walls
• Free chlorides, present in pore fluids
 FACTORS AFFECTING CI
INGRESS
• Environmental factors
– Temperature
– External chloride concentration
Chloride profile
Temperature

OPC Chloride Content in

Rate of chloride

Concrete
transmission

Concrete

PFA

Temperature °C Depth from concrete surface

• Concrete characteristics
• Water cement ratio
• Concrete grade
• Curing
• Inclusion of cement replacement
• Blended cement

OPC Content % GGBS Content % Water Relative chloride

binder ratio diffusivity
100 0 0.6 100
100 0 0.5 45
100 0 0.4 20
60 40 0.6 2.5
40 60 0.6 5
20 80 0.6 1
 FACTORS AFFECTING
INITIATION
• Chloride content
– By free chloride content, water soluble
– Low risk when <0.4% by wt of cement
– Medium risk, between 0.4 to 1.0%
– High risk, >0.1%

• Alkalinity of pore fluids

– Cl/OH ratio but difficult to measure
– Cl/OH < 0.6  OK
– Cl/OH > 0.6  corroded
 PITTING CORROSION
O2 H2O
OH- OH-
Fe2+

O2 + H2O O2 + H2O

Acid forms Pit

2e-

Anode Fe + 2Cl  Fe2+ + 2Cl- + 2e

Followed by Fe2+ Cl2 + 2H2O  Fe(OH)2 + 2H+ + 2Cl-
Or in the presence of oxygen 6Fe2+ Cl2 + O2 + 8H2O  2Fe3O4 + 12H- + 12Cl-
Cathode ½ O2 + H2O + 2e  2OH-
 FACTORS AFFECTING
CORROSION
• Availability of chloride
• Free chloride content  rate and severity
• Chloride ion diffusivity to pits
• Ease of Cl passage to pits  rate
• Oxygen/moisture availability
• Fuel cathodic reaction
• Availability of hydroxyl ions OH
• Concrete resistivity
• Affected magnitude of currents flows
• Affected by moisture content and binders

• Concrete type and grade

Corrosion after 12 months salt spray exposure
70
Corrosion rate m/yr

60
OPC concrete PFA concrete
50

40

30
20

10

20 30 40 60 20 30 40 60
Design strength, N/mm2
 CARBONATION INDUCED
CORROSION
• Process of carbon by diffusion
– Ingress of carbon dioxide by diffusion
• 0.03% CO2 by volume in atmosphere
– Reaction with concrete pore fluids  carbonic acids
• H2O + CO2  HCO3 + H-
• HCO3  CO3 + H
– Carbonic acid reacts with alkaline constituents of
concrete  neutralization
• Ca(OH)2 + 2H + CO3  CaCO3 + 2H2O
(high alkaline pH = 12.5 – 13)
 FACTORS INITIATING
CORROSION
• pH drops to around 8.0
• Breakdown of passivation
• Corrosion occurs with moisture
• 75 – 80% RH required
• Electrochemical process
• Same as before
• Effect of pH on stability of steel

1.5

1.0 PASSIVATION
Electrode potential (Eh), v

Fe3O2
0.5 Steel in
concrete
typically
0 CORROSION

Fe2+
-0.5
Fe3O4
-1.0 IMMUNITY
CORROSION
Fe
-1.5

2 4 6 8 10 12 14 pH
 CORROSION RATE
• Factors affecting corrosion rate
• Relative humidity
• Temperature
• Cement content
• Degree of hydration
• Binder type
• Effect of environmental humidity on
corrosion

101 w/c = 0.9

Carbonated concrete
100 Wetting
Cell current A/cm2

Concrete cover = 4mm

10-1

10-2

10-3

70 80 90 100
Relative Humidity, %
• Effect of environmental humidity on
corrosion

10-1
Corrosion intensity, A/cm2

100

10-1

10-2

10-3

40 60 80 100 P
Relative humidity, %
• Effect of temperature on corrosion
Amount of rust after 150 days exposure, g/m2

70

60

50

40
30

20

10
0
55% 75% 85% 95%

Relative humidity
• Effect of alkalinity on corrosion
0.8
Rate of corrosion g/m2 Per day
0 0.2 0.4 0.6

0 8 10 12
pH
 PREVENTIVE METHODS
• Galvanized and coated reinforcement
– Galvanized by zinc, chromium, aluminium,
etc.
– Coated by epoxy, similar polymers
– Costly
• Cathiodic treatment
– Proved to be efficient but costly as well
• Quality of concrete
– Constituent (more alkaline), solid compacted
Galvanized
Cathodic protection