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CORROSION OF REINFORCED CONCRETE

(advanced topics)
-macro-corrosion vs. micro-corrosion
-an example of corrosion rate analytical model
-crack effect
Ha-Won Song
Professor
School of Civil and Environmental Engineering
Yonsei Univ., Seoul 120-749, KOREA

Basics
There is some reinforced
concrete structures exposed
under the severe
environmental conditions.

The steels in concrete are


corroded.

Pier, 60 years

Cl
Concrete

Steel Corrosion in Concrete


Anode
Fe Fe2++2eCathode O2+2H2O+4e- 4OH-

eeAnode

Steel
Cathode

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Basics (cont.)

The corrosion start time


could be estimated by
analyzing the permeation
of chloride ions in concrete.

Corrosion start
Crack by
corrosion

Depassivat
(CTL)

Cl- content (wt%)

It is necessary to check the


durability of the reinforced
concrete throughout long
term.

Degradation

Cl- penetration

ion Time

1.0
0.8

Simulation
Measurement

0.6
0.4
0.2
0

0
10
20
30
Distance from surface (cm)
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Corrosion initiation
pH of Portland cement = 12.5 ~ 13
Cl-

Cl-

Concrete depassivation
bound ClSteel

Cl-

free Cl-

Passivation film
Fe2+ + 2Cl-

FeCl2

FeCl2 + 2H2O Fe(OH) 2 + 2H + + 2Cl-

Chloride Threshold Level (CTL)

Acidification
A pH fall
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Location of Defect and Steel Element

Element-1 Element-2
Steel
Crack

Concrete
Cl-

O2
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Effect of cracks
Corrosion Reaction
Anode :
Cathode :

Fe Fe 2+ + 2e -

O2+ 2 H 2O+ 4e - 4OH Crack

Change of Diffusivity
Cl-

O2

ClCl-

O2

O2

Chloride

Oxygen

Corrosion Current Density

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Corrosion rate due to cracks


It is necessary to predict the corrosion rate
considering the macrocell corrosion at the
bending crack.
cf) C. Andrade, I. R. Maribona, S. Feliu, J. A. Gonzalez, and S. Feliu, Jr (1992),
N. Sato (1995)

Cl

Cl

Concrete

Concrete
C

Micro
-cell

Micro
-cell

Micro
-cell

Anode

Macro-cell
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Corrosion rate model


The basic model which estimates the corrosion rate in
the reinforced concrete with the crack can be
proposed.

Flow

Construction of model
Verification using specimen
mortar
concrete
Confirmation of engineering value of model
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Influence on Corrosion Rate


Output data

Corrosion Rate

Microcell Corrosion Rate

Macrocell Corrosion Rate

Input data
Anodic
Cathodic
Electric Resistance
Polarization Polarization between Anode and Cathode
Curve
Curve
Polarization
Resistance

Concrete
Resistance

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Example of Polarization Curve


Potential (V)

0.1

-0.1

Cl : 0%
-

Cl : 6%

-0.3
-

Cl : 3%

Cl : 15%

-0.5

-0.7
0.00001 0.0001 0.001

0.01

0.1

Current (micro A/cm )


anodic polarization curves of steel in
saturated hydraulic calcium oxide
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Influence on Corrosion Rate


Output data

Corrosion Rate

Microcell Corrosion Rate

Macrocell Corrosion Rate

Input data
Anodic
Cathodic
Electric Resistance
Polarization Polarization between Anode and Cathode
Curve
Curve
Polarization
Resistance
Parameter for specimen test Crack

Concrete
Resistance

Humidity

W/C

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Divided Rebar & Corrosion Cell


A
C

: Anode
: Cathode

Macrocell
C
A

C
C

A
C

C
C

C
C

Microcell

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Analysis Procedure of
Microcell Corrosion
Steel

Rp

Rp
Concrete
Crack

Potential (V)

Element-1 Element-2
Cathodic polarization curve

EC2
EA2

EC 2 E A 2 = (Rp2 + Rp2 ) I micro


unknown

Potential loss
Anodic polarization curve

Imicro

Current (A)
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analysis Procedure of
Macrocell Corrosion
C

Rp

Rp
Rc

Potential (V)

Element-1 Element-2
Cathodic polarization curve

EC1

EA2

Potential
loss
Anodic polarization curve

Imacro

EC' 1 E A' 2 = (Rp1 + Rc + Rp2 ) I macro

Current (A)

unknown
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Polarization resistance:

The slope at the origin of the


polarization curve is defined as the
polarization resistance, Rp:

a
c

Rp =
=
di

app ,c 0 2.3 i corr ( a + c )

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Tafels extrapolation
technique corrosion rate
0

I corr =

a c
2 .3 R P ( a + c )

-100

Anodic curve

Icorr

corrosion rate

anodic curve slop

cathodic curve slop

RP

polarization resistance

Potential(mV)

-200
-300

Corrosion potential

-400

Cathodic curve

-500
-600
0.01

0.1

1
10
Current()

100

1000

Corrosion rate

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Verification with Mortar Specimen Configuration


Lead wire
Mortar

Element No.
1
234
0.5
20

Defect
(0.4mm, 0.2mm width)

Special divided
steel bar

5
6.0

Epoxy resin
[ cm ]

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Experimental and Analytical Cases

Control

No

Crack width
(mm)

No crack

0.2

0.4

Humidity
(RH%)

90

60

90

W/C
(%)

50

30

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Measurement Method of
Polarization Curves
Stainless board

Potentiostat

Reference electrode
(Ag/AgCl)

Gulvanostat

Steel element

Mortar
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Comparison of Polarization Curve


(1) Influence of Crack Width

0.4
0.2

0.6

0.4mm

No

Potential (V)

Potential (V)

0.6

0.2mm

0
-0.2
-0.4

0.4
0
-0.4
-0.6

-0.8
-1

-0.8
0.0001

0.001

0.01

0.1

Current density (mA/cm2 )

Anodic

0.4mm

-0.2

-0.6

0.00001

No

0.2

0.2mm

-1
0.00001

0.0001

0.001

0.01

0.1
2

Current density (mA/cm )

Cathodic

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Comparison of Polarization Curve


0.6

0.6

0.4

0.4

0.2

60%

Potential (V)

Potential (V)

(2) Influence of Humidity

0
-0.2

90%

-0.4

0.2
0
-0.2
-0.4

-0.6

-0.6

-0.8

-0.8

-1
0.00001

0.0001

0.001

0.01

0.1
2

60%
90%

-1
0.00001 0.0001

0.001

0.01

0.1

Current density (mA/cm )

Current density (mA/cm 2)

Anodic

Cathodic

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Comparison of Polarization Curve


0.6

0.6

0.4

0.4

0.2

30%

Potential (V)

Potential (V)

(3) Influence of W/C

50%

-0.2
-0.4

0
-0.2
-0.4

50%

-0.6

-0.6

-0.8

-0.8
-1
0.00001

30%

0.2

0.0001

0.001

0.01

0.1
2

Current density (mA/cm )

Anodic

-1
0.00001

0.0001

0.001

0.01

0.1
2

Current density (mA/cm )

Cathodic

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Measurement Method of
Polarization Resistance
Stainless board

Potentiostat

Reference electrode
(Ag/AgCl)

Frequency Response
Analyzer

i
Mortar
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

10000

1000

Crack

100

10

Wcr=0.4mm

Wcr=0.2mm

1
No crack

Polarization resistance (kOhm cm2)

Comparison of
Polarization Resistance

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Measurement Method of
Mortar Resistance
Potentiostat
Frequency Response
Analyzer

Mortar
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

8
6
4
RH90%, W/C50%

W/C30%

RH60%

Control*

Wcr=0.2mm

No crack

Mortar resistance (kohm)

Comparison of Mortar Resistance

*Wcr=0.4mm, RH90%, W/C50%


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analysis of
Microcell Corrosion Current
Potential (V)

0
-0.2
-0.4

Anodic
polarization
curve

Polarization Resistances
as potential loss

-0.6

Cathodic
polarization
curve

-0.8
-1
0.0001

0.001 Imicro 0.01

0.1

Current density (mA/cm2)


C A
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Potential (V)

Analysis of
Macrocell Corrosion Current
0

polarization resistances
-0.2 and mortar resistance

Anodic polarization
curves

-0.4
-0.6

Cathodic
polarization curves

-0.8
-1

Imacro
0.0001 0.001
0.01
0.1
Current density (mA/cm 2 )

C
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analyzed Corrosion Current Density


(microA/cm2)

Steel element

Microcell

Macrocell

0.4

-0.4

0.1

-2.5

5.0

17.0

1.4

5.7

0.1

-1.3
*Macrocell:
+ anode, -

cathode

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Distribution of
Analyzed Corrosion Current Density
Defect
Corrosion current density
(microA/cm2)

20
15
10

Macrocell

Microcell

0
-5
-4

-2

Steel location (cm)


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analyzed Corrosion Current Density


(microA/cm2)

Steel element
No

Microcell

Macrocell

Total

0.4

-0.4

0.4

0.1

-2.5

0.1

5.0

17.0

22.0

1.4

5.7

7.1

0.1

-1.3

0.1

*Macrocell:
+ anode, -

cathode

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Measurement Method of
Real Macrocell Corrosion Current

Ii-1.i
A

i-1

Ii+1.i
A

Non resistance
ammeter

i+1
Mortar

cf)
P. Schiebl, &
M. Raupach

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Measured total corrosion current


density (micro A/cm 2 )

Comparison between
Analyzed and Measured Values
100
10

No crack
Wcr=0.2mm
Control*
RH60%
W/C30%

1
0.1

*Wcr=0.4mm,
RH90%,
W/C50%

0.01
0.01
0.1
1
10
100
Analyzed total corrosion current density (micro A/cm 2 )
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Verification with Concrete Specimen Configuration

Bending crack
Element-No.

Special divided
steel(D10)
Concrete
Reinforcing
Lead line
bar

10
1

5
0.3

34 56 78
1.5

10

Epoxy resin

31.7
40

3
5

5
10

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

[cm]

Mixture Proportions of Concrete


W/C s/a
(%) (%)

Unit weight (kg/m3)

(g/m3)
Chem. Ad.

SP

WR

30

45

179 597

704

864

4770

50

49

185 370

848

886

111

70

53

191 273

954

848

821

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Experimental and Analytical Cases


No

Crack width (mm)

No crack

0.1

8
Control

9
10

W/C (%)
50
30

0.4

50
70

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Analysis of
Microcell Corrosion Current
Anodic
polarization
curve

0.2

Potential( V)

0
-0.2

polarization resistances

-0.4
Cathodic
polarization
curve

-0.6
-0.8
-1
-1.2
0.0001

Imicro
0.001

0.01

0.1

Current ( micro A/cm )


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analysis of
Macrocell Corrosion Current
0.2

Potential ( V)

0
-0.2

polarization resistances
and mortar resistance

Anodic
polarization
curve

-0.4
-0.6

Cathodic
polarization
curve

-0.8
-1
-1.2
0.0001

Imacro

0.001

0.01

0.1

Current (micro A/cm2)


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Analyzed Corrosion Current Density


(micro A/cm2)

Steel element
No

Crack part

Microcell Macrocell Total

0.3

-1.2

0.3

0.1

-0.5

0.1

0.7

3.7

4.4

2.2

7.2

9.4

0.1

-0.8

0.1

0.1

2.0

2.1

0.1

-1.8

0.1

0.2

-1.2

0.2

0.5

-0.4

0.5

10

0.1

-0.7

0.1

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Distribution of
Analyzed Corrosion Current Density
density (microA/cm2)

Corrosion current

Crack

8
6

Macrocell

4
2

Microcell

0
-2
0

10

20

30

Steel location (cm)


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Measured total corrosion current


density (micro A/cm2)

Comparison between
Analyzed and Measured Values
100
10

No crack
Wcr=0.2mm
W/C30%
Control
W/C70%

1
0.1
0.01

*Wcr=0.4mm,
W/C50%

0.001
0.001 0.01

0.1

10

100

Analyzed total corrosion current density

(micro A/cm2 )
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Defect (except No)


25
(microA/cm2)

Total corrosion current density

Influence of Crack

20
15
10

0.2mm

0.4mm
cf)
A. W. Beeby
(1983)

No

0
-4

-2

0
2
Steel location (cm)

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Total corrosion current density


2
(microA/cm )

Influence of Humidity
Defect

25
20

90%

15
10

60%

5
0
-4

-2

Steel location (cm)


Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Total corrosion current density


(microA/cm2)

Influence of W/C
Defect

25
20

50%

15
10

30%

5
0
-4

-2

Steel location (cm)

Concrete Materials, Mechanics &


Engineering Lab., Yonsei Univ.

Application of the Model


to Existing Structure
Crack

Concrete
Steel bar

Input data

Part

Sound
Sound

Defect
Defect

Anodic
polarization curve
Cathodic
polarization curve
Polarization
resistance
Concrete
resistance

Rp

Rp 1

Rp1 < Rp2

Rp 2

Analytically divided
into element
considering crack
and soundness.

From database, input


data ordered material
condition and
environmental condition.

Rc
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.