ICDS12 Lisbon Conference on Durable Structures

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation

LNEC Lisbon Portugal 31 May - 1 June 2012
DURABLE STRUCTURES
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LNEC Lisbon 31 May - 1June 2012
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MECHANISMS INVOLVED IN CHLORIDE

TRANSPORT THROUGH CONCRETE
SIMULATIONS OF THEIR EFFECTS ON
CHLORIDE PROFILES
O.Amiri & A. At-Mokhtar

University of La Rochelle CNRS LaSIE FRE 3474, France
IC
Durable Structures: From Construction to Rehabilitation

ICDS12 Lisbon: 31 May - 1 June 2012
DURABLE STRUCTURES
LNE
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OUTLINE
1/ Introduction : corrosion of steel in reinforced structures

2/ Limitations of the simplified models: Second Ficks law
3/ Multiphysics approach - an alternative?
4/ Difficulties of identification of the inputs of the model
5/ Simulation of chloride profile: influence of main parameters
6/ Conclusions
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The steel in concrete is protected by 3 ways

the concrete cover
the basicity of concrete (pH 13)
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the existence of a passive film on steel
What is
the problem ??
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Chlorides
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Example of degradation
Corrosion of steel in the bridge
pier P26 (R bridge, built on
1988 : La Rochelle (France)
Economic Issues: OCDE countries

4% of PIB spent in the
Framework of structures repair
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Limitations of second Ficks Law
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Solution in the case of infinite medium

(where D considered constant)
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Although many studies have shown the limitations of this law,

it is often used to predict chloride ingress: Simplicity
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Limitations of second Ficks Law
Physical limitations
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Interactions between the ions of the pore solution neglected

Pore solution considered as ideal solution
Convection (drying and wetting cycles) not considered
Electrical Double Layer (EDL) effect neglected
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Typical chloride profile obtained for field samples and

chloride profile predicted by Ficks diffusion model (Marchand et al, 2009)
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The diffusion is not the sole phenomenon involved

in the penetration of chlorides:
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Chloride transport in unsaturated concrete:

Multiphysics Approach
Main Hypothesis:
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Medium tri-phasic (solid, liquid, gas), the solid phase is

considered compact (without deformations
Phase change only between the liquid and the gas phases
Transfer isotherm
Approach : Modeling according 3 steps :
Transfer in liquid phase

Transfer in gas phase
Coupling
With the consideration of physical
phenomena mentioned previously
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1 - Liquid phase (water + ions):

Water (l) :
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Inputs of the model
Ions (i = Cl-, Na+, K+, OH-) :
Outputs of the model
Nernst Planck Equation
Ionic Activity
electrostatic
Interactions
Convection
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Diffusion
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2 Gas phase (air + vapor) :

Water Vapor (v):
Air (a) :
2n
f res ( o , l ) -2o o l
3 - Interface liquid - gas
(Millington, 1960)
Clapeyron Equation for a saline

solution
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Identification of the model inputs

Summary of the transport equations :
l ; pv ; pa ; CClf ;
CNaf ; CKf ; COHf
Experimental
parameters
CCl, b = f(CCl,f ) ;
DeCl, sat ; kg ; o
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The outputs
Bibliographical
parameters
krl ; krg ; frs ;

pc = f( l ) ; i ;
al ; kl ; DeCl
(electroneutrality condition)
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Influence of the diffusion coefficient
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In saturation, the main driving of chloride transport is the diffusion
The least variation of the diffusion coefficient generates important

differences in Chloride concentration:
The method of determination of D is important
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Determination of diffusion coefficient by migration test
- Chloride Dosage
- Electrical Current measurement
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Chloride Flux measurement in downstream compartment
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(Andrade, 93; Amiri et al, 97)
Chloride Flux measurement in upstream compartment
Chloride Flux measurement by electrical current
(Truc, 2000)
(Friedmann et al, 2004)
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Let us consider the Advantages and Disadvantages of the different

Methods
Dosage in downstream
Dosage in upstream
Electrical
Advantages
taking into account the

chlorides binding with cement
matrix
- rapid
- anodic reactions avoided
- high accuracy
(no dosage
required)
-multi-species
approach
Disadvantages
- need of electrodes with good

quality (expensive method)
- mono-species approach
- Renewal of solutions
- Inaccuracy of chloride
dosage due to the risk of
release of Cl2 and formation
of ClO
- need of several dilutions

(inaccuracies)
-mono-species approach
-the chlorides binding
with cement matrix
neglected
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Method
-the migration
test is carried out
in 2 steps (time
consuming)
-renewal of
solutions
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Comparison between simplified and physical models
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Cement paste (w/c = 0.5) immersed in saline solution during 100 Days (Sergi et al, 2002)
Good agreement between experimental and multiphysics model in

the case of humidification
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comparison between the model and experimental results obtained on mortar

submitted to 2 days humidification and 1 month drying (Francy, 98)
Good agreement between experiments and model

in the case of drying-wetting cycles
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Simulation of chloride profile :

The tested materials
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Simulation of chloride profile in two concretes: C22; C30 :

manufactured during MEDACHS project
Density
(g/cm3)
Materials
Coefficient
diffusion
Gas
Permeability
water/cement
Porosity
W/C
porosity
Dsat (m2/s)
K (m2)
C22
2.1
0.63
0.14
5.2*10-12
2*10-17
C30
2.2
0.5
0.1
1*10-12
9*10-18
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Simulation of chloride profile:

Influence of wetting and drying
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Chloride transport is accelerated when drying period is longuer

Comparatively to saturated case, the chloride ingress is accelerated of 20 years
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Similar behavior than C22:

The critical concentration is reached 5 years rather
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Influence electrostatic interactions
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The chloride transport is accelerated slightly: interaction potential

The effect could increase if concrete contains slag, fly ash...?
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Influence of chloride binding
Whatever the binding considered, the kinetic chloride ingress is decreased

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Effect of water permeability
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Concrete C22 submitted to a wetting during 3 months
Great influence of water permeability: driver of convection
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Influence of water adsorption isotherm
The chloride ingress depends on water isotherm:

GAB and BET: whatever the saturation type Bradley: high saturation
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Influence of the saturation of the material
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The saturation of the material controls the chloride penetration:

when the material is not saturated, convection occurs
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Influence of the concrete cover
The least variation of the concrete cover generates important differences in [Cl-]
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Conclusions
1. Multiphysics approach is more realistic but requires several

inputs
2. The chloride profile is influenced by the:
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Chemical binding of cement matrix with chlorides

Initial saturation degree of the concrete and water isotherm and
water permeability
Thickness of the concrete cover
Longer drying, shorter wetting
Electrostatic interactions
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Required improvements
1. Actually modeling requires more experimental validation,

for example in the cases of tide, splash and spray zones:
Only very few studies were carried out until now
2. To reduce the empiricism of some inputs, the
heterogeneity of the material should be taken into
account
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Thank you
LNE
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ICDS12 Lisbon Conference on Durable Structures

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ICDS12

International Conference DURABLE STRUCTURES: from construction to rehabilitation

LNEC Lisbon 31 May - 1June 2012

MECHANISMS INVOLVED IN CHLORIDE

O.Amiri & A. At-Mokhtar

Durable Structures: From Construction to Rehabilitation

LNEC Lisbon 31 May - 1June 2012

1/ Introduction : corrosion of steel in reinforced structures

LNEC Lisbon 31 May - 1June 2012

The steel in concrete is protected by 3 ways

the basicity of concrete (pH 13)

the existence of a passive film on steel

LNEC Lisbon 31 May - 1June 2012

Economic Issues: OCDE countries

LNEC Lisbon 31 May - 1June 2012

Limitations of second Ficks Law

Solution in the case of infinite medium

Although many studies have shown the limitations of this law,

LNEC Lisbon 31 May - 1June 2012

Limitations of second Ficks Law

Interactions between the ions of the pore solution neglected

LNEC Lisbon 31 May - 1June 2012

Typical chloride profile obtained for field samples and

The diffusion is not the sole phenomenon involved

LNEC Lisbon 31 May - 1June 2012

Chloride transport in unsaturated concrete:

Medium tri-phasic (solid, liquid, gas), the solid phase is

Approach : Modeling according 3 steps :

Transfer in liquid phase

LNEC Lisbon 31 May - 1June 2012

1 - Liquid phase (water + ions):

Inputs of the model

Ions (i = Cl-, Na+, K+, OH-) :

Outputs of the model

Nernst Planck Equation

LNEC Lisbon 31 May - 1June 2012

2 Gas phase (air + vapor) :

3 - Interface liquid - gas

Clapeyron Equation for a saline

LNEC Lisbon 31 May - 1June 2012

Identification of the model inputs

krl ; krg ; frs ;

LNEC Lisbon 31 May - 1June 2012

Influence of the diffusion coefficient

In saturation, the main driving of chloride transport is the diffusion

The least variation of the diffusion coefficient generates important

The method of determination of D is important

LNEC Lisbon 31 May - 1June 2012

Determination of diffusion coefficient by migration test

- Electrical Current measurement

LNEC Lisbon 31 May - 1June 2012

Chloride Flux measurement in downstream compartment

(Andrade, 93; Amiri et al, 97)

Chloride Flux measurement in upstream compartment

Chloride Flux measurement by electrical current

(Friedmann et al, 2004)

LNEC Lisbon 31 May - 1June 2012

Let us consider the Advantages and Disadvantages of the different

taking into account the

- need of electrodes with good

- need of several dilutions

LNEC Lisbon 31 May - 1June 2012

Comparison between simplified and physical models