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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

DS

CHLORIDE TRANSPORT THROUGH


CEMENTITIOUS MEMBRANES USING
PULSED CURRENT
B. Daz a, X.R. Nvoa a, B. Puga a, V. Vivier b
a

Grupo ENCOMAT, Universidade de Vigo, ETSEI, Campus Univ., Spain,


LISE UPR 15 du CNRS,-4 place Jussieu, 75252 Paris Cedex 05, France

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DURABLE STRUCTURES

LNEC Lisbon 31 May - 1June 2012

MOTIVATION

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Most of the corrosion related problems in


marine environments are due to chlorides.

The diffusion coefficient of chlorides is a


key parameter in the estimation of
service life.
Electrochemical chloride extraction
and realkalinisation are passivityrestoration techniques under development

Cathodic protection and cathodic


prevention are widely used techniques
in corrosion control in structures exposed
to the marine environment.
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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

12

LNEC Lisbon 31 May - 1June 2012

BACKGROUND

Two main hydrated phases are present in hydrated cement paste:


calcium hydroxysilicate,
(C-S-H) 3CaOSiO2nH2O
alumina-ferric oxide monosulphate, (AFm) 3CaO(Al,Fe)2O3CaSO4nH2O

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Chlorides in concrete can be:


Chemically bonded (Friedels salt)
Adsorbed (at the C-S-H gel layers)
Free (important in rebars corrosion)

Friedels salt results from the transformation of the AFm phase:

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2 Cl- + 3CaO(Al,Fe)2O3CaSO4 .10H2O 3CaO(Al,Fe)2O3CaCl2 .10H2O + SO42-

DURABLE STRUCTURES

LNEC Lisbon 31 May - 1June 2012

BACKGROUND

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Cementitious materials are of porous


nature. Hardened OPC paste has about
15% porosity.
Most of the porosity is concentrated in
the nanometer size range.

The size of gel pores and nano-pores


approaches that of the double layer
(Debye length), 2 nm.
(S. Chatterji, M. Kawamura, Cem. Conc. Res. 22(1992)774)

Double layer properties will influence


the electrokinetic phenomena induced
by migration experiments.
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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

BACKGROUND
Porous cementitious materials
can be modelled as a compact
cementitious matrix in parallel
with the porous structure.

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The physical image: an


electrical equivalent circuit with
resistive
and
capacitive
parallel paths.

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LNEC Lisbon 31 May - 1June 2012

M. Cabeza, M. Keddam, X. R. Nvoa, I. Snchez, H. Takenouti,


Electrochim. Acta 51 (2006) 18311841

Bulk
Bulk

C1

Percolating
pores

R1

C2

R2

Occluded
pores

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The percolating porosity is


closely linked to gel pores, thus
in the few nm range: ionic
migration will be affected by
pore wall charge (double layer
effects).

DURABLE STRUCTURES

LNEC Lisbon 31 May - 1June 2012

BACKGROUND

B. Daz, X.R. Nvoa, M.C. Prez,


Cem. Conc. Composites 28 (2006) 237245

NaOH
pH 12
1M NaCl

NaOH pH 12, 1M NaCl

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NaOH
pH 12

The high frequency domain (MHz)


corresponds to the contribution of
the bulk. The low frequency (kHz)
to the pore structure.

R1, percolating porosity

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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100 nm
= 10-5 cm

DURABLE STRUCTURES

LNEC Lisbon 31 May - 1June 2012

EXPERIMENTAL

AC/DC

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Cl-

[OH-]= 0.5M
(NaOH+KOH)
NaCl 1M

[OH-]= 0.5M
(NaOH+KOH)

CATHOLYTE

ANOLYTE

AC: 0.1, 1, 10 kHz

0
DC

-0.3 mA.cm-2

-0.6 mA.cm-2
50% duty cycle
t

2.5 cm

Z: 40 MHz

10Hz

Cement paste: CEM I 52.5R, w/c = 0.5


Periodic impedance measurements: 40 MHz to 10 Hz.
Periodic speed of sound measurements. MIP at the end of the tests.
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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

12

LNEC Lisbon 31 May - 1June 2012

DS

RESULTS

The non-steady state period is longer (twice) under AC migration.

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The steady state period higher slope under AC.

DURABLE STRUCTURES

LNE
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LNEC Lisbon 31 May - 1June 2012

The high frequency impedance spectra evolve with testing time.


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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

The resistivity of the sample varies along the experiment.


Non-SS and SS are clearly differentiated. Synchronised with Cl- flux

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The frequency of the AC signal affects the magnitude of the resistivity.

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DURABLE STRUCTURES

LNE
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LNEC Lisbon 31 May - 1June 2012

B. Daz, L. Freire, X.R. Nvoa, B. Puga, V. Vivier


Cem. Conc. Res. 40 (2010) 14651470

The geometry of the cell was chosen so that:


Accurate R1 values could be obtained
Almost no current flow at the edges reference material for MIP.
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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

12

LNEC Lisbon 31 May - 1June 2012

Conduction
through
capillary
pores
(dissolution of

Reference
Anode
Cathode
Bulk

Pore size / nm

Conduction
enhanced
through gel
pores

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portlandite)

AC 10 kHz

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Relative contribution to porosity / %

DC

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DURABLE STRUCTURES

LNE
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LNEC Lisbon 31 May - 1June 2012

Sound waves (0.5 MHz) emitted/collected in direction normal to the


current flux. v0~ 1 km.s-1.

The speed of sound increases more under DC condition (higher watersaturation degree higher porosity (degradation))
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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

12

LNEC Lisbon 31 May - 1June 2012

CONCLUSIONS

The pulsed current can enhance the transport


through the gel pores.
The frequency of pulses shall match the of pores.

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The frequency of pulses modifies the percolating


resistivity, which indicates that different levels of the
gel pores network are reached.

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Impedance Spectroscopy allows to follow the


structural changes associated to the transport/
bonding of chlorides

DURABLE STRUCTURES

LNEC Lisbon 31 May - 1June 2012

LNE
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CHLORIDE TRANSPORT THROUGH


CEMENTITIOUS MEMBRANES USING
PULSED CURRENT
B. Daz a, X.R. Nvoa a, B. Puga a, V. Vivier b

Grupo ENCOMAT, Universidade de Vigo, ETSEI, Campus Univ., Spain,


LISE UPR 15 du CNRS,-4 place Jussieu, 75252 Paris Cedex 05, France

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