Lnec - ICDS12: Chloride Transport Through Cementitious Membranes Using Pulsed Current

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
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
IC
DURABLE STRUCTURES
MOTIVATION
LNE
C
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.
2
ICDS12
DURABLE STRUCTURES
12
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
DS
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:
IC
2 Cl- + 3CaO(Al,Fe)2O3CaSO4 .10H2O 3CaO(Al,Fe)2O3CaCl2 .10H2O + SO42-
DURABLE STRUCTURES
BACKGROUND
LNE
C
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.
4
ICDS12
DURABLE STRUCTURES
BACKGROUND
Porous cementitious materials
can be modelled as a compact
cementitious matrix in parallel
with the porous structure.
DS
The physical image: an

electrical equivalent circuit with
resistive
and
capacitive
parallel paths.
12
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
IC
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
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
LNE
C
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
DURABLE STRUCTURES
DS
12
IC
100 nm
= 10-5 cm
DURABLE STRUCTURES
EXPERIMENTAL
AC/DC
LNE
C
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.
8
ICDS12
DURABLE STRUCTURES
12
DS
RESULTS
The non-steady state period is longer (twice) under AC migration.
IC
The steady state period higher slope under AC.
DURABLE STRUCTURES
LNE
C
The high frequency impedance spectra evolve with testing time.

1
0
ICDS12
DURABLE STRUCTURES
DS
12
The resistivity of the sample varies along the experiment.

Non-SS and SS are clearly differentiated. Synchronised with Cl- flux
IC
The frequency of the AC signal affects the magnitude of the resistivity.
1
1
DURABLE STRUCTURES
LNE
C
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.
1
2
ICDS12
DURABLE STRUCTURES
12
Conduction
through
capillary
pores
(dissolution of
Reference
Anode
Cathode
Bulk
Pore size / nm
Conduction
enhanced
through gel
pores
IC
portlandite)
AC 10 kHz
DS
Relative contribution to porosity / %
DC
1
3
DURABLE STRUCTURES
LNE
C
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))
1
4
ICDS12
DURABLE STRUCTURES
12
CONCLUSIONS
The pulsed current can enhance the transport

through the gel pores.
The frequency of pulses shall match the of pores.
DS
The frequency of pulses modifies the percolating

resistivity, which indicates that different levels of the
gel pores network are reached.
IC
Impedance Spectroscopy allows to follow the

structural changes associated to the transport/
bonding of chlorides
DURABLE STRUCTURES
LNE
C
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
1
5

Lnec - ICDS12: Chloride Transport Through Cementitious Membranes Using Pulsed Current

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lnec - ICDS12: Chloride Transport Through Cementitious Membranes Using Pulsed Current

Uploaded by

Copyright:

Available Formats

ICDS12

International Conference DURABLE STRUCTURES: from construction to rehabilitation

LNEC Lisbon 31 May - 1June 2012

CHLORIDE TRANSPORT THROUGH

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

LNEC Lisbon 31 May - 1June 2012

Most of the corrosion related problems in

The diffusion coefficient of chlorides is a

Cathodic protection and cathodic

LNEC Lisbon 31 May - 1June 2012

Two main hydrated phases are present in hydrated cement paste:

Chlorides in concrete can be:

Friedels salt results from the transformation of the AFm phase:

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

LNEC Lisbon 31 May - 1June 2012

Cementitious materials are of porous

The size of gel pores and nano-pores

Double layer properties will influence

The physical image: an

LNEC Lisbon 31 May - 1June 2012

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

The percolating porosity is

LNEC Lisbon 31 May - 1June 2012

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

NaOH pH 12, 1M NaCl

The high frequency domain (MHz)

R1, percolating porosity

LNEC Lisbon 31 May - 1June 2012

LNEC Lisbon 31 May - 1June 2012

AC: 0.1, 1, 10 kHz

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

LNEC Lisbon 31 May - 1June 2012

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

The steady state period higher slope under AC.

LNEC Lisbon 31 May - 1June 2012

The high frequency impedance spectra evolve with testing time.

LNEC Lisbon 31 May - 1June 2012

The resistivity of the sample varies along the experiment.

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

LNEC Lisbon 31 May - 1June 2012

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

The geometry of the cell was chosen so that:

LNEC Lisbon 31 May - 1June 2012

Relative contribution to porosity / %

LNEC Lisbon 31 May - 1June 2012

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

LNEC Lisbon 31 May - 1June 2012

The pulsed current can enhance the transport

The frequency of pulses modifies the percolating

Impedance Spectroscopy allows to follow the

LNEC Lisbon 31 May - 1June 2012

CHLORIDE TRANSPORT THROUGH

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

You might also like