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Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 1 1

Carbonation 8 Chloride Carbonation 8 Chloride
Penetration of Concrete Penetration of Concrete
Structures Structures
Dr. Tommy Lo Dr. Tommy Lo
City University of Hong Kong City University of Hong Kong
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 2 2
Durable concrete must have the ability to Durable concrete must have the ability to
withstand the potentially deteriorative withstand the potentially deteriorative
conditions to which it can reasonably be conditions to which it can reasonably be
expected to be exposed. expected to be exposed.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 3 3
Definition of Concrete Durability Definition of Concrete Durability
Resistance to physical and chemical Resistance to physical and chemical
deterioration of concrete resulting from deterioration of concrete resulting from
!nteraction with environment !nteraction with environment - - external external
!nteraction between constituents !nteraction between constituents - - internal internal
Protection of embedded steel from Protection of embedded steel from
corrosion processes corrosion processes
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 4 4
Durability Durability
Concrete Deterioration Concrete Deterioration
Physical Physical
Deterioration Deterioration
Chemical Chemical
Deterioration Deterioration
Reinforcement Reinforcement
Corrosion Corrosion
Carbonation Carbonation
Chlorides Chlorides
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 5 5
Nechanism of Carbonation Nechanism of Carbonation
Ca(OH) Ca(OH)
2 2
+ CO + CO
2 2
CaCO CaCO
3 3
+ H + H
2 2
O O
involves a physiochemical reaction involves a physiochemical reaction
between atmospheric carbon dioxide and between atmospheric carbon dioxide and
the calcium hydroxide generated in the calcium hydroxide generated in
cement hydration. The precipitation of cement hydration. The precipitation of
calcium carbonate as shown in the calcium carbonate as shown in the
following equation reduces the pH level of following equation reduces the pH level of
concrete. concrete.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 6 6
Nechanism of Carbonation Nechanism of Carbonation
Step 1 Step 1 H H
2 2
O+CO O+CO
2 2
= HCO = HCO
3 3
- -
+ H + H
+ +
HCO HCO
3 3
- -
= CO = CO
3 3
2 2- -
+ H + H
+ +
Step 2 Step 2 Ca(OH) Ca(OH)
2 2
+ 2H + 2H
+ +
+ CO + CO
3 3
2 2- -
= CaCO = CaCO
3 3
+2H +2H
2 2
O O
This neutralisation reaction penetrates This neutralisation reaction penetrates
gradually gradually into into the concrete surface. the concrete surface.
Penetration Penetration Rate Rate = k x time = k x time
1f2 1f2
2
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 7 7
Change in Ph Change in Ph
The atmospheric carbon dioxide diffuses The atmospheric carbon dioxide diffuses
into the hardened concrete through pores into the hardened concrete through pores
and when carbonation reaction takes place, and when carbonation reaction takes place,
the alkalinity of the concrete reduces from the alkalinity of the concrete reduces from
10 to below 9. 10 to below 9.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 8 8
Factors affecting carbonation Factors affecting carbonation
Humidity Humidity - - ideally 50 ideally 50- -70 70
lower, not enough water lower, not enough water
higher water inhibits CO higher water inhibits CO
2 2
diffusion diffusion
Temperature Temperature - - worse in hot worse in hot
environments environments
Concentration of CO Concentration of CO
2 2
gas in atmosphere gas in atmosphere
Normally 0.03 but increasing annually Normally 0.03 but increasing annually
Higher in cities, due to motor vehicles and Higher in cities, due to motor vehicles and
fossil fuel burning fossil fuel burning
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 9 9
Testing Nethod Testing Nethod
The measurement of carbonation depth using
the phenolphthalein solution was carried out by
spraying the indicator on the split surface of the
concrete cylinder. The solution became a pink
color in the carbonated concrete and can be
differentiated from the uncarbonated concrete,
giving a distinct boundary marking the
carbonation front. A carbonation depth upto an
accuracy of 0.5 mm can be identified with the
naked eye.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 10 10
Samples sprayed with phenolphthalein solution
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Nechanism Nechanism- - phenolphthalein solution method phenolphthalein solution method
The The colourless acidfbase indicator colourless acidfbase indicator
(phenolphthalein solution) monitoring the (phenolphthalein solution) monitoring the
carbonation depth is by capturing the carbonation depth is by capturing the
depth at which the pH is about 9. depth at which the pH is about 9.
!t indicates the boundary at which the !t indicates the boundary at which the
carbonated front meets with the carbonated front meets with the
uncarbonated uncarbonated concrete, where concrete is concrete, where concrete is
alkaline. alkaline.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 12 12
Limitation Limitation
T There exists a partially carbonated zone here exists a partially carbonated zone
where the pH where the pH value is not easily detected value is not easily detected
using phenolphthalein using phenolphthalein indicator. Past indicator. Past
evidence has shown that carbon dioxide evidence has shown that carbon dioxide
could react at the depths greater than could react at the depths greater than
those indicated by those indicated by phenolphthalein phenolphthalein
indicator indicator
3
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FT!R FT!R !nnovative Approach !nnovative Approach
FT FT- -!R spectroscopy is a powerful tool for !R spectroscopy is a powerful tool for
determining the structure of the functional determining the structure of the functional
groups that build up the molecules. When groups that build up the molecules. When
the !R the !R- -light passes through the sample, light passes through the sample,
each functional group resonates in its each functional group resonates in its
characteristic absorption frequencies in characteristic absorption frequencies in
the infrared region of the electromagnetic the infrared region of the electromagnetic
spectrum. spectrum.
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Equipment Equipment FT FT- -!R !R
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4000.0 3000 2000 1500 1000 400.0
30.0
40
50
60
70
80
90
100
110
120
131.4
cm-1
%T
Concrete Concrete
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C Carbonation arbonation - - transformation of the transformation of the
C=O bonds of CO C=O bonds of CO
2 2
to the formation of to the formation of
C C O bonds in the CaCO O bonds in the CaCO
3 3
. .
T The three C he three C O bonds in the inorganic O bonds in the inorganic
carbonate of the CaCO carbonate of the CaCO
3 3
are arranged in are arranged in
a a trigonal trigonal planar pattern. planar pattern.
T The characteristic peak of the C he characteristic peak of the C O O
functional group in the wave number functional group in the wave number
range of 1410 range of 1410 1510 cm 1510 cm
- -1 1
was was used to used to
identify carbonation in a complex identify carbonation in a complex
concrete composite. concrete composite.
C
++
O
2-
Ca
2+
Carbonation Carbonation
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 17 17
4000.0 3000 2000 1500 1000 400.0
30.0
40
50
60
70
80
90
100
110
120
131.4
cm-1
%T
Peak 1+00~1500 Peak 1+00~1500
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 18 18
produces a scient produces a scientif ific measurement of ic measurement of
carbonation depth carbonation depth
providing a convenient tool for cross providing a convenient tool for cross- -
examination examination
overcoming the deficiency of results from overcoming the deficiency of results from
conventional analytical methods conventional analytical methods
cannot give a continuous line representing cannot give a continuous line representing
the carbonation front the carbonation front
!R spectrum analysis !R spectrum analysis
4
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 19 19
Test program Test program
T To study the effects of initial curing on the o study the effects of initial curing on the
depth of carbonation. depth of carbonation.
Three Three mix mix A, B and C with A, B and C with wfc wfc ratios of 0.38, ratios of 0.38,
0.+6 and 0.5+ 0.+6 and 0.5+
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For each grade For each grade: :
8 numbers of 100mm cubes 8 numbers of 100mm cubes and and
8 units of 100 8 units of 100 200 mm high cylinders 200 mm high cylinders
stored in water at 27 stored in water at 27 3 3

C C
a after 28 days, the cylinders were coated with epoxy fter 28 days, the cylinders were coated with epoxy
resin to ensure that the carbon dioxide could only diffuse resin to ensure that the carbon dioxide could only diffuse
into the concrete from two ends of the sample into the concrete from two ends of the sample
T The specimens were transferred to an enclosed chamber he specimens were transferred to an enclosed chamber
to accelerate the carbonation process. The concentration to accelerate the carbonation process. The concentration
of carbon dioxide in the chamber was kept at 2 and of carbon dioxide in the chamber was kept at 2 and
was monitored weekly with a portable infrared carbon was monitored weekly with a portable infrared carbon
dioxide analyzer. dioxide analyzer.
Test method Test method
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 21 21
Powder samples were taken from the Powder samples were taken from the
cylinder at depths of 0, 1.5, 3.0, +.5, 6.0, cylinder at depths of 0, 1.5, 3.0, +.5, 6.0,
8.0, 10.0, 12.0, 1+.0, 17.0, 20.0, and 30 8.0, 10.0, 12.0, 1+.0, 17.0, 20.0, and 30. .0 0
mm measured from the surface. The !R mm measured from the surface. The !R
spectrum of each powder sample was spectrum of each powder sample was
mixed with mixed with KBr KBr in the proportion of 1 : 10 in the proportion of 1 : 10
to facilitate quantitative measurement of to facilitate quantitative measurement of
carbonation depth. carbonation depth.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 22 22
Carbonation depth determined using FT-!R
(air cured concrete, wfc=0.5+)
30-day carbonation age
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Carbonation depth determined using FT-!R
(air cured concrete, wfc=0.5+)
60-day carbonation age
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Carbonation depth determined using FT-!R
(air cured concrete, wfc=0.5+)
90-day carbonation age
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Carbonation depth determined using FT-!R
(water cured concrete, wfc=0.5+)
30-day carbonation age
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 26 26
Carbonation depth determined using FT-!R
(water cured concrete, wfc=0.5+)
60-day carbonation age
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 27 27
Carbonation depth determined using FT-!R
(water cured concrete, wfc=0.5+)
90-day carbonation age
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 28 28
C Comparison omparison PhenolphthaleinfFT!R PhenolphthaleinfFT!R ( (water water) )
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 29 29
C Comparison omparison PhenolphthaleinfFT!R PhenolphthaleinfFT!R ( (air air) )
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 30 30
Carbonation depth increased with time Carbonation depth increased with time
[ [phenolphthalein solution phenolphthalein solution| |
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Carbonation depth increased with time Carbonation depth increased with time
[ [FT FT- -!R Spectrum !R Spectrum| |
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 32 32
Comparison of carbonation rate constant K Comparison of carbonation rate constant K
[1] Roy SK, Poh KB, Northwood DO. Durability of concrete accelerated carbonation and weathering studies. Building and Environment
1999;34:597606.
[2] Roy SK, Northwood DO, Poh KB. E!ect of plastering on the carbonation of a 19 year old reinforced concrete building. Construction and
Building Materials 1996;10(4):26772.
[3] Balayssac JP, Detriche ChH, Grandet J. E!ect of curing upon carbonation of concrete. Construction and Building Materials 1995;9(2):915.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 33 33
Differences (90 days Differences (90 days Carbonation depth Carbonation depth) )
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 34 34
Schematic model of carbonation front using Schematic model of carbonation front using
phenolphthalein indicator and !R spectrum analysis phenolphthalein indicator and !R spectrum analysis
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 35 35
Carbonation depth by way of an !R
spectroscopic test can be determined by
observing the occurrence of CO
characteristic peaks relative to the
background noise at wave number 1+15. !R
spectrometry gives more consistent results
with lower variations in measurement than a
phenolphthalein solution. The carbonation
rate constant found by !R spectrum analysis
was 23.9 higher than that obtained using
the phenolphthalein indicator.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 36 36
Our findings suggested that FT-!R
spectrum analysis provides a
useful tool for providing early
warnings of carbonation in
structural surveys.
Compared with carbonation test
using Phenolphthalein indicator,
using FT-!R analysis is more
accurate.
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Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 37 37
Concrete & Steel Corrosion
Carbonation
Others than sea water
e. g. de-icing salts
Chlorides Chlorides
Sea water
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 38 38
Factors affecting chloride attack Factors affecting chloride attack
Concentration of chlorides Concentration of chlorides - - corrosion will corrosion will
not occur below a threshold level not occur below a threshold level
(somewhere between 0.1 and 0.+) (somewhere between 0.1 and 0.+)
Humidity, alternate wetting and drying Humidity, alternate wetting and drying
Temperature Temperature - - worse in hot climates worse in hot climates
Concrete permeability and chloride Concrete permeability and chloride
binding capacity, cement content and binding capacity, cement content and
type type
PFA and PFA and SF SF will help resist chloride will help resist chloride
ingress ingress
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 39 39
Tests of Chloride ions diffusion Tests of Chloride ions diffusion
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 40 40
Type of Cement Type of Cement Paste Paste
C
o
e
f
f
C
o
e
f
f
o
f

c
h
l
o
r
i
d
e

d
i
f
f
u
s
i
o
n

(
c
m
o
f

c
h
l
o
r
i
d
e

d
i
f
f
u
s
i
o
n

(
c
m
2 2
s s
- -
1 1
x

1
0
x

1
0
- -
9 9
) )
30 30
60 60
0 0
30 30
50 50 70 70
Strength ( Strength (M MP Pa a) )
OPC
PFA 30%
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 41 41
Mechanism of chloride Mechanism of chloride- -induced corrosion induced corrosion
Anode Reaction Anode Reaction
Fe Fe 2 2e e Fe Fe
2+ 2+
Cathode Reaction Cathode Reaction
2H 2H
2 2
O + O O + O
2 2
+ + + +e e +OH +OH
- -
H
2
O
H
2
O
O
2
O
2
Cl
-
Cl
-
OH
- OH
-
Cathode Cathode
Anode
e
-
e
-
Fe
2+
rust rust
Cl
-
Cl
-
Cl
-
Cl
-
Cl
-
Cl
-
Cl
-
Fe Fe
2+ 2+
+ 2Cl + 2Cl
- -
FeCl FeCl
2 2
FeCl FeCl
2 2
+ 2H + 2H
2 2
O O Fe(OH) Fe(OH)
2 2
+ 2HCl + 2HCl
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 42 42
Sources of Chlorides Sources of Chlorides
Contact with sea water Contact with sea water
From de From de- -icing salts icing salts
From beach or sea dredged aggregates From beach or sea dredged aggregates
From accelerators (chloride From accelerators (chloride- -based based
admixtures now prohibited) admixtures now prohibited)
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Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 43 43
Factors affecting chloride attack Factors affecting chloride attack
Concentration of chlorides Concentration of chlorides - - corrosion will corrosion will
not occur below a threshold level not occur below a threshold level
(somewhere between 0.1 and 0.+) (somewhere between 0.1 and 0.+)
Humidity, alternate wetting and drying Humidity, alternate wetting and drying
Temperature Temperature - - worse in hot climates worse in hot climates
Concrete permeability and chloride Concrete permeability and chloride
binding capacity, cement content and binding capacity, cement content and
type type
PFA and PFA and SF SF will help resist chloride ingress will help resist chloride ingress
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 44 44
Relation between permeability and waterJcement ratio for cement pastes
Ref.: Neville A. N., Properties of Concrete (3rd ed.), 1981
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 45 45
Relation between permeability and capillary porosity of cement paste
Ref.: Neville A. N., Properties of Concrete (3rd ed.), 1981
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 46 46
Test program Test program
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 47 47
The specimens after 28 days were cut into two The specimens after 28 days were cut into two
parts parts
The vertical surface of concrete cylinder was The vertical surface of concrete cylinder was
sealed by epoxy to avoid the diffusion of sealed by epoxy to avoid the diffusion of
chloride ion through this surface. chloride ion through this surface.
Test cylinders were soaked in the salt solution Test cylinders were soaked in the salt solution
for one month and two months. for one month and two months.
At each month, specimens were taken out from At each month, specimens were taken out from
the salt solution and dried for 2+ hours at room the salt solution and dried for 2+ hours at room
temperature and humidity. The surface of the temperature and humidity. The surface of the
specimens were cleaned by cloth to remove the specimens were cleaned by cloth to remove the
salt crystal. salt crystal.
Potentiometric Potentiometric Titration Test and Titration Test and AgNO AgNO
3 3
Solution Solution
Spray Test were taken to determine the chloride Spray Test were taken to determine the chloride
content at different depth and the maximum content at different depth and the maximum
depth of penetration. depth of penetration.
60 days ponding test
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 48 48
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Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 49 49
Surface Chloride level Surface Chloride level
(By (By Potentiometric Potentiometric Titration test) Titration test)
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 50 50
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 51 51
By AgNO
3
Solution Spray Test
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 52 52
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 53 53
Depth of Chloride Penetration of N1, N2 and N3 under Air Curing after 2 Nonths
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 54 54
Depth of Chloride Penetration of N+, N5 and N6 under Air Curing after 2 Nonths
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Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 55 55
Depth of Chloride Penetration of N2 under Air Curing
and Water Curing after 2 Nonths
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 56 56
Comparison of Depth of Chloride Penetration Between N1 and N+
under Air Curing after 1 Nonths
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 57 57
Depth of Chloride Penetration of N3 under Air Curing
after 1 and 2 Nonths !mmersion
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 58 58
Chloride ingress profiles
(by Potentiometric Titration Test)
The 2-month chloride ingress profiles
are shown by following figures. The
limit of chloride content of concrete is
0.1 by mass of cement. A horizontal
red line is drawn in each figure to indicate
the depth of penetration at 0.1 limit.
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 59 59
Chloride ingress profiles
(by Potentiometric Titration Test)
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 60 60
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4000.0 3000 2000 1500 1000 400.0
30.0
40
50
60
70
80
90
100
110
120
131.4
cm-1
%T
FT!R FT!R Chloride penetration ? Chloride penetration ?
Annual Concrete Seminar 2005 Annual Concrete Seminar 2005 70 70
Thank You! Thank You!