Carbonation & Chloride

Penetration ofConcrete
Structures
Dr Tommyo
CityUniversityofHong Kong
Annual Concrete Sem inar 2005 1
Definition ofConcrete Durability
1 Resistance to physical and
chemical deterioration ofconcrete
resulting from
1 Interaction with environment - e ternal
2 Interaction between constituents- internal
2 Protection ofembedded steel
from corrosion processes
Annual Concrete Sem inar 2005 3
Durable concrete must have the abilityto
withstand the potentially deteriorativ
conditionsto whic it can reasonablybe e
pected to be e posed
Annual Concrete Sem inar 2005 2
Durability
Concrete Deterioration
Physical Chemical Reinforcement
Deterioration Deterioration Corrosion
Carbonation Chlorid es
Annual Concrete Sem inar 2005 4
Mechanism
ofCarbonation
Ca(0H
!
" C0
!
#
CaC0
$
" H
!
0
involvesa
physiochemical
reaction between
atmosphericcarbo
n dio ide and the
calcium hydro ide
generated in
cement hydration
%he precipitation
of calcium
carbonate
asshown in the
following e&uation
reducesthe pH
level of concrete
Annual Concrete Sem inar 2005
Mechanism
ofCarbonation
1 'tep (
H
!
0"C0
!
) HC0
$
-
" H
"
HC0
$
-
)
C0
$
!-
"
H
"

2 'tep !
Ca(0H
!
" !H
"
"
C0
$
!-

1=
Ca
C
0
$
"
!
H
!
0

3 %hisneutra
lisation
reaction
penetrates
graduallyinto
the concrete
surface
4 Penetration
Rate ) * time
(l!

Annual Concrete Sem inar 2005 6
1
Change in Ph
%he atmosphericcarbon dio ide difuses into
the hardened concrete through pores and
when carbonation reaction ta*esplace+ the
al*alinityofthe concrete reducesfrom ( to
below,
Annual Concrete Sem inar 2005 7
actorsafectingcarbonation
1 Humidity- ideally- -. /
1 lower+ not enough water
2 higher water inhibitsC0
!
difusion
2 %emperature - worse in
hot environments
3 Concentration ofC0
!
gasin
atmosphere
1 0ormally $/ but increasingannually
2 Higher in cities+ due to motor
vehiclesand fossil fuel burning
Annual Concrete Sem inar 2005 8
TestingMetho
d
%he measurement
ofcarbonation depth
using the
phenolphthalein
solution wascarried
out by sprayingthe
indicator on the split
surface ofthe concrete
cylinder %he solution
became a pin* colorin
the carbonated
concrete and can be
diferentiated from the
uncarbonated
concrete+ giving a
distinc boundary
mar*ing the
carbonation front
1carbonation depth
upto an accuracyof
-mm can be identified
with the na*ed ey
Annual Concrete Sem inar 2005
Samples sprayed
with
phenolphthalein
solution
Annual Concrete Sem inar 2005 10
Mechanism
!
"henol"htha
lein solution
method
%he
colourle
ss
acidlbas
e
indicato
r
(phenol
phthalei
n
solution

monitori
ngthe
carbona
tion
depth is
by
capturin
g the
depth at
whic the
pH
isabout
,
It
indicates
the
boundary
at whic
the
carbonat
ed front
meets
with the
uncarbon
ated
concrete+
where
concrete
is
al*aline
Annual Concrete Sem inar 2005
oimitation
%here e
istsa
partially
carbona
ted
2one
where
the pH
value
isnot
easilyde
tected
usingph
enolpht
halein
indicato
r Past
evidenc
hassho
wn that
carbon
dio ide
could
react at
the
depthsg
reater
than
those
indicate
d by
phenolp
hthalein
indicato
r
Annual Concrete Sem inar 2005 12
2
T#$#nnovative %""roach
3%-IRspectroscopyisa powerful tool for
determiningthe structure ofthe functional
groupsthat build upthe molecules 4hen the
IRlight- passesthrough the sample+ each
functional group resonates in its
characteristic absorption fre&uencies in the
infrared region ofthe electromagnetic
spectrum
Annual Concrete Sem inar 2005 13
&ui"ment T!#$
Annual Concrete Sem inar 2005 14
Concrete
131.4
120
110
Carbo
nation
Carbonation -
transformation of the
C=OO bonds of CO2
to the formation of '
(!
CO bonds in the
CaCO3.
100
90
%T 80
70
60
T
h
e
three C
O bonds
in the
i
n
C
a
(
)
50
40
30.0
4000.0
Annual Concrete Sem inar 2005
T
h
e

c
h
a
r
a
c
t
e
r
i
s
t
i
c

p
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a
k

o
f

t
h
e

C

O

f
u
n
c
t
i
o
n
a
l

g
r
o
u
p

i
n

t
h
e

w
a
v
e

n
u
m
b
e
r

r
a
n
g
e

p
o
s
i
t
e
.
131.4
120
110
100
90
%T 80
70
60
50
40
30.0
4000.0
Annual Concrete Sem inar 2005
I
R
s
p
e
c
t
r
u
m

a
n
a
l
y
s
i
s
1
prod
uc
es
a
sci
en
tifi
c
m
ea
su
re
m
en
t
of
ca
rb
on
ati
on
de
pt
h
2
pro
vi
di
n
g
a
c
o
n
v
e
ni
e
nt
to
ol
fo
r
cr
o
s
3
4
Annual Concrete Sem inar 2005 18
Test "rogram
1 %o studythe efectsofinitial curingon the
depth ofcarbonation
2 %hree mi 1+ 5and C with wlcratiosof $6+
7and -
Annual Concrete Sem inar 2005 19
Powder samples were ta*en from the
cylinder at depthsof + ( -+ $ + -+ 7 + 6 + ( + (! +
( + (. + ! + and $ mm measured from the
surface %he IR spectrum ofeach powder
sample was mi ed with 55r in the proportion
of( 8 ( to facilitate &uantitative measurement
of carbonation depth
Annual Concrete Sem inar 2005 21
*'daycarbonation! age
Carbonation de"th determined usingT!#$
+air cured concrete, -lc. /0
Annual Concrete Sem inar 2005 23
%est method
3or each grade8
1 6numbersof( mm cubesand
2 6unitsof( <9! mm high cylinders
3 stored in water at !..$
$
C
4 after !6 days+ the cylinderswere coated with epo y
resin to ensure that the carbon dio ide could onlydifuse into
the concrete from two endsofthe sample
5 %he specimenswere transferred to an enclosed
chamber to accelerate the carbonation process%he
concentration ofcarbon dio ide in the chamber was*ept at
!/ and wasmonitored wee*lywith a portable infrared
carbon dio ide analy2er
Annual Concrete Sem inar 2005 20
1'daycarbonation! age
Carbonation de"th determined usingT!#$
+air cured concrete, -lc. /0
Annual Concrete Sem inar 2005 22
2'daycarbonation! age
Carbonation de"th determined usingT!#$
+air cured concrete, -lc. /0
Annual Concrete Sem inar 2005 24
4
1'daycarbonation! age *'daycarbonation! age
Carbonation de"th determined usingT!#$
Carbonation de"th determined usingT!#$
+-ater cured concrete, -lc. /0 +-ater cured concrete, -lc. /0
Annual Concrete Sem inar 2005 25 Annual Concrete Sem inar 2005 26
2'daycarbonation! age Com"arison Phenol"hthaleinlT#$+-ater0
Carbonation de"th determined usingT!#$
+-ater cured concrete, -lc. /0
Annual Concrete Sem inar 2005 27 Annual Concrete Sem inar 2005 28
Com"arison Phenol"hthaleinlT#$+air0
Annual Concrete Sem inar 2005 29
Carb
onati
on
de"t
h
incre
ased
-ith
time
3"he
nol"
hthal
ein
soluti
on4
Annual Concrete Seminar 2005 30
5
Com"arison ofcarbonation rate constant K
Carbonation de"th increased -ith time
3T!#$S"ectrum4
[1] Roy SK, Poh KB, Northwood DO. Durability of concrete accelerated carbonation and weathering studies. Building and Environment
1999;34:597 606 .
[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):267 72 .
[3] Balayssac JP , Detriche ChH, Grandet J . E!ect of curing upon carbonation of concrete. Construction and Building Materials 1995;9(2):91 5 .
AnnualAnnua ConcreteConcrete SeminarSemnar 20052005 31 Annual Concrete Sem inar 2005 32
Diferences+2 daysCarbonation de"th0
Annual Concrete Sem inar 2005 33
Schematicmod
el ofcarbonation
front using
"henol"hthalein
indicator and
#$s"ectrum
analysis
Annual Concrete Sem inar 2005 34
Carbonation depth by way of an IR
spectroscopic tes can be
determined by observing the
occurrenc of C 0 characteristic
pea*s relativ to the bac*ground
noise at wave number ( (- IR
spectrometry gives more
consistent results with lower
variationsin measurement than a
phenolphthalein solution %he
carbonation rate constant found
byIRspectrum analysis was!$ ,/
higher than that obtained using the
phenolphthalein indicator
Annual Concrete Sem inar 2005
1 0u
r
finding
ssugge
sted
that 3%
-IR
spectru
m
analysi
s
provide
s a
useful
tool for
providi
ng
early
warnin
gs of
carbon
ation in
structu
ral
survey
s
2 C
ompar
ed
with
carbo
nation
tes
using
Pheno
lphthal
ein
indicat
or+
using
3% -IR
analys
is is
more
accur
ate
Annual Concrete Sem inar 2005 36
6
Concrete & Steel Corrosion
Carbonation
Chlorides
Others than sea water
Sea water
e. g. de-icing salts
Annual Concrete Sem inar 2005 37
actorsafectingchloride attac5
6 Concentration ofchlorides- corrosion will
not occur belowa threshold level (somewhere
between ( and /
1 Humidity+ alternate wettingand drying
2 %emperature - worse in hot climates
3 Concrete permeabilityand
chloride bindingcapacity+ cement
content and type
4 P31and '3will helpresist chloride
ingress
Annual Concrete Sem inar 2005 38
TestsofChlori
de
ionsdifusion
Annual Concrete Sem inar 2005
1
0

)
-
9
Ty"e ofCement Paste
(
c
m

s
2
-
1
60
OPC
o
f

c
h
l
o
r
i
d
e
PFA 30%
0
C
o
e
f
f
30 50 70
Strength (MPa)
Annual Concrete Sem inar 2005 40
Mechani
sm
ofchlorid
e!
inducedc
orrosion
6 %node
$eaction
6
Cathode
$eaction
e (e 7 e
()
e
()
) (Cl
eCl( ) (H
H(8 8(
!
! Cl Cl
Cl
Cathode 8H
!
rust rust
e !
Annual Concrete Seminar 2005
S
o
ur
c
e
s
of
C
hl
or
id
e
s
1 Co
ntac
with
sea
water
2 3ro
m de-
icingsalt
s
3 3ro
m
beach
or sea
dredge
d
aggreg
ates
4
3r
o
m

a
c
c
e
l
e
r
a
t
o
r
s
(
c
h
l
o
r
i
d
e
-
b
a
s
e
d

a
d
m
i
t
u
r
e
s
n
o
w
p
r
o
h
i
b
i
t
e
d

Annual Concrete Sem inar 2005 42

7
actorsafectingchloride attac5
6 Concentration ofchlorides- corrosion will
not occur belowa threshold level (somewhere
between ( and /
1 Humidity+ alternate wettingand drying
2 %emperature - worse in hot climates
3 Concrete permeabilityand
chloride bindingcapacity+ cement
content and type
6 P31and '3will helpresist chloride ingress $elation bet-een "ermeabilityand-ater9cementratioforcement"astes
$ef: ;eville % M, Pro"ertiesofConcrete +1rd ed 0, <2=<
Annual Concrete Sem inar 2005 43 Annual Concrete Sem inar 2005 44
$elation bet-een "ermeabilityandca"ilary"orosityofcement"ast
$ef: ;eville % M, Pro"ertiesofConcrete +1rd ed 0, <2=<
Annual Concrete Sem inar 2005 45
Test "rogram
Annual Concrete Sem inar 2005 46
* days"ondingtes
6 %he specimensafter !6dayswere
cut into two parts
6 %he vertical surface ofconcrete
cylinder was sealed by epo y to
avoid the difusion of chloride ion
through thissurface
6 %est cylinderswere soa*ed in the
salt solution for one month and two
months
6 1t each month+ specimenswere
ta*en out from the salt solution and
dried for ! hoursat room
temperature and humidity %he
surface ofthe specimenswere
cleaned bycloth to remov the salt
crystal
6 Potentiometric%itration %est and
1g00
$
'olution 'pray%est were
ta*en to determine the chloride
content at diferent depth and the ma imum
AnnualConcrete Sem inar 2005 47
depth ofpenetration
Annual Concrete Sem inar 2005 48
8
Surface Chloride level
+KyPotentiometricTitration test0
Annual Concrete Sem inar 2005 49 Annual Concrete Sem inar 2005 50
Ky%g;'
1
Solution S"rayTest
Annual Concrete Sem inar 2005 51 Annual Concrete Sem inar 2005 52
De"th ofChloride Penetration ofM<, M( and M1 under %ir Curingafter ( Months
Annual Concrete Sem inar 2005 53
De"th ofChloride Penetration
ofM , M/and M*under %ir
Curingafter ( Months
Annual Concrete Sem inar 2005 54
9
Com"arison ofDe"th ofChloride Penetration Ket-een M< and
M De"th ofChloride Penetration ofM( under %ir Curing under %ir Curingafter < Months
and >ater Curingafter ( Months
Annual Concrete Sem inar 2005 55 Annual Concrete Sem inar 2005 56
Chloride ingress"rofiles
+byPotentiometricTitration Test0
The ( !month chloride ingress"rofiles
are sho-n byfollo-ingfigures The limit
ofchloride content ofconcrete is <?
bymassofcement %hori@ontal red line
isdra-n in each figure to indicate the de"th
of"enetration at <? limit
De"th ofChloride Penetration ofM1 under %ir Curing
after < and ( Months#mmersion
Annual Concrete Sem inar 2005 57 Annual Concrete Sem inar 2005 58
Chloride ingress"rofiles
+byPotentiometricTitration Test0
Annual Concrete Seminar 2005 59 Annual Concrete Sem inar 2005 60
10
Annual Concrete Sem inar 2005 61 Annual Concrete Sem inar 2005 62
Annual Concrete Sem inar 2005 63 Annual Concrete Sem inar 2005 64
Annual Concrete Sem inar 2005 65 Annual Concrete Sem inar 2005 66
11
Annual Concrete Sem inar 2005 67 Annual Concrete Sem inar 2005 68
T#$Chloride "enetration
131.4
120
110
100
90
%T 80
70
60
50
40
30.0
4000.0 3000 2000 1500 1000 400.0
cm-1
Annual Concrete Sem inar 2005 69
Tha
n5
o
u
Annual Concrete Sem inar 2005 70
1
2