Durable c onc rete mus t have the abilityto

Carbonation & Chloride withstand the potentially deteriorative

conditionsto whic h it can reas onablybe
Penetration ofConcrete e pec ted to be e posed
Struc tures
Dr Tommyo o
CityUniv
ersityofHongKong

Annua
Annuall Concrete Sem inar 2005
Seminar 1 Annua
Annuall Concrete Sem inar 2005
Seminar 2

Durability
Def
inition ofConc
rete Durability
Concrete Deterioration
Resistanc e to physic
al and chemic al
deterioration ofc oncrete res
ultingfrom
I
nterac
tion with environment - e ternal Physical Chemical Reinforcement
I
nterac
tion between c onstituents- internal Deterioration Deterioration Corrosion

Protection ofembedded s
teel f
rom
corros
ion proc es
ses
Carbonation Chlorides

Annua
Annuall Concrete Sem inar 2005
Seminar 3 Annua
Annuall Concrete Sem inar 2005
Seminar 4

Mec
hanis
m ofCarbonation Mec
hanis
m ofCarbonation
Ca(0H)2 + C02 CaC03 + H20 Step1 H20+C02 = HC03- + H+
HC03- = C032- + H+
involvesa phys iochemical reac tion
between atmos phericcarbon dio ide and Step2 Ca(0H)2 + 2H+ + C032-
the c alc
ium hydro ide generated in = CaC03 +2H20
cement hydration The prec ipitation of Thisneutralisation reaction penetrates
calc ium c arbonate asshown in the graduallyinto the concrete s urf
ace
followingequation reduc esthe pH level of Penetration Rate = k time1l2
conc rete
Annua
Annuall Concrete Sem inar 2005
Seminar 5 Annua
Annuall Concrete Sem inar 2005
Seminar 6

1
 Change in Ph Fac
torsaf
fec
tingc
arbonation
The atmos phericc arbon dio ide dif fuses Humidity-
midity- ideally5 --7
7%
into the hardened c onc rete through pores lower, not enough water
and when c arbonation reac tion takesplace, higher water inhibitsC02 dif
fus
ion
the alkalinityofthe c oncrete reduc esfrom Temperature - wors e in hot
1 to below9 environments
Conc entration ofC02 gasin atmos
phere
Normally 3% but inc reasingannually
Higher in c ities
, due to motor vehic
lesand
f
os sil f
uel burning
Annua
Annuall Concrete Sem inar 2005
Seminar 7 Annua
Annuall Concrete Sem inar 2005
Seminar 8

Tes
tingMethod
The meas urement ofc arbonation depth us ing
the phenolphthalein s olution wasc arried out by
sprayingthe indic ator on the split s
urf ace ofthe
conc rete cylinder The s olution bec ame a pink
col orin the c arbonated c onc rete and c an be
differentiated from the unc arbonated c oncrete,
giving a dis tinct boundary marking the
carbonation f ront Ac arbonation depth upto an
acc uracyof 5mm c an be identif ied with the
naked eye
Samples sprayed with phenolphthalein solution
Annua
Annuall Concrete Sem inar 2005
Seminar 9 Annua
Annuall Concrete Sem inar 2005
Seminar 10

Mec
hanis
m-
m- phenolphthalein s
olution method
o
imitation
The colourless ac idl
base indic
ator
(phenolphthalein solution) monitoringthe There e is tsa partiallycarbonated z one
carbonation depth is by c apturing the where the pH value isnot eas ilydetected
depth at which the pH isabout 9 usingphenolphthalein indic ator Pas t
evidenc e hass hown that carbon dio ide
could reac t at the depthsgreater than
It indic ates the boundary at whic h the those indic ated by phenolphthalein
carbonated f ront meets with the indic
ator
unc arbonated c onc rete, where c
onc
rete is
alkaline

Annua
Annuall Concrete Sem inar 2005
Seminar 11 Annua
Annuall Concrete Sem inar 2005
Seminar 12

2
 quipment FT-
T-IR
R I
FTI
R nnov
ativ
e Approac
h

T-I
FT-I Rs pec troscopyisa powerf ul tool for
determiningthe s tructure ofthe func tional
groupsthat build upthe molec ules When
the I R--lig
light pas sesthrough the s ample,
eac h f unc tional group res onates in its
charac teris tic abs orption f requenc ies in
the infrared region ofthe elec tromagnetic
spec trum
Annua
Annuall Concrete Sem inar 2005
Seminar 13 Annua
Annuall Concrete Sem inar 2005
Seminar 14

131.4
Conc
rete Carbonation
120
Carbonation - transformation of the
C =O bonds of CO2 to the formation of
C=O 02-
110
CO
O bonds in the CaCO3.
100 C+
Ca2+
90
CO bonds in the inorganic
The three CO
%T
80 carbonate of the CaCO3 are arranged in
70 a trigonal planar pattern.
60

50
The characteristic peak of the CO
CO
functional group in the wave number
40
14101510 cm was used to
range of 14101510 1
30.0
4000.0 3000 2000 1500 1000 400.0
identify carbonation in a complex
cm-1 concrete composite.

Annua
Annuall Concrete Sem inar 2005
Seminar 15 Annua
Annuall Concrete Sem inar 2005
Seminar 16

131.4
Peak1 15 I
Rspec
trum analys
is
120

110
produc es a s cientif
ientific meas urement of
100
carbonation depth
90 providing a c onvenient tool f or c ross
-
%T
80 e amination
70
overcomingthe def iciencyofres ultsfrom
60
conventional analytical methods
50

40

30.0
4000.0 3000 2000 1500 1000 400.0
cannot give a c
ontinuousline repres
enting
cm-1
the c
arbonation f
ront

Annua
Annuall Concrete Sem inar 2005
Seminar 17 Annua
Annuall Concrete Sem inar 2005
Seminar 18

3
 Tes
t method
Tes
t program
For eac h grade:
rade:
To studythe ef fectsofinitial c
uring on the 8numbersof1 mm c ubesand
depth ofcarbonation 8unitsof1 <x2 mm high c ylinders
Three mi A, Kand C with wl cratiosof
cratiosof 38, stored in water at 27733C
6and 5 after 28 days , the c ylinderswere c oated with epo y
resin to ens ure that the c arbon dio ide c ould onlydif f
us e
into the c onc rete from two endsofthe s ample
The s pec imenswere trans ferred to an enc los ed chamber
to ac celerate the c arbonation proc essThe c onc entration
ofc arbon dio ide in the c hamber waskept at 2% and
wasmonitored weeklywith a portable inf rared c arbon
dio ide analyz er

Annua
Annuall Concrete Sem inar 2005
Seminar 19 Annua
Annuall Concrete Sem inar 2005
Seminar 20

30d
- aycar
bonat
ion age

Powder s amples were taken f rom the

cylinder at depthsof , 1 5, 3 , 5, 6 ,
8 , 1 , 12 , 1 , 17 , 2 , and 3
mm meas ured f
rom the s urf
ace The IR
spec trum ofeac h powder s ample was
mi ed with KKr in the proportion of1 : 1
to f acilitate quantitative measurement of
carbonation depth

Carbonation depth determined us

ingFT-I
R
(air c
ured c
onc
rete, wl
c= 5)
Annua
Annuall Concrete Sem inar 2005
Seminar 21 Annua
Annuall Concrete Sem inar 2005
Seminar 22

60d
- aycar
bonat
ion age 90d
- aycar
bonat
ion age

Carbonation depth determined us

ingFT-I
R Carbonation depth determined us
ingFT-I
R

(air c
ured c
onc
rete, wl
c= 5) (air c
ured c
onc
rete, wl
c= 5)
Annua
Annuall Concrete Sem inar 2005
Seminar 23 Annua
Annuall Concrete Sem inar 2005
Seminar 24

4
 30d
- aycar
bonat
ion age 60d
- aycar
bonat
ion age

Carbonation depth determined us

ingFT-I
R Carbonation depth determined us
ingFT-I
R
(water c
ured c
onc
rete, wl
c= 5) (water c
ured c
onc
rete, wl
c= 5)
Annua
Annuall Concrete Sem inar 2005
Seminar 25 Annua
Annuall Concrete Sem inar 2005
Seminar 26

90d
- aycar
bonat
ion age Comparis
on Phenolphthaleinl
FTI
R(
R(water)
ater)

Carbonation depth determined us

ingFT-I
R
(water c
ured c
onc
rete, wl
c= 5)
Annua
Annuall Concrete Sem inar 2005
Seminar 27 Annua
Annuall Concrete Sem inar 2005
Seminar 28

Comparis
on Phenolphthaleinl
FTI
R(
R(air)
air) Carbonation depth increas ed with time
[phenolphthalein s
olution]
tion]

Annua
Annuall Concrete Sem inar 2005
Seminar 29 Annual
Annual Concrete Seminar
Sem inar 2005 30

5
 Comparis
on ofc
arbonation rate c
ons
tant K
Carbonation depth inc
reas
ed with time
[FT-
T-IRSpec trum]
m]

[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
Annual Concrete Seminar
Sem inar 2005 31 Annua
Annuall Concrete Sem inar 2005
Seminar 32

Dif
ferenc
es(9 day
sCarbonation depth)
th) Schematicmodel ofc arbonation f
ront using
phenolphthalein indic
ator and I
Rs pectrum analys
is

Annua
Annuall Concrete Sem inar 2005
Seminar 33 Annua
Annuall Concrete Sem inar 2005
Seminar 34

Carbonation depth by way of an I R

spec troscopic test c an be determined by
0ur f indingss ugges ted that FT-IR
obs erving the oc currenc e of C0 spec trum analys is provides a
charac teristic peaks relative to the us eful tool f or providing early
bac kground nois e at wave number 1 15 I R warnings of c arbonation in
spec trometry gives more c onsistent results structural surveys
with lower variationsin meas urement than a
phenolphthalein s olution The c arbonation Comp ared with c arbonation tes t
rate c ons tant f
ound byI Rs pectrum analys is us ing Phenolphthalein indic ator,
was23 9% higher than that obtained us ing us ing FT-I R analys is is more
the phenolphthalein indic ator ac curate
Annua
Annuall Concrete Sem inar 2005
Seminar 35 Annua
Annuall Concrete Sem inar 2005
Seminar 36

6
 Fac
torsaf
fec
tingc
hloride attac
k
Concrete & Steel Corrosion
Conc
entration ofc
hlorides-
hlorides- corrosion will
not oc
cur belowa thres
hold level
(somewhere between 1 and %)
Humidity, alternate wettingand drying
Carbonation Chlorides
Temperature - wors e in hot climates
Conc rete permeabilityand c hloride
bindingc apac ity, c
ement c ontent and
Others than sea water type
Sea water
e. g. de-icing salts
PFAand SFw Fwill helpres is
tc hloride
ingress
Annua
Annuall Concrete Sem inar 2005
Seminar 37 Annua
Annuall Concrete Sem inar 2005
Seminar 38

Tes
tsofChloride ionsdif
fus
ion Ty
pe ofCement Pas
te
-9)
-1 x 10-9
Coeff of chloride diffusion (cm2s-1

60

30 OPC

PFA 30%

0
30 50 70
Strength (M
(MPa)

Annua
Annuall Concrete Sem inar 2005
Seminar 39 Annua
Annuall Concrete Sem inar 2005
Seminar 40

Mechanism ofchl
oride-
e-inducedcor
rosion
Anode Reac tion Cathode Reac
tion Sourc
esofChlorides
Fe 2e Fe2+ 2H20 + 02 + e 0H-
Fe2+ + 2Cl- FeCl2 Contact with sea water
From de-ic
de-icings alts
FeCl2 + 2H20 Fe(0H)2 + 2HCl
H2O O2 O2 H2O
From beac h or sea dredged aggregates
-
Cl
From ac c
elerators(c hloride-bas
hloride-bas
ed
-
Cl -
Cl
-
Cl -
Cl
-
-
Cl -
Cl admi turesnowprohibited)
Cl OH-
Cat
hode OH- Cat
hode

r
ust r
ust
-
Cl
Fe2+
e- e-
Annual
Annual Concrete Seminar
Sem inar 2005 Anode 41 Annua
Annuall Concrete Sem inar 2005
Seminar 42

7
 Fac
torsaf
fec
tingc
hloride attac
k
Conc
entration ofc
hlorides-
hlorides- corrosion will
not oc
cur belowa thres
hold level
(somewhere between 1 and %)
Humidity, alternate wettingand drying
Temperature - wors e in hot climates
Conc rete permeabilityand c hloride
bindingc apac ity, c
ement c ontent and
type
PFAand SFw
Fwill helpres
istc
hloride ingres
s Rel
ation bet
ween per
meabil
ityandwat
er/cementr
atiof
orcementpast
es

Ref: Neville A M, PropertiesofConc

rete (3rd ed ), 1981
Annua
Annuall Concrete Sem inar 2005
Seminar 43 Annua
Annuall Concrete Sem inar 2005
Seminar 44

Tes
t program

Rel
ation bet
ween per
meabil
ityandcapil
lar
ypor
osit
yofcementpast
e
Ref: Neville A M, PropertiesofConc
rete (3rd ed ), 1981
Annua
Annuall Concrete Sem inar 2005
Seminar 45 Annua
Annuall Concrete Sem inar 2005
Seminar 46

6 dayspondingtes
t
The s pec imensaf ter 28dayswere c ut into two
parts
The v ertic al s urface ofc oncrete c ylinder was
sealed by epo y to avoid the dif fusion of
chloride ion through thiss urface
Tes t c ylinderswere s oaked in the s alt solution
for one month and two months
A t eac h month, s pecimenswere taken out f rom
the s alt s olution and dried f or 2 hoursat room
temperature and humidity The s urfac e ofthe
spec imenswere c leaned byc loth to remove the
salt c rys tal
P otentiometricTitration
otentiometricTitration Tes t and AgN03 Solution
SprayTes t were taken to determine the c hloride
contentSeminar
Annua
Annuall Concrete Sem
at dif
inar 2005
ferent depth and the ma imum 47 Annua
Annuall Concrete Sem inar 2005
Seminar 48
depth ofpenetration

8
 Surfac e Chloride level
(KyP
yPotentiometricTitration
otentiometricTitration tes
t)

Annua
Annuall Concrete Sem inar 2005
Seminar 49 Annua
Annuall Concrete Sem inar 2005
Seminar 50

KyAgN03 Solution SprayTes

t

Annua
Annuall Concrete Sem inar 2005
Seminar 51 Annua
Annuall Concrete Sem inar 2005
Seminar 52

Depth ofChloride Penetration ofM1, M2 and M3 under Air Curingaf

ter 2 Months Depth ofChloride Penetration ofM , M5and M6under Air Curingaf
ter 2 Months

Annua
Annuall Concrete Sem inar 2005
Seminar 53 Annua
Annuall Concrete Sem inar 2005
Seminar 54

9
 Comparis
on ofDepth ofChloride Penetration Ketween M1 and M
Depth ofChloride Penetration ofM2 under Air Curing under Air Curingafter 1 Months
and Water Curingaf ter 2 Months
Annua
Annuall Concrete Sem inar 2005
Seminar 55 Annua
Annuall Concrete Sem inar 2005
Seminar 56

Chloride ingres
sprof iles
(byPotentiometricTitration Tes
t)

The 2-month c hloride ingressprof iles

are s hown byf ollowingf igures The
limit ofchloride content ofc oncrete is
1% bymas sofc ement Ahorizontal
red line isdrawn in eac
hf igure to indic
ate
the depth ofpenetration at 1% limit
Depth ofChloride Penetration ofM3 under Air Curing
af
ter 1 and 2 MonthsI mmersion
Annua
Annuall Concrete Sem inar 2005
Seminar 57 Annua
Annuall Concrete Sem inar 2005
Seminar 58

Chloride ingres
sprof
iles
(byPotentiometricTitration Tes
t)

Annual
Annual Concrete Seminar
Sem inar 2005 59 Annua
Annuall Concrete Sem inar 2005
Seminar 60

10
Annua
Annuall Concrete Sem inar 2005
Seminar 61 Annua
Annuall Concrete Sem inar 2005
Seminar 62

Annua
Annuall Concrete Sem inar 2005
Seminar 63 Annua
Annuall Concrete Sem inar 2005
Seminar 64

Annua
Annuall Concrete Sem inar 2005
Seminar 65 Annua
Annuall Concrete Sem inar 2005
Seminar 66

11
Annua
Annuall Concrete Sem inar 2005
Seminar 67 Annua
Annuall Concrete Sem inar 2005
Seminar 68

131.4
R Chloride penetration
FTI
R
120

110

100

Thankou
90

80
%T

70

60

50

40

30.0
4000.0 3000 2000 1500 1000 400.0
cm-1

Annua
Annuall Concrete Sem inar 2005
Seminar 69 Annua
Annuall Concrete Sem inar 2005
Seminar 70

12