CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 24%253, 1993. Printed in the USA.

0008-8846~3. $6.00+00. Copyright © 1993 Pergamon Press Lid.

CHLORIDE BINDING CAPACITY AND BINDING ISOTHERMS

OF OPC PASTES AND MORTARS

TANG Luping* and Lars-Olof NILSSON

Division of Building Materials
Chalmers University of Technology
S-412 96 Gothenburg, SWEDEN

(Refereed)
(Received March 5. 1991; in f'mal form Dec. 1, 1992)

ABSTRACT
A method for evaluating chloride binding capacity of concrete was
proposed based on the adsorption from solution and chloride binding
isotherms of OPC pastes and mortars with water-cement ratio 0.4, 0.6 and
0.8. The experimental results show that the chloride binding capacity
of concrete strongly depends on the content of CSH gel in the concrete,
regardless of the water-cement radio and the addition of aggregate. The
relationship between the bound chloride and the free chloride can be
described by Freundlich isotherm at high free chloride concentrations
and Langmuir isotherm at low free chloride concentrations.

INTRODUCTION

It is well known that the chlorides, no matter whether added during mixing or
later transported into concrete, can be bound to the hydrated products in
concrete by physisorption and chemisorption. This is called chloride binding
capacity of concrete. Chloride-induced corrosion is recognized as a major problem
with regard to the service life of reinforced concrete. The threshold chloride
level for onset of chloride-induced corrosion is generally expressed by total
chloride content per weight unit cement. It is apparent that chloride binding
capacity of concrete has influence on the threshold chloride level, since only
unbound, or free, chloride ions in pore solution can possibly destroy the passive
film on the surface of the steel bar and initiate corrosion.

Although Richartz (i) analyzed the mechanism of chloride ions binding to hydrated
products in hardened cement paste twenty years ago, only in the last decade or
so, has more attention been paid to chloride binding capacity. Tuutti (2) found
that the bound chloride in relation to the free chloride could be independent
of the water-cement ratio for mortar if the bound chloride was counted per weight
unit cement. The experimental data reported by Page and Vennesland (3) showed
that the bound chloride in OPC paste was about 40% to 60% of total chloride
content. Pereira and Hegedus (4) suggested using Langmuir isotherm to determine
the reaction rates of chloride ions with selected concretes. Recently, Tritthart
(5) investigated the influence of various factors on the chloride binding
capacity. He also found that the proportion of bound chloride remained
approximately constant regardless of the water-cement ratio, in agreement with
what Tuutti (2) found.

The literature review shows that the relationship between bound chlorides and

as a guest researcher from the Department of Building Materials, Chongqing Institute of Architecture and Engineering,
Chongqing, China.

247
248 L. Tang and L.-O. Nilsson Vol. 23, No. 2

free chlorides is still not very clear. One of the reasons is perhaps due to the
difficulty of determining the bound chloride fraction. This paper attempts to
find a new approach to evaluate the chloride binding capacity.

EXPERIMENTAL

The common method of determining the chloride binding capacity involves

dissociating the free chloride fraction from the total chloride content by
analyzing the pore solution squeezed out from the concrete under high pressure.
However, it would be very difficult by this method to obtain the binding
characteristics of chloride ions which penetrate into concrete. Therefore, a
new method based on the adsorption from solution was developed in this study.
Materials
The chemical composition and physical properties of ordinary portland cement used
in this study are listed in Table I. The dolomite sand without any chloride,
passing through 1 mm sieve, was chosen as fine aggregate. For both OPC pastes
and mortars (cement:sand = 1:2), deionized water was used and the water-cement
ratios were 0.4, 0.6 and 0.8.

TABLE 1 Composition and Properties of Ordinary Portland Cement

SiO= Al~s Fe~3 CaO MEO K~ Fineness Specific Loss on

(Blaine) Eravity iEnition
:: z z ~: x ~: ,~/kg z

19.9 5.3 2.8 62.1 1.3 1.3 340 3.13 2.31

Preparation of specimens
After moulded in a plastic pipe mould of size o ls
470x140 mm, the specimen was subjected to
continuous rotation at about i0 rpm for 24 OPC paste
hours about a horizontal axis to prevent w/c=0.4
significant segregation, then demoulded and
cured with plastic pipe under saturated lime
water at room temperature (about 22 °C). v0.1
C

Preparation of samples -~
=
In order to obtain the intrinsic binding
capacity, the attention should be paied to
avoiding carbonation and overheating. After .c ~J
curing for about 6 weeks, the central region of ~0.0s
the specimen was wet-crashed and water-sieved .=
into 0.25-2 mm particles. The particulate
samples were vacuum dried in a desiccator
filled with silica gel at room temperature for O
about 3 days to remove most of the water, then
stored in a desiccator with decarbonized air at
II%RH kept by saturated LiCI solution for at 0 . . . . I . . . . i , , , ,

0 5 10 15
least 7 days so that only a monolayer of water
was adsorbed on the gel (6). Immersion Time (day)
Test methods and procedures
Chloride adsorption isotherm. About 25 g FIG. 1
particulate sample dried at II%RH was put into Relation between adsorption
a given weight cup, then the cup was vacuumed equilibrium and time
within a desiccator for 2 hours before filled
with a given concentration NaCI solution
saturated with Ca(OH)2. The volume of solution filled inside the cup was
calculated from the increment of the weight of the cup and the density of the
Vol. 23, No. 2 CHLORIDES, BINDING CAPACITY, PASTES, MORTARS 249

solution. The cup was covered and stored at 20 °C for equilibrium. According
to our preliminary experiment, the adsorption equilibrium could be reached in
the first seven days, as shown in Fig.l. Theissing et al. (7) also found the
equilibrium could be reached within 10-14 days. Therefore, two week time is
enough for various samples to reach the adsorption equilibrium. After
equilibrium, the inside solution was pippetted to determine the chloride
concentration by potentiometric titration using 0.01 N AgNO 3 and chloride
selective electrode. The content of bound chlorides was calculated by the
following equation.
35.45v(co-c I) (i)
Cb W

where Cb: bound chloride content, mg/g-sample;

V: volume of solution, ml;
co, c1: initial concentration and equilibrious concentration of
chloride solution, mol/l;
W: weight of dry sample, g.

The weight of dry sample can be calculated from the difference in weight of the
sample dried in a desiccator at II%RH and in an oven at 105 °C. Since for most
cases the CSH gel in concrete predominates the adsorption, at least physical
adsorption, it is useful to express the bound chloride content by unit weight
of the gel. In this case, the sample weight W in Eq.(1) should be substituted
by the weight of the gel W~I.

(i+w2) fc= w (2)

w~., 1+ w2 f c=

where W2: non-evaporable water, assuming W 2 = 0.25:

~: degree of hydration;
fo: cement content in concrete by weight,

f~ Wc~en~ (3)
Wcement+Waggregaces
The hydration degree of the paste was determined by ignition method, with the
same assumption of W 2 = 0.25, as in Eq.(2). The ignition loss of cement was also
taken into account for necessary correction. The hydration degree of the mortar
was assumed as the same as that of the paste with the corresponding water-cement
ratio.

The adsorption isotherm can be drawn from the data Cb and ci, through a series
of test with different initial concentration.

Chloride desorption isotherm. After the adsorption test, the surplus solution
in the cup was removed as much as possible, and about 200 ml deionized water
saturated by Ca(OH) 2 was added to the cup. Then the cup was stored at 20 °C for
new equilibrium before the inside solution was peppetted and analyzed in the same
way described above. The bound chloride content in this case can be calculated
by the following equation.
35.45 [CoV-CI ~ - C 2 (V+~/-V') ] (~)
cb' w
where V': volume of solution removed out, including first pippetted, ml;
V": volume of deionized water added, ml.

Water desorption isotherm. The pore structures of the samples were determined
by water desorption isotherms. About 120 g particulate sample dried at II%RH
was put into a cup, then the cup was vacuumed for 24 hours before filled with
distilled water. The water-saturated sample was distributed among seven weighing
cups, then the weighing cups were put into seven different RH chambers with
relative humidity from 11% to 95% individually and stored at 20 °C for about two
months to obtain the constant weight. The detailed structures of RH chambers and
other procedures of water desorption experiment was described by Xu (8). D.H.
method (9) was used to calculate pore size distribution and surface area. The
250 L.Tang and L.-O.Nilsson Vol.23, No. 2

shape of pores was assumed as parallel plate. The thickness of adsorption layers
was determined by the following semiempirieal relationship (i0), which
corresponds more with the experimental data published by different researchers
(ii).
t- 3.48
[log (~ s ) ] ix3 (5)
P
where t: average thickness of adsorption layers, A;
p/p,: relative pressure.

RESULTS AND DISCUSSION

The experimental results are shown in Table 2 and Figs.2 to 6 individually. It

should be noted that the free chloride concentration in pore solution is assumed
equal to that in equilibrious solution.

TABLE 2 Some Experiment Results

w/c ~ ~ Water content (wtZ) Surface area Remark

95ZRH II%RH n{/g-sample m2/g-gel

0.4 1 0.58 22.54 6.73 99.9 159 Paste

0.6 1 0.66 27.18 6.82 110.9 157 Paste
0.8 1 0.67 27.53 7.47 103.2 145 Paste
0.4 1/3 0.58 8.64 2.48 36.5 160 Mortar
0.6 1/3 0.66 10.12 2.56 38.6 150 Mortar
0.8 1/3 0.67 10.39 2.76 39.7 152 Mortar

10 w/c-0.40PC paste
o

..-'"'0. s ~ []
w/c =0.60PC paste
o
w/c=0.80PC paste

c:s:w= 1:2:0.4 Mortar

c:s:w= 1:2:0.6 Moctm"

C:S;W- 1:2:0.8 Mortar

.g 4 Z

cO

0
0 0.2 0.4 0.6 0.8
Free Chloride (mol/I -solution)

FIG. 2
Chloride adsorption isotherms of OPC pastes and mortars
(in unit weight of sample)
Vol. 23, No. 2 CHLORIDES, BINDING CAPACrI~, PASTES, MORTARS 251

16 w / c = 0 . 4 0 P C paste
o
w / c - O . 6 0 P C paste
14 o
0
O3 wlc=O.8OPC paste
C:S:W=1:2:0.4 M o r t ~
o3
c : s : w - 1:2:0.6 Mortar

0 c : s : w = 1:2:0.8 Mortar
"0 8
o
o
"o
e- 4

o
O0 2

0 , I , I , I , I
0 0.2 0.4 0.6 0.8
Free Chloride (mol/I -solution)

FIG. 3
Chloride adsorption isotherms of OPC pastes and mortars
(in unit weight of CSH gel)

0.5, wlc-0.40PC paste

w / c = 0 . 6 0 P C paste
0,4
r"
/ w / c - 0 . 8 0 P C Paste
/
~031
O3
0 0.21

0.1

0 J J i , , , , i i i
10 20 30 50 100 200 300 500

d (A)

FIG. 4
Differential pore size distributions of OPC pastes

It seems the same conclusion as Tuutti's (2) can be obtained from Fig.2 that the
water cement ratio has some influence on the isotherms of pastes, but has
little influence on the isotherms of the mortars, and the binding capacity of
the pastes is apparently higher than that of the mortars. When the content of
bound chlorides is expressed by unit weight of CSH gel, however, it is found that
no matter the pastes or the mortars with different water cement ratios, they have
almost the same chloride binding isotherm, as shown in Fig.3. As seen from Table
2 and Fig.4, although the pore size distributions of various samples are much
different, the surface areas of the CSH gel in different samples are almost the
same, because a large size pore does not make an apparent contribution to the
total area. These findings show that the chloride binding mainly occurs through
the interface between pore solution and hydrated products in concrete and the
binding capacity strongly depends on the content of CSH gel regardless of the
water-cement ratio and even the addition of aggregate.
252 L. Tang and L.-O. Nilsson Vol. 23, No. 2

2O w/c=0.4 adsorption
D
IOgCb = O.386410gc + 1.412 w/c=O 6 adsorption
A 0
10 w/c =0.8 adsorption
r2=O.g53 I ,,'~" Z~
C~ w/c=O 4 clesorption
O~
w/c =0.6 desorption
g 5

w/c=O 8 desorption
"10
z._
o QI
..C: 2
0
Q
IogCb =0.37881ogc+ 1.140
¢E
-'t
m
O
I
r2=0.996

0.5 I
0.001 0002 0.~5 0.01 0,02 0.05 0.1 0.2 05
Free Chloride (mol/I -solution)
Fig. 5
Freundlich isotherms of OPC pastes

1.2 w/c=0.40PC paste

[3
1/Cb =0.002438/C+0. 1849 w/c=0.60PC paste
0
w/c=0.80PC Paste
~--- , z~

~ , 0.8
Cr~
E
jC~30.6

(~0.4
.f-

0.2

I , I , I ,
1~ 2~ 3~ 4~
1/c (I-solution/rnol-CI)

FIG. 6
iangmuir isotherms of OPC pastes

In this study, the simple proportional relationship between the bound chloride
and the free chloride, as conventionally assumed, was not found. Alternatively,
it is found that, the relationship mentioned above obeys Freundlich isotherm at
the free chloride concentrations higher than 0.01 mol/l, as shown in Fig.5, that
is,
logCb_alogc+ b (6)
where a, b: adsorption constants.
And it obeys Langmuir isotherm at the concentrations lower than 0.05 mol/l, as
Vol. 23, No. 2 CHLORIDES, BINDING CAPACITY, PASTES, MORTARS 253

shown in Fig.6, that is,

!. i .±+ ~_!_ (7)
Cb k C ~ c Cbm
where k: adsorption constant;
C~: bound chloride content at saturated monolayer adsorption.
This indicates that if the chloride concentration in solution is very low, only
monolayer adsorption occurs, but when the concentration is higher than 0.05
mol/l, the adsorption becomes complex.
It can be seen from Fig.5 that the chloride desorption isotherm has almost the
same slope, but the larger intercept as compared with the adsorption isotherm.
This might confirm that some chlorides have been irreversibly bound to the
hydrated products by chemical reaction.

CONCLUSIONS

i. Chloride binding capacity of OPC concrete is strongly dependent on the

content of CSH gel in concrete regardless of the water-cement ratio and
the addition of aggregate.
2. The relationship between the bound chloride and the free chloride can be
well described by chloride binding isotherm which obeys Freundlich
equation at high free chloride concentrations (>0.01 mol/l) and Langmuir
equation at low concentrations (<0.05 mol/l).

3. Of the bound chlorides, some are irreversibly combined into hydrated

products by chemical reaction, and others can unbind as the free chloride
concentration decreases.

REFERENCES

i. W. Richartz, Zement-Kalk-Gips, 22 (I0), 447 (1969).

2. K. Tuutti, "Corrosion of steel in concrete", p.263, Swedish Cement and
Concrete Research Institute (CBI), Stockholm, No.4.82 (1982).
3. C.L. Page and O. Vennesland, Materials and Structures, 16 (91), 19 (1983).
4. C.J. Pereira and L.L. Hegedus, 8th Intl. Symp. Chem. Reaction EnEE. ,
Publication Series No. 87, 427 (1984).
5. J. Tritthart, Cem. Concr. Res., 19 (5), 683 (1989).
6. V.S. Ramachandran, R.F. Feldman and J.J. Beaudoin, "Concrete Science",
p.19, Heyden & Son Ltd., London (1981).
7. E.M. Theissing, P.v. Hest-Wardenier and G. de Wind, Cem. Concr. Res.,
(6), 683 (1978).
8. Xu Aimin, "The structure and some physical properties of cement mortar
with fly ash", Licentiate thesis, p.27, Chalmers University of Technology
(1990).
9. D. Dollimore and G.R. Heal, J. Appl. Chem., 14, 109 (1964).
i0. C. Huang, Q. Zhang and J. Yan, J. Chinese Silicate Inst., ! (4), 333
(1979).
ii. J. Hagymassy jr., S. Brunauer and R.Sh. Mikhail, J. Colloid and Interface
Sci., 29 (3), 485 (1969).