CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 724-742, 1993. Printed in the USA.

0008-8846/93. $6.00+00. Copyright 1993 Pergamon Press Ltd.

CALCULATION OF CHLORIDE DIFFUSION COEFFICIENTS IN CONCRETE

FROM IONIC MIGRATION MEASUREMENTS

C. A N D R A D E
Institute "Eduardo Torroja" of Construction Sciences
CSIC - Madrid - Spain

(Communicated by J.P. Skalny)

(ReceivedJuly 21, 1992)
ABSTRACT

A critical review is offered on the Rapid Chloride

P e r m e a b i l i t y Test standarized by AASHTO, p o i n t i n g out its
limitations and errors but recognizing its c o n t r i b u t i o n
to the developing of a simple and quick test for chloride
migration. Then another review is made on the
electrochemical fundaments of the p r o c e s s e s d e v e l o p p e d
in concrete when an electrical field is a p p l i e d and on
the basic equations of mass transport (Nernst-Plank and
Nernst-Einstein) which can be applied to c a l c u l a t e ionic
movements. The limitations and assumptions needed for a
simplified resolution of these equations, are presented,
as well as numerical examples of c a l c u l a t i o n of the
Effective Diffusion Coefficient of chlorides, De~, in
steady state condition. Finally, c o n s i d e r a t i o n s on the
p o s s i b i l i t y of calculation of Dc~ from simple r e s i s t i v i t y
m e a s u r e m e n t s are also offered.

INTRODUCTION

P e n e t r a t i o n of chlorides through concrete is one of the factors

which aims to the depassivation of reinforcing bars and therefore,
may shorten the life of the structure. The time needed by these
ions to reach the rebar depends first, on the m e c h a n i s m of
intrusion and secondly, on the external c o n c e n t r a t i o n of the
chlorides and the microstructure of the concrete.

W h e n concrete is completely water saturated, chlorides p e n e t r a t e

by a pure diffusion mechanism, being the difference in
concentration, the driving force. However in partial saturated
concrete, chlorides may penetrate by absorption and capillary
forces or d i s s o l v e d in the microdrops of marine fogs. These last
ones m o r e complex penetration mechanisms, are not going to be
c o n s i d e r e d in present paper.

724
Vol. 23, No. 3 CHI.)RIDE DIFFUSION,AASHTOTEST, RESISTIVH'Y 725

In t h e c a s e of p u r e d i f f u s i o n the c a l c u l a t i o n of t h e p e n e t r a t i o n
r a t e of c h l o r i d e , has b e e n m a i n l y s t u d i e d by m e a n s of e x p e r i m e n t s
a s s u m i n g e i t h e r s t e a d y - s t a t e or n o n - s t e a d y - s t a t e flow. In t h e case
of s t e a d y - s t a t e c o n d i t i o n s (1-5), u s u a l l y a t h i n d i s c of c e m e n t
paste is i n t r o d u c e d in b e t w e e n the two c h a m b e r s of a n a m e d
" d i f f u s i o n cell", and first Fick's law is a p p l i e d (6) in o r d e r to
calculate an Effective Diffusion Coeficient, D~, (diffusion
c o e f f i c i e n t in a p o r o u s medium):

dC dC(x)
-J(x) = = Dc~ [i]
dt dx

T h i s m e t h o d o l o g y p r e s e n t s some l i m i t a t i o n s w h i c h m a y be s u m a r i z e d
as follows: a) c e m e n t p a s t e and not c o n c r e t e is u s e d w h i c h can lead
to u n r e a l i s t i c results, b) it is t i m e - c o n s u m i n g and t a k e s w e e k s to
o b t a i n one result, c) a c o n s t a n t c o n c e n t r a t i o n in the c h a m b e r
c o n t a i n i n g c h l o r i d e s from the b e g i n n i n g s h o u l d be m a i n t a i n e d .

In t h e c a s e of n o n - s t a t i o n a r y c o n d i t i o n s , c o n c r e t e b l o c k s or
specimens can be u s e d w h i c h r e s u l t s in m u c h m o r e realistic
c o n d i t i o n s . T h e s e c o n c r e t e b l o c k s are m a i n t a i n e d in c o n t a c t w i t h
a s o l u t i o n of c o n s t a n t c h l o r i d e c o n c e n t r a t i o n and the c h l o r i d e
p r o f i l e a l o n g the time is measured. In this case s e c o n d F i c k ' s law
is a p p l i e d to c a l c u l a t e the, an A p p a r e n t D i f f u s i o n C o e f f i c i e n t D a
(6):

ac(x) a2c
-J(x) = = D a - .... [2]
at ax 2

This equation is u s u a l l y solved applying the following boundary

conditions:

cx= c,, x = 0, t > 0

and the initial condition: [3]

Cx= 0, x > 0, t = 0

O b t a i n i n g the f o l l o w i n g s o l u t i o n w h i c h is the m o s t w i d e l y u s e d (7-

11).
Cx x
= 1 - erf [4]
C, 2(Dat) I/2

T h i s t y p e of t e s t also r e s u l t s v e r y t i m e - c o n s u m i n g and m a i n t a i n s
s e v e r a l u n c e r t a i n t i e s on the r i g o r o u s a p p l i c a t i o n of F i c k ' s law.
S o m e a u t h o r s (12) r a t h e r p r e f e r to c o m p a r e c h l o r i d e p r o f i l e s t h a n
c a l c u l a t e D,.

In a d d i t i o n , in b o t h s t e a d y and n o n - s t e a d y t e s t c o n d i t i o n s , it is
not u s u a l l y c a l c u l a t e d the r e a c t i o n or a d s o r p t i o n of c h l o r i d e s by
c e m e n t phases. T h i s c i r c u n s t a n c e is c o n s i d e r e d of m i n o r i n f l u e n c e
726 C. Andrade Vol. 23, No. 3

although few researchers (13-14) do take into account. Thus,

A t k i n s o n (3) refers to it by defining: a) a Da: A p p a r e n t Diffusion
Coefficient in a porous medium, which considers the average
c o n c e n t r a t i o n gradients of the diffusing substance, t h e r e f o r e the
a d s o r p t i o n phenomena, and b) a Di: Intrinsic D i f f u s i o n Coefficient
w h i c h tries to take into account the average flux per unit of area,
and therefore, the volume fraction of porosity.

There are also a variety of improvement p r o p o s a l s to these two

basic approaches (15-18) which make much more complex the
c a l c u l a t i o n of the chloride D,.

Electrical methods

B e c a u s e of testing "natural" chloride p e n e t r a t i o n results time-

consuming, attempts have been made to calculate the D a from
resistivity measurementes (3)(19) or to accelerate the rate of
penetration of chloride ions by applying a n - e l e c t r i c a l field
(1)(20-29).

B o t h k i n d of test types will be commented in present paper in order

to a n a l y s e their possibilities and limitations. First a critical
r e v i e w will be done on the test known as "AASHTO TEST" (30)
explaining why its mode of operation leads to erroneous
conclusions. Secondly a brief summary will be made on the basic
k n o w l e d g e needed to understand migration phenomena in electrolytes.
Finally, a proposal will be presented on how to c a l c u l a t e Diffusion
C o e f f i c i e n t from electrical (migration) m e a s u r e m e n t s and which are
the t h e o r e t i c a l limitations. Numerical examples will be given.
E x t e n s i v e experimental trials will be needed to verify whether the
a s s u m p t i o n s taken in the numerical examples are r e l i a b l e or not.

CRITICAL REVIEW OF THE RAPID CHLORIDE PERMEABILITY TEST

That chlorides move quicker troughout the concrete when an

electrical field is applied arose from earlier experiments,
(31)(32) on that known at present as chloride removal (33)(34).
Actually, this fact on chloride migration was already experienced
by m a n y r e s e a r c h e r s using electrochemical techniques (as cathodic
p r o t e c t i o n (12) for instance). However, it was W h i t i n g who, (20-
21)(30) p r o p o s e d a "Rapid Chloride Permeability Test" in order to
o b t a i n in few hours an appraisal on concrete permeability. This
s t a n d a r d test has promoted a strong controversy (28)(29), w i t h more
heat than light in clarifying the meaning of the test and its
a b i l i t y to predict concrete resistance to p e r m e a t i o n of chlorides.
The real fact is that the test is increasingly being used although
e v e r y b o d y recognizes some still unknown uncertainties.

S u m m i n g up, this test uses a thick (usually 5 cm) c o n c r e t e disc

b e t w e e n two electrodes (usually copper meshes) in an arrangement
similar to that of the diffusion cell. Sodium chloride (3% per
weight) is added to one of the chambers and NaOH of about 0.i M to
the other. Then, an electrical field of 60V is r e c o m m e n d e d to be
a p p l i e d between electrodes and the amount of coulombs recorded
Vol. 23, No. 3 CHLORIDE DIFFUSION, AASHTO TEST, RESISTIVITY 727

a l o n g 6 h o u r s of testing, are m e a s u r e d . The t e s t d e f i n e s t h a t a

h i g h e r a m o u n t of c o u l o m b s r e p r e s e n t s a h i g h e r p e r m e a b i l i t y of the
c o n c r e t e to the c h l o r i d e s .

Movement of ions in concrete under an electrical field

L e t us a n a l y s e n o w step by step w h a t h a p p e n s from the b e g i n n i n g of

t h e e x p e r i m e n t and try to e x p l a i n w h a t is w r o n g in the test.

W h e n t h e c o n c r e t e d i s c is i n t r o d u c e d in the cell, b e f o r e any

e l e c t r i c a l f i e l d is a p p l i e d a d i f f u s i o n (leaching) is p r o d u c e d
m a i n l y of OH- ions due to t h e i r h i g h ionic m o b i l i t y as f i g u r e 1 a
shows. T h i s d i f f u s i o n due the d i f f e r e n c e in c o n c e n t r a t i o n s of
d i f f e r e n t ions m a y be m a i n t a i n e d a l o n g the e x p e r i m e n t .

In a d d i t i o n , w h e n the e l e c t r i c a l field is applied, m i g r a t i o n of all

ions o c c u r s t o w a r d s the o p p o s i t e sign e l e c t r o d e (figure ib). Not
o n l y c h l o r i d e s move, but all the ions do and the t o t a l c u r r e n t is
spent in the a d d i t i o n of all t h e s e m o v e m e n t s w h i c h w i l l be
commented later. Therefore, diffusion plus m i g r a t i o n happens
s i m u l t a n e o u s l y as f i g u r e 1 c depicts. The final r e s u l t w i l l d e p e n d
on t h e r e l a t i v e i m p o r t a n c e of both m o v e m e n t s .

T h e n the p r o c e s s e s d e v e l o p p i n g (36) in the cell w h e n an e l e c t r i c a l

f i e l d is applied, are the f o l l o w i n g (figure 2):

a) Electrode processes -

a.l) M e t a l d i s s o l u t i o n - w h i c h g e n e r a t e s o x y d e s at t h e a n o l y t e
(possitive electrode chamber), if the anode is an
o x i d a b l e metal, as for i n s t a n c e copper. In the c a s e of
g r a p h i t e e l e c t r o d e s the p r o c e s s w i l l be: C --> CO + CO 2.

a.2) E v o l u t i o n of gases - as e l e c t r o l y s i s of water, in b o t h

anolyte and catholyte, generating 02 a n d H 2. This
e v o l u t i o n w i l l stirr the s o l u t i o n in b o t h c h a m b e r s .

The r e a c t i o n s o c u r r i n g are the w e l l known:

possitive electrode - 2H20 --> 202 + 4H + 4e

negative electrode - 2H20 + 2 e --> H 2 + 20H

In the case of u s i n g not c o r r o d i b l e e l e c t r o d e s as Pt, the

w a t e r e l e c t r o l y s i s will be the o n l y e l e c t r o d i c process.

Not o n l y w a t e r e l e c t r o l y s i s but o x i d a t i o n of Cl a l s o m a y
h a p p e n if the v o l t a g e is h i g h e n o u g h to p r o d u c e Cl 2
evolution.

possitive electrode: - 2Ci --> Cl 2 + 2 e

728 C. Andrade Vol. 23, No. 3

As well as oxygen reduction following the known

reaction,

negative electrode: 202 + H20 + 4e" -> 4OH

All these reactions tends to maintain the total

e l e c t r o n e u t r a l i t y of the e x p e r i m e n t w h i c h is one of the
f u n d a m e n t a l s of e l e c t r o c h e m i c a l r e a c t i o n s .

CQncrete

No +
, , , - - - C I -

OH-
Na

a) DIFFUSION

Concrete

~--- CI-

No+-~,.

b) MIGRATION

Concrete (~
Y//.//I
OH-
NQ

~ - - 0H-
V/N/ "o'-

c) DIFFUSION + MIGRATION

Figure i. M a s s transport processes in concrete.

Vol. 23, No. 3 CHLORIDE DIFFUSION,AASHTOTEST, RESISTIVITY 729

(~) HEAT=IZ.Rohm (~
:" No+._...

0 00

2 H20 "-" 0 2 0 2 H + No 2 H 2 0 - " H2t+ 2OH-

CI "-" CI2~ 02+ 2H20 "" 4OH"

Cu--Cu +I
F
Figure 2. Processes occurring when an electrical field is applied
in a diffusion cell: Joule effect, anode dissolution,
electrolysis of the electrolite (gas e v o l u t i o n at
electrodes and reduction reactions) and ionic m i g r a t i o n
and diffusion.

b) Migration -

The third process happening in a cell is the m o v e m e n t of

ions in the electrolyte in order to carry the e l e c t r i c i t y
passing through the cell. Therefore, migration is
developed and diffusion may appear if this m i g r a t i o n
leads to concentration differences.

As it was mentioned, not only chlorides move but all ions

take part in migration in a proportion what is known as
their "transport or transference number".

T r a n s f e r e n c e number -

Let us try to explain something here about this

parameter. The transference number of an ion m o v i n g under
the action of an external electrical field is defined by
the "proportion of the current carried by this ion in
relation to the current carried by the rest of the ions"
(36). It is formulated as:

i, %%xj
t~. . . . . . . [5]
i Z ZCX A

Hence, the transference number is a function of the ionic

m o b i l i t y or the equivalent conductivity. This means that
OH- ions will carry much more p r o p o r t i o n of current than
Cl- ones due to the ionic conductivity of OH" is 198,5 o h ~
l'cm2"eq-] and that of C I is 76,34 ohm-*.cm2.eq-I (36). This
fact is very important in the case of concrete because
730 C. Andrade Vol. 23, No. 3

it m e a n s that the m a i n p r o p o r t i o n of the c u r r e n t w o u l d

be t a k e n by O H ions and not by the Cl and t h e r e f o r e ,
h y d r o x y d e s m i g h t b e h a v e as a " s u p p o r t i n g e l e c t r o l y t e " .

Therefore, only if c h l o r i d e t r a n s f e r e n c e n u m b e r s are

c a l c u l a t e d is p o s s i b l e to s p e c i f i c a l l y d e d u c e c h l o r i d e
t r a n s p o r t feasability, w h i c h is not t a k e n into a c c o u n t
by the R a p i d C h l o r i d e P e r m e a b i l i t y t e s t w h i c h only
r e c o r d s the total a m o u n t of c u r r e n t (that c o r r e s p o n d i n g
to the m o v e m e n t of all ions). In a d d i t i o n w h e n f l o w i n g
t h r o u g h the c o n c r e t e the c h l o r i d e s m a y r e a c t w i t h the C3A
and t h e r e f o r e a s t a t i o n a r y flow c a n n o t be a c h i e v e d u n t i l
all r e a c t i v e sites are saturated.

Movement of c a t i o n s -

An a d d i t i o n a l a s p e c t to be s t r e s s e d n o w is r e l a t e d to the
" a n o m a l o u s " D i f f u s i o n C o e f f i c i e n t t h a t is m e a s u r e d in the
c a s e of the c a t i o n s of small ionic radius, as Na and K
(i). T h i s b e h a v i o u r is v e r y w e l l d e s c r i b e d by B o c k r i s
(36) and G l a s s t o n e (37) c o n s i d e r i n g t h a t t h e s e ions
m i g r a t e solvated, that is, due to its s m a l l ionic radius,
Na and K d i f f u s e or m i g r a t e surrounded by w a t e r
m o l e c u l e s , as they n o r m a l l y are in solution. T h a t m a k e s
t h e i r m o v e m e n t m o r e d i f f i c u l t and t h e r e f o r e , D v a l u e s
s m a l l e r t h a n t h o s e of c h l o r i d e ions are r e p o r t e d (i).

T h i s fact also e x p l a i n s w h y w a t e r m a y c o n c e n t r a t e at the

cathode, as was s o m e t i m e s n o t i c e d in the c a s e of c a t h o d i c
p r o t e c t i o n . Na and K m i g r a t i o n m e a n s t h a t a net f l o w of
water (electroosmosis) is also s i m u l t a n e o u s l y p r o d u c e d .

T h i s fact can be also a p p l i e d to e x p l a i n the b a s i c

process of electrochemical realkalization: there,
h y d r o x y d e s are p r o d u c e d at the r e b a r a c t i n g as cathode,
and s o l v a t e d Na ions m o v e from the e x t e r n a l c a r b o n a t e
s o l u t i o n in order to b a l a n c e the e l e c t r i c a l c h a r g e s and,
finally they support the r e c o n s t r u c t i o n of a N a O H
solution around the rebars. Anyway, as water is
simultaneously r e d u c e d at the c a t h o d e t o g e t h e r w i t h
oxygen, the d i l u t i o n e f f e c t m a y be b a l a n c e d .

In the case of the m i g r a t i o n test, h a v i n g t w o c h a m b e r s

w i t h solutions, the e f f e c t of i n c r e a s i n g w a t e r a r o u n d the
r e b a r is not noticeable, but in the c a s e of c o n c r e t e
( c a t h o d i c p r o t e c t i o n , r e a l k a l i z a t i o n or c h l o r i d e removal)
the e f f e c t w i l l be d e p e n d e n t of the p o t e n t i a l a p p l i e d or
the l a s t i n g of the t r e a t m e n t . A c o n s e q u e n c e of this
e f f e c t in the case of c a t h o d i c p r o t e c t i o n , is t h a t the
r e s i s t i v i t y will i n c r e a s e at the a n o l y t e (and t h e r e f o r e
d e c r e a s i n g the e f f i c i e n c y of the a n o d e s ) a n d a dilution
of the s o l u t i o n a r o u n d the cathode, and t h e r e f o r e a
" b u f f e r i n g " of the i n c r e a s e in pH v a l u e on the c a t h o l y t e ,
m a y happen.
Vol. 23, No. 3 CHLORIDE DIFFUSION, AASHTO TEST, RESISTIVITY 731

S u m m i n g up w h a t has been said up to now, when an electrical field

(direct current) is applied between two electrodes p l a c e d both
sides of a concrete block, several phenomena d e v e l o p as figure 2
depicts:

a) The anodic material, if possible, dissolves and gases may evolve

at b o t h electrodes, b) all ions of the electrolyte m o v e in order
to carry the current passing through the cell and to m a i n t a i n
e l e c t r o n e u t r a l i t y c) in addition heat is produced as a consequence
of the current flow.

At the sight of these comments, it can be deduced that, the

R a p i d C h l o r i d e Permeability test contains the following errors:

i) It accounts the total current and not that corresponding to

the chloride flow.

2) W h e n integrating the total current from the b e g i n n i n g of the

e x p e r i m e n t it does not distinguish between chloride flow plus
r e a c t i o n and simple flow.

3) The high voltage drop used (60v) induces heat (23)(27) which
in turn changes the flow speed.

T h e r e f o r e a m i g r a t i o n test of this type cannot at all inform on

transport of chlorides (38) and much less on p o r o s i t y or
"permeability" of the concrete specimen.

CALCULATION OF DIFFUSION COEFFICIENTS FROM MIGRATION MEASUREMENTS

A l t h o u g h it has been mentioned the errors involved in the "Rapid

C h l o r i d e P e r m e a b i l i t y Test" which invalidates its d e d u c t i o n s , i t
m u s t be r e c o g n i z e d the importance of its aim of shortening the time
n e e d e d to test concrete resistance to ionic diffusion, and how much
W h i t i n g ideas have estimulated the discussion on this area.

Now an attempt is presented on how to calculate, not he

"permeability", but the Diffusion Coefficient from an electrical
m e a s u r e m e n t similar to that described in the AASHTO test. Diffusion
c o e f f i c i e n t is the parameter which may characterize a concrete in
order to p r e d i c t its long term performance, that is, its resistance
to the p e n e t r a t i o n of ions. The calculation of D from electrical
measurements has to be based in the fundamental of transport
p r o c e s s e s in electrolytes, very well established in the traditional
books of E l e c t r o c h e m i s t r y Science (36)(37)(39-43).

There, it appears that the general equation for t r a n s p o r t processes

in s o l u t i o n is that named Nernst-Planck (36) equation which can be
w r i t t e n as:

0Cj (X) ZjF 0E (X)

-J~(x) = % + %q + qv(x) [6]
0x RT 0 (x)
732 C. Andrade Vol. 23, No. 3

J(x) = u n i d i r e c t i o n a l flux of species j (mol/cm2s)

= d i f f u s i o n c o e f f i c i e n t of species j (cm2/s)
= v a r i a t i o n of c o n c e n t r a t i o n (mol/c~)
ax = v a r i a t i o n of d i s t a n c e (cm)
Zj = e l e c t r i c a l c h a r g e of species j
F = F a r a d a y ' s n u m b e r (coul/eq)
R = gas c o n s t a n t (cal.voltl.eq l)
T = a b s o l u t e t e m p e r a t u r e (~)
= b u l k c o n c e n t r a t i o n of the species j ( m o l / c m 3)
= v a r i a t i o n of p o t e n t i a l (V)
V = a r t i f i c i a l or forced v e l o c i t y of ion (cm/s)

w h i c h m e a n s that the u n i d i r e c t i o n a l (x) flux of a p a r t i c u l a r ion

(5) is a f u n c t i o n of its d i f f u s i o n plus its m i g r a t i o n c o m p o n e n t s
and p l u s the flux due to convection. That is:

Flux = d i f f u s i o n + migration + convection

T h e r e f o r e this e q u a t i o n allows the c a l c u l a t i o n of D f r o m the total

ionic f l u x recorded.

However, some c o n s i d e r a t i o n s have to be m a d e b e f o r e an a p p r o p r i a t e

a p p l i c a t i o n of e q u a t i o n [6] is tried.

These are:

A) The n e e d to p r o v i d e the c o n d i t i o n s for s t e a d y - s t a t e flow

(equation [6] as it is, is f o r m u l a t e d for s t e a d y state
conditions).

B) The r e a c t i o n of c h l o r i d e s w i t h the C3A and t h e r e f o r e the

d e f i n i t i o n of D as an " A p p a r e n t D", D a w h e n it t a k e s it
into account, or an E f f e c t i v e one, D~, w h e n it m e a s u r e s
the net c h l o r i d e flow w i t h o u t reaction.

c) L i m i t s of a c c u r a c y due to the high ionic strengths of

c o n c r e t e p o r e solution.

D) The p o t e n t i a l d i f f e r e n c e applied should be small enough

to a v o i d Joule effect.

NaO NaCI NeOH~ _ N a C i

STATIONARY FLOW NON-STATIONARY FLOW

Figure 3. S t a t i o n a r y and n o n - s t a t i o n a r y flow in f u n c t i o n of the
s p e c i m e n t h i c k n e s s and time of testing.
Vol. 23, No. 3 CHLORIDE DIFFUSION, AASHTO TEST, RESISTIVITY 733

Stationary flow - in order to apply e q u a t i o n [6] in its

p r e s e n t formulation, a s t e a d y - s t a t e flow has to be e s t a b l i s h e d
as f i g u r e 3 depicts. If n o n - s t a t i o n a r y flow is p r o d u c e d , then
the v a r i a t i o n w i t h the d i s t a n c e of the c h l o r i d e c o n c e n t r a t i o n ,
s h o u l d be also t a k e n into a c c o u n t a i m i n g to an e q u a t i o n in
p a r t i a l d e r i v a t i v e s of second order s i m i l a r to s e c o n d Fick's
law.
B) R e a o t i o m - the first c h l o r i d e ions t r a v e r s i n g the c o n c r e t e
d i s c w i l l react w i t h AC 3 and t h e r e f o r e an e r r o n e o u s D m a y be
c a l c u l a t e d as has been d e t e c t e d in the case of p u r e d i f f u s i o n
cells. In order to n e g l e c t this fact, the c a l c u l a t i o n of D has
to be m a d e w h e n a linear increase of c h l o r i d e s is r e c o r d e d in
the c h a m b e r not c o n t a i n i n g them at the beginning, t h a t is to
r e c o r d the c h l o r i d e flow when the r e a c t i v e AC 3 was s a t u r a t e d
w i t h the first m i g r a t i n g Cl (figure 4).
e) I o n i c s t r e n g t h - In order to take into a c c o u n t the h i g h ionic
s t r e n g t h of the c o n c r e t e pore solution, two m a i n a s p e c t s h a v e
to be considered: a) that a c t i v i t i e s i n s t e a d of c o n c e n t r a t i o n
m u s t be c o n s i d e r e d and therefore, either a selective ion
electrode for chloride is used or activities must be
c a l c u l a t e d , for instance as is s u g g e s s t e d in (44), and b) the
i n f l u e n c e of the ionic s t r e n g t h in the t r a n s p o r t number, ~,
and in the v a l u e itself of D ~ should be c o n s i d e r e d .

Let us a g a i n try to a n a l y z e this a s p e c t of the i n f l u e n c e of

the ionic s t r e n g t h on D w i t h m o r e detail. It has been
e s t a b l i s h e d that D is not a constant, but a f u n c t i o n of the
c o n c e n t r a t i o n of the solution (36) and therefore, h i g h ionic
s t r e n g t h i n f l u e n c e s D value. In a r e c e n t p a p e r (44) a s i m p l e
w a y to c a l c u l a t e activity factors from conductivity
m e a s u r e m e n t s has been offered, and t h e r e f o r e a t r i a l w i l l be
p r e s e n t e d in the n u m e r i c a l examples, on h o w Dc~ v a r i a t i o n w i t h
c o n c e n t r a t i o n is calculated.

tool
cm =. sg Cl- in the
catholite

I ~ , ! r w ,

TIME
Figure 4. Flux (J) of c h l o r i d e s leaving the c a t h o d i c chamber along
time.
734 C. Andrade Vol. 23, No. 3

Anyway, it is important to stress that being the concrete pore

solution a very concentrated one, the influence of ionic
strength cannot be neglected in the calculation.
D) J o u l e e f f e c t - The potential difference applied to drive
m i g r a t i o n should be as high to promote a quick enough m o v e m e n t
of chlorides, and as small as to avoid a waste in heating. Ten
to fifteen volts could be a sensible compromise.
Solving Nernst - Plank equation

Really a rigourous solution for equation [6] cannot be a c h i e v e d in

solutions as concentrated as concrete pore solution (36)(43). In
polielectrolytes (more than binary solutions) a rigourous
a p p l i c a t i o n of flux equation [6] fails, an even m o r e if the
s o l u t i o n is concentrated, because D has to take into account
interaction of all ionic species. Therefore at least two main
d i f f i c u l t i e s arise when facing our particular problem: 1) first
that of the high ionic strength previously commented and 2) how to
apply the e q u a t i o n to a particular ion and not to the solution as
a whole (19).

A semirigourous calculation might be undertaken using two p o s s i b l e

aproaches:

a) To consider phenomenological Onsager's equations (36), or

b) To use a M e a n D for the whole electrolyte (43).

Both approaches lead to unsatisfactory solutions for the sake of

practical purposes. The first because needs many and s o p h i s t i c a t e d
m a t h e m a t i c a l equations and the second, because does not allow to
d i f f e r e n t i a t e between the different ions.

Thus, w i t h the aim of looking for a simple and p r a c t i c a l solution,

a simplified approach should be tried. This will be based in
several assumptions able to overcome previous difficulties.

Simplified calculation of De~

The several assumptions which have to be taken into account in

order to solve equation [6] are (36)(39-43):

i. Only what happens inside the concrete disc is influencing the

measurements. This assumption may be accepted from the fact
that ionic mobilities in solution are 3 or 4 orders of
m a g n i t u d e higher than in the concrete and therefore, for the
sake of the measurement, the slowest process is the only
c o n s i d e r e d relevant.

2. The t e r m dealing with convection in e q u a t i o n [6] can be

neglected. This seems not difficult to be accepted, if only
w h a t happens inside the concrete disc is considered.

3. The diffusion component of equation [6] is considered

negligible in comparison to that due to migration. As well,
Vol. 23, No. 3 CHLORIDE DIFFUSION, AASHTO TEST, RESISTIVITY 735

e l e c t r o n e u t r a l i t y in this e x p e r i m e n t is m a i n t a i n e d by m e a n s
of the electrodic processes (gas evolution or metal
dissolution) and t h e r e f o r e counter diffusion or m e m b r a n e
e f f e c t s are not considered.

4. The c o n c r e t e disc is thin enough to a l l o w to r e a c h a s t e a d y -

s t a t e c o n d i t i o n is few hours, w h i c h in turns m e a n s that all
r e a c t i v e AC 3 in the disc is s a t u r a t e d w i t h the first d i f f u s i n g
c h l o r i d e s and therefore, after the t r a n s i e n t i n i t i a l period,
a linear flux of c h l o r i d e s along time, is e s t a b l i s h e d (figure
4), This allows to make the term a E/a 1 = AE/I, b e i n g 1 the
c o n c r e t e disc thickness, and ~E the p o t e n t i a l applied.

5. The c o n c e n t r a t i o n of c h l o r i d e s in one c h a m b e r of the cell is

m u c h h i g h e r than in the other. That is, c h l o r i d e c o n c e n t r a t i o n
in the c a t h o l i t e should be high and that in the anolite, zero.
T h i s a l l o w s to a c c e p t that the c o n c e n t r a t i o n (activity better)
of c h l o r i d e s in one side of the cell r e m a i n s c o m p a r a t i v e l y
constant.

O n c e all t h e s e a s s u m p t i o n s are considered the equation can be

expressed in the f o l l o w i n g way:

mol ZF ~E
Total flux = -J( ...... ) . . . . . . . De,CoL .... [7]
sg'cm 2 RT 1

where i= disc thickness and Ca is the activity of chloride

ions.

The equation may be also writen:

JRT 1
De,= [8 ]
z F Ccl ~E

in w h i c h all p a r a m e t e r s are known and J can be c a l c u l a t e d from an

e x p e r i m e n t a l test in w h i c h the amount of c h l o r i d e s is m o n i t o r e d
a l o n g the time. Thus, from a plot s i m i l a r to that of f i g u r e 4, the
flux J can be c a l c u l a t e d from the slope of the linear part.

Calculation of D~ from the value of intensity. Nernst-Einstein

equation

A n o t h e r w a y to c a l c u l a t e D ~ is from the r e c o r d i n g of the i n t e n s i t y

d u r i n g the experiment, b e c a u s e it is also well e s t a b l i s h e d (36)(39-
43) t h a t the flux of a m i g r a t i n g species is also p r o p o r t i o n a l to
the t o t a l intensity:

itj
J= [9]
nF

b e i n g the t r a n s f e r e n c e number (of the c h l o r i d e in this p a r t i c u l a r

case) the p r o p o r t i o n a l i t y factor. Therefore, on the c o n t r a r y from
the v a l u e of J o b t a i n e d in an e x p e r i m e n t a l test, it is p o s s i b l e to
736 C. Andrade Vol. 23, No. 3

calculate the t r a n s f e r e n c e number ~, and by s u b s t i t u t i o n of

e q u a t i o n [9] in e q u a t i o n [7], the f o l l o w i n g is obtained:

itcl ZF AE
= . . . . Def
t Ccl . . . .
[i0]
nF RT 1

T h i s e x p r e s s i o n r e s u l t s s i m i l a r to N e r n s t - E i n s t e i n (32) e q u a t i o n
but a p p l i e d for a single ionic species t h r o u g h the use of the
t r a n s f e r e n c e number:

RT RT itcl 1 1
Def~ A cl = [ii]
nF 2 nF 2 AE A C~Z

b e i n g A = cross s e c t i o n area of the c o n c r e t e disc. This e q u a t i o n

o p e n s the d o o r to the p o s s i b i l i t y of c a l c u l a t i o n of D i f f u s i o n
Coefficients from a simple measurement of resistivity or
c o n d u c t i v i t y p r o v i d i n g that ~ of the p a r t i c u l a r ion c o u l d be
accurately calculated (see n u m e r i c a l example later on). This
approach would represent a very p r o m i s i n g s i m p l e way for the
future, if the t h e o r e t i c a l d i f f i c u l t i e s of c a l c u l a t i n g a c c u r a t e
t r a n s f e r e n c e n u m b e r s of c h l o r i d e ions in concrete, c o u l d be solved.

Even, as it w i l l be p r e s e n t e d at the n u m e r i c a l example, this

e q u a t i o n s e r v e s for an a p p r o x i m a t e c a l c u l a t i o n of the order of
m a g n i t u d e of D from w a t e r s a t u r a t e d c o n c r e t e r e s i s t i v i t y values,
o n c e p r o p e r a c c o u n t of the influence of the ionic s t r e n g t h of pore
s o l u t i o n is c o n s i d e r e d (3)(44)(45)(46).

F i n a l l y it has to be m e n t i o n e d that, if the c a l c u l a t i o n is m a d e

f r o m r e s i s t i v i t y m e a s u r e m e n t s the r e a c t i o n w i t h the AC 3 is also
m i s l e d and therefore, the v a l u e s o b t a i n e d are t h o s e of Den and not
of D a.

0.1M NoOH 0.5 M NoCl

0.5m
Figure 5. S i m p l e r e p r e s e n t a t i o n of the cell for testing chloride
migration.
Vol. 23, No. 3 CHLORIDE DIFFUSION,AASH'ID TEST, RESISTIVITY 737

NUMERICAL EXAMPLES

Nernst-Plank equation

Figure 5 depicts an e x a m p l e in w h i c h N a C l 0 . 5 M is added to the

catholyte of a m i g r a t i o n c e l l a n d N a O H 0.1 M to the anolyte. The
following parameters are assumed:

Cross-section area: 30 c m 2

D, = i0 -s cm2.sg -I
R 1 . 9 8 7 2 c a l ' m o l l ' ~ ~I
F = 2 3 0 6 3 cal'volt'1"eq "I
Z = 1

Applied potential between electrodes A E = 12 V

Concrete thickness 1 = 0,5 cm.

Considering the activity equal to the concentration, the flux

produced for a concrete having a D~ of 10 .8 cm2.s -I w o u l d be:

( i ) (23063) (10 .8) (0.5X10 3) (12) mol

J = = 0,47 x 10 .8
(1.9872) (293) (0.5) s.cm 2

T h i s is t h e o r d e r of m a g n i t u d e of t h e f l u x t h a t w i l l b e r e c o r d e d
in t h i s k i n d of e x p e r i m e n t s , and a period of s e v e r a l h o u r s of
t e s t i n g a r e n e e d e d in o r d e r t o m i n i m i z e e r r o r s in m o n i t o r i n g it.

In figure 6 a graphic representation of t h e v a r i a t i o n of f l u x J

w i t h t h o s e of D~, C a n d ~ E b e i n g t h e r e s t of p a r a m e t e r s constant,
is g i v e n . It is a p p a r e n t t h a t an i n c r e a s e of A E f r o m 2 t o 20 v o l t s ,
c a n i n c r e a s e o n e o r d e r of m a g n i t u d e t h e flux. A s w a s r e f e r e d in (i)
a potential of 2 volts almost does not influences the pure
diffusional flux.

As an example too, in (47) c h l o r i d e fluxes are reported of t h e

o r d e r of a b o u t i0 m m o l / d a y f o r a c o n c r e t e c u r e d at 20C a n d w i t h a
w / c = 0,5. T h u s t a k e n i n t o a c c o u n t t h e e x p e r i m e n t a l conditions used
b y t h e a u t h o r s a n d a s s u m i n g a n s t a t i o n a r y flow, t h e D ~ v a l u e s w o u l d
r e s u l t t h e s e n s i b l e v a l u e of:

Dc~ = 3.1 x i0 -s cm2/s

Calculation from intensity values

The theoretical calculation of c h l o r i d e t r a n s f e r e n c e n u m b e r in a

solution 0.2M NaOH + 0.5M NaCl from equation [5] w i l l give a value
of:

(0.5)(76.34)
to = ,= 0. 338
(o.5) (50.1)+(0.5) (76.34)+(o.2) (198)+(0.2) (50.1)
738 C. Andrade Vol. 23, No. 3

C = 0.5 mol/cm s D= 10-Scm?-/s D =lO-ScmZ/s

AE=lEV AE=IZV C=0,5mol/cm 3
t=0.5cm L = 0.5cm L =0,Scm
rnol
cm2.sg
10-o

10-~ J f
10-1o
, ! , , , v r r

I0 -7 I0 -s I0 -9 0.I 0.3 0.5 20 40 60

D (crag/s) C(mol/cm 3) AE (V)

NERNST- PLANK EQUATION

Figure 6. R e p r e s e n t a t i o n of the c h l o r i d e flux after N e r n s t - P l a n k
e q u a t i o n [6] (migration term) in f u n c t i o n of c h l o r i d e
a c t i v i t y values.

A s s u m i n g t h e n this v a l u e as a r e f e r e n c e one, the i n t e n s i t y value

w h i c h has to be r e c o r d e d to o b t a i n a flux of 0.47 x i0 g mol/cm2"s
w o u l d be, f o l l o w i n g e q u a t i o n [9]:

JnF (0.47) (i0 s) (i) (96500)

i = = = 1.338.10 .3 A / c m 2
tcl 0.338

using these values in e q u a t i o n [i0] De~ can be calculated, as is

shown next.

Nernst-Einstein equation
F i g u r e 7 shows a g r a p h i c r e p r e s e n t a t i o n of N e r n s t - E i n s t e i n e q u a t i o n
[ii] a s s u m i n g a s o l u t i o n 0.2 M N a O H plus of NaCl w i t h a c t i v i t y
v a l u e s of 0.i, 0.35 and 0.5 m o l / c m 3 and a c h l o r i d e t r a n s f e r e n c e
n u m b e r of 0.338:

This representation let us deduce that D varies with the

concentration as is theoretically stated (36), being the
r e s i s t i v i t y the m o s t i n f l u e n c i n g parameter.

In o r d e r to a p p l y this e q u a t i o n the c o n c r e t e has to be w a t e r

s a t u r a t e d to a s s u r e p u r e d i f f u s i o n p e n e t r a t i o n m e c h a n i s m . C a p i l l a r y
f o r c e s a p p e a r i n g in p a r t i a l l y dry c o n c r e t e w i l l i n t r o d u c e other
m e c h a n i s m s of c h l o r i d e p e n e t r a t i o n w h i c h c o u l d v a r y the p r e d i c t i o n ,
which, as was a f o r e m e n t i o n e d , opens the door to the c a l c u l a t i o n of
D coefficient from simple, but proper resistivity values
(3) (45) (46).
Vol. 23, No. 3 CHLORIDE DIFFUSION,AASHTOTEST, RESISTIVITY 739

DCi4C~,g) A a = 0 . 1 mol/cm 3
o a=0.3,5 ,,
x 0=0.5 ,,

10 - 4

10-5

10-e
10-7

lO-e

P
i 10 ,6' ,6' 16" (ohm .cm-1)
NERNST-EINSTEIN EQUATION

Figure 7. Graphic representation of Nernst-Einstein equation [i0]

in function of chloride activity values.

Summing up, Nernst-Plank equation has to be used when values of

chloride flux along time in a Migration Cell, are a c c u r a t e l y
recorded, providing steady-state conditions are established.
Alternatively, Nernst-Einstein equation may be used w h e n instead
of chloride flux, intensity values are accurately recorded, steady-
state conditions are operating and the chloride t r a n s f e r e n c e number
is also accurately calculated.

CONCLUSIONS

More than conclusions, the following paragraphs are a summary of

comments which can be drawn up from a thorough study of basic books
on e l e c t r o c h e m i s t r y and a careful meditation on their a p p l i c a t i o n
to the p a r t i c u l a r case of concrete.

The Rapid Chloride Permeability Test (AASHTO) in its present

formulation cannot inform on concrete permeability to
chlorides. The recording of the total current p a s s i n g across
the cell is a function of the amount and type of ions, but not
of the chloride flux or chloride mobility.

The calculation of ionic migration can be only r i g o r o u s l y

r e s s o l v e d in homogeneous, binary and dilute solutions.
Concrete and concrete pore solution is a p o l i e l e c t r o l y t e with
high ionic strength and therefore, a rigourous c a l c u l a t i o n
cannot be performed or results very difficult.
740 C. Andrade Vol. 23, No. 3

However, as a p p r o x i m a t e values may be e n o u g h for p r a c t i c a l

purposes, simplified ways of calculation of Diffusion
Coefficient of c h l o r i d e s may be tried. This s u p p o s e s the
a c c e p t a n c e of some a s s u m p t i o n s and u n c e r t a i n t i e s .

Thus, a s s u m i n g some simplifications, N e r n s t - P l a n k and N e r n s t -

E i n s t e i n e q u a t i o n s can be used in a d i s p o s i t i o n s i m i l a r to a
d i f f u s i o n cell (migration cell): the m a i n b e i n g to a c c e p t that
c o n v e c t i o n does not o p e r a t e inside the c o n c r e t e and that
d i f f u s i o n is n e g l i g i b l e c o m p a r e d to m i g r a t i o n w h e n e l e c t r i c a l
f i e l d s h i g h e r than 10v are operating.

F r o m equations, [8] and [ii], E f f e c t i v e D i f f u s i o n C o e f f i c i e n t ,

De, , can be c a l c u l a t e d in an e x p e r i m e n t of few days. N e r n s t -
P l a n k e q u a t i o n can be used w h e n only c h l o r i d e flux a l o n g time
is r e c o r d e d and N e r n s t - E i n s t e i n e q u a t i o n w h e n i n t e n s i t y v a l u e s
and c h l o r i d e t r a n s f e r e n c e numbers are a c c u r a t e l y a p p l i e d and
measured respectively.

An extensive experimental program, which at p r e s e n t is

b e i n g c a r r i e d out by the author, is n e e d e d to c h e c k w h e t h e r
the a s s u m p t i o n s c o n s i d e r e d are c o r r e c t or not.

F i n a l l y it has to be m e n t i o n e d that the same e q u a t i o n s can be

a p p l i e d to c a l c u l a t e ionic m o v e m e n t s in the case of c a t h o d i c
p r o t e c t i o n , c h l o r i d e removal or r e a l k a l i z a t i o n , a l t h o u g h in these
cases a n o n - s t a t i o n a r y p r o c e s s is e s t a b l i s h e d w h i c h m a k e s m o r e
s o p h i s t i c a t e d the s o l u t i o n of e q u a t i o n [6] and [ii]. S p e c i a l l y
seems v e r y a t t r a c t i v e the r e s s o l u t i o n in the case of c h l o r i d e
removal, because it may give the t h e o r e t i c a l t i m e n e e d e d to
d e c r e a s e the a m o u n t of c h l o r i d e s below a c e r t a i n t h r e s h o l d .

ACKNOWLEDGEMENTS

The a u t h o r is g r a t e f u l to several r e s e a r c h e r s for t h e i r c o m m e n t s

and e x p e r i m e n t a l trials. First she is g r a t e f u l to Dr. J. G a l v e l e
of A r g e n t i n a for the d i s c u s s i o n on the p r e l i m i n a r y s t a t e s of the
p a p e r and the c o m m e n t s i n t r o d u c e d in the final version. T h a n k s are
also g i v e n for the d i s c u s s i o n s to her c o l l e a g u e s at the Institute:
Dr. S. Gofii and Dr. C. Alonso, and finally to Mr. M.A. S a n j u ~ n for
his e x p e r i m e n t a l trials.

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