Materials and Structures/Mat6riaux et Constructions, Vol.
29, October 1996, pp 476-484
A comparison of chloride ion diffusion coefficients
derived from concentration gradients and non-steady
state accelerated ionic migration.
C. Andrade 1, D. W h i t i n g 2
(1) Instituto de Ciencias de la ConstruccionEduardo Torroja, Madrid, Spain
(2) Construction TechnologyLaboratories, Skokie, Illinois, USA
A B S T R A C T
A method for electrical indication of the ability of con-
crete to resist chloride ion penetration was first developed
in the USA in the late 1970's. The test method (AASHTO
T 277) related chloride ion diffusion to the measurement of
electrical charge passed through a test specimen in a rela-
tively short period of time. In this paper, chloride concen-
tration profiles obtained from specimens used in the initial
development of the method are used to compute apparent
chloride diffusion coefficients, Dapp, by application of ionic
migration principles. These coefficients are compared to
Dapp calculated from fitting data obtained from 90-day
ponding tests carried out on companion specimens not
subjected to application of electrical currents.
It is shown that there is a strong linear relationship for
conventional concretes between coefficients calculated
from chloride concentration gradients produced either by
long-term ponding or by accelerated ingress of chloride
into the test specimens. Also included in the comparative
study are effective diffusion coefficients, Deft, based on the
measurement of specimen resistance and calculated using
Einstein's equation. Results indicate that values calculated
by any of the techniques yield lower values for diffusion
coefficients than those obtained from longer-term pond-
ing. It is shown, however, that rankings of concretes on the
basis of diffusion coefficient are similar for both calculated
and measured values. Large errors occur in calculated coef-
ficients in cases where anomalies exist in measured chlor-
ide gradients. These errors are related to the dependence of
calculated diffusion coefficients on chloride concentration
ratios. For specialty polymer concretes, mechanisms of
penetration of chloride into concrete may be different in
the presence of an applied electrical field.
These differences may be the result of the short test
time in the AASHTO T 277 procedure as well as of the
relatively high voltage used. These effects prevent the
Editorialnote
CarmenAndradeis theDirectoroftheInstitutoEduardoTorrojawhichis a RILEM TitularMember.Dr. Andrade,whowas the 1986RILEM Medallist,has
for manyyearshadgreatresponsibilitieswithinRILEM. Chairladyof theAdvisoryTechnicalCommitteeuntil I993, she is nowa memberof the Coordinating
Committee. She is activein 116-PCD TechnicalCommitteeon Permeabilityof Concreteas a Criterionof its Durabilityand has beenappointedChairdladyof
154-EMC TechnicalCommitteeonElectrochemicalTechniquesforMeasuringMetallicCorrosion.CarmenAndradewasappointedPJLEM Fellowin 1995.
0025-5432/96 9 RILEM
R :SUM
Une m~thode d'essai de la re'sistance du b~ton 3 la
p~n~tration des chlorures a ~t~ raise au point aux l~tats-
Unis ~ latin des ann~es 1970. La m~thode ( A A S H T O
T 277) relie la diffusion des chlorures ~ la quantit~ de
charge ~lectrique qui passe ~ travers l'~chantillon pendant
une assez courte dur~e. Darts ce travail, on utilise les pro-
ills de concentration de chlorures obtenus pour calculer le
coefficient de diffusion, Dapp, en utilisant les principes de
migration ionique. Ces Dapp sont, ~ leur tour, compares
avec les r~sultats de Dapp obtenus h partir d'un essai de
diffusion naturelle pendant 90 jours.
On montre qu'il existe, pour les b~tons convention-
nels, une tr~s bonne correlation de tous les coefficients de
diffusion calculus ~ part# des profils de concentration pro-
cluits ou par essais de diffusion naturetle ~ long terme ou
par entree acc~l&~e des chlorures clans les {prouvettes. On
inclut aussi clans la comparaison les coefficients de diffu-
sion effective, Deft, bas~s sur la mesure de la r~sistance
~tectrique et calculSs seton t'Squation d'Einstein. Les
r~sultats montrent que les coefficients de diffusion ainsi
calculus ont des valeurs in)&ieures ~ celles obtenues par
diffusion naturelle. La classification relative de la r~sis:
tance des b~tons aux chlorures est pourtant la m~me. Des
erreurs importantes se produisent quancl Ies pwfits pr~sen-
tent des anomalies. Elles proviennent de l'influence des
taux de concentration en chlorures sur les coefficients de
diffusion. Pour les borons aux polym~res, les mScanismes
de p~n~tration des chlorures peuvent ?tre diff&ents si un
courant ~lectrique est applique.
Toutes ces diff&ences peuvent 8tre imput~es ~ la courte
dur~e des essais A A S H T O T 277 et au voltage asse;;:
~levd qui est utilisO. Ces circonstances empSchent le b~ton
d'atteindre la mgme concentration superficielle Cs que
clans le cas de la diffusion naturelle. On trouve des valeurs
anormalement hautes quand le b~ton est trop r~sistif ou
476
Andrade,Whiting
concrete from reaching the same chloride surface con-
centration, Cs, as in longer-term (90-day) ponding.
Anomalously high D.app valves are computed when the
concrete is too resisnve or has been surface treated. In
these cases, the Cs valves are far greater than those
obtained during 90-day ponding.
iiiiii}
i*
1. INTRODUCTION
Corrosion of reinforcing steel in concrete continues to
be a serious problem worldwide. One of the primary
causes of this corrosion is the chloride ion [CI-], which
destroys the natural passivity of steel in the highly-alkaline
concrete environment, thus leading to the formation of
corrosion products which exert large tensile forces on the
concrete matrix and ultimately lead to the cracking and
spalling of concrete in chloride-contaminated atmos-
pheres. The time of the initiation of corrosion [1] is con-
trolled by the depth of the concrete cover and the time
taken for chloride ions to penetrate this cover. Since the
cover of concrete over reinforcing bars is generally speci-
fied by agencies, such as US [2] or European [3] codes, the
major variable determining the time-to-corrosion is then
the permeability of the concrete to chlorides. This "per-
meability" may be a function of the absorption of unsatu-
rated concrete through capillary processes in the near sur-
face layers [4], and of the diffusion of chloride through the
saturated or nearly-saturated concrete at somewhat greater
depths up to the reinforcing steel. Both mechanisms,
absorption and diffusion, should be taken into account
when chloride penetration rates are model]ed or tested.
However, very few models consider both mechanisms and
only diffusion is generally modelled by means of solving
Fick's second law:
or a2C
-D (1)
at aX2
assuming a semi-infinite medium and the following ini-
tial and boundary conditions :
Cx = 0, x _>0, t=0 (2)
Cx=Cs, x=0, t>0 (3)
which leads to the generally-accepted solution :
Cx erfc x
C-7 = 2v/-D-7 (4)
Considerable previous work has been carried out in
order to develop data on chloride diffusion coefficients for
concrete [5-10]. However, more recently, attempts have
been made to use short-term experiments to predict prac-
tical long-term concrete performance. It is questionable
whether short-term experiments give results reliable
enough to be used for such predictions, and possibly such
short-term experiments may only help to quantify differ-
477
qu'il a refu un traitement de surface. Dans ces cas, la
concentration supe~'cielle Cs est beaucoup plus grande
que clans les essais de diffusion a 90jours.
ences between concretes rather than accurately predict
future performance.
With the aim of comparing concretes of various com-
positions with respect to their relative resistance against
chloride penetration, in the late 1970's a technique for
determining the relative permeability of concretes to
chloride ions was developed under contract to the Federal
Highway Administration (FHWA). The method was later
standardized by the American Association of State
Highway and Transportation Officials (AASHTO) as
AASHTO T 277 [11], and in 1993 a revised version was
standardized by ASTM as C 1202 [12]. Both methods rely
on measuring the amount of electrical charge passing
through a saturated 100-ram diameter slice of concrete
50 mm thick during a 6-hour test period under an applied
potential of 60 Vdc. The initial development report [13]
noted that the test was primarily qualitative in nature and
should only be used to rank concretes in terms of their rel-
ative ability to permit ingress of chloride ions and not to
predict the quantitative amount of chloride which could
pass into the concrete. However, the test has been
employed, especially in the US, for specification purposes,
using the data presented in the original report to construct
limits of acceptance based on the amount of charge passed
(in coulombs) over the six-hour test period. Variants of the
test developed by Zhang et al. [14] and Detwiler et al. [15]
have also been proposed. Because of this, considerable crit-
icism of the test has been recently occurring in both the
US [16] and Europe [17].
Recent work [18] has been carried out with the aim
of clarifying the fundamental meaning of this test and of
contributing to the understanding of the processes
occurring when an electrical field is applied to the con-
crete, such as that occurring during cathodic protection,
chloride removal or realkalization. In the cited study,
Nernst-Plank and Nernst-Einstein equations were used
to calculate diffusion coefficients from a migration test
(AASHTO T 277) either under steady-state [18] or
non-steady-state conditions [19]. Therefore, it appears
feasible to calculate chloride diffusion coefficients (D
values) from chloride profiles or from electrical resistivi-
ty of the concrete.
The objective of the study described in this paper is
to determine the relationships between diffusion coeffi-
cients calculated from electrical parameters of the
AASHTO test and calculated from the profiles of chlo-
ride actually entering the concrete under short-term
(i.e., using 60 Vdc potential) and long-term (90-day
Materials and Structures/Mat~riaux et Constructions,Vol. 2 9 , October 1996

Table 1 - Mix proportions and characteristics of fresh concretes used in the study
Mi~ure Type Cement(kgm -3) Water(kgm -3) Additive(s)(kgm -3) Slump(mm) Aircontent(%)

CON6 w/c=O.60 390 234 - 198 8.0

CON4 w/c=0.40 390 156 - 50 7.9
CON32 w/c=0.32 490 160 WRA-I.1 6.7
LMC latex-modified 390 94 SBR latex- 58 182 7.7
ISC internally-sealed 390 216 wax beads - 71 86 3.7
PC polymer resin- 20 % w/w - catalyst- 0.4 % w/w - -
PIC polymer-impregnated 390 195 PMMA- 5% w/w 81 5.2

ponding) exposures. As the authors had access to the
original data used in the AASHTO T 277 test develop-
ment, it was felt that this information would be especial-
ly pertinent to current discussions relating to the signifi-
cance and use of the AASHTO procedure as well as
serving to suggest modifications that may improve its
suitability as a predictive indicator of chloride penetra-
tion into concrete.
2. MATERIALS, MIX PROPORTIONS AND
SPECIMEN PREPARATION
2.1 Materials
Eight types of concrete were selected for this com-
parative study (see Table 1). Three were conventional
concretes (CON6, C O N 4 , CON32) with water-to-
cement (w/c) ratios ranging from 0.6 to 0.32. The other
five concrete types were modified by the addition of dif-
ferent types of polymers and special treatments.
All concretes, with the exception of the single-poly-
mer concrete (PC) mixture, were produced with ASTM
C 150 Type I Portland cement. Coarse aggregate was a
dense, crushed limestone. Fine aggregate was a natural
siliceous sand. The polymer modifier used in the latex-
modified concrete (LMC) was a 48% aqueous emulsion
of styrene-butadiene latex. Beads of a 75:25 blend of
paraffin and montan wax were used in the internally-
sealed concrete (ISC).
An air-entraining agent based on neutralized Vinsol
resin was used in all concretes except the LMC and ISC
mixes. A lignin-based water reducer was used in the low
w/c ratio concrete. The PC mix was produced with a
polyester monomer binder and minus 2 m m silica sand
in a proportion of 20:80 by mass. A methyl ethyl ketone
(MEK) accelerator was used at 2 % by weight of resin
binder. The polymer-impregnated concrete (PIC) was
produced using a methyl methacrylate (MMA)/trimethyl
propylyl tri-methacrylate (TMPTMA) monomer mix in
a proportion of 95:5 by mass. The monomer system was
catalyzed with a 1% benzoyl peroxide initiator.
2.2 Mix proportions
Mix proportions for all concretes produced for this
study are given in Table 1. With the exception of mixes
CON32 and PC, all concretes were produced having a
cement content of 390 kg/m3. The low w/c ratio mix
(CON32) is typically used for bridge deck overlay appli-
cations, and heaW vibration is used to consolidate this
zero-slump concrete. The last four mixes in Table 1 rep-
resent specialty concretes either in use or under consid-
eration for use by the FHWA during the period when
this work was initially carried out (mid to late 1970's). At
the time, latex-modified concrete (LMC) was just
beginning to be widely used as a bridge deck protective
system [20]. Internally-sealed concrete (ISC), using wax
beads which are subsequently melted inside the concrete
after hardening, had been developed by the FHWA [21].
The sixth mix used, polymer concrete (PC), had also
been developed during the same time period for the
FHWA [22] and others [23], and continues to be used in
thin (12 to 25 mm) deck topping applications. The final
type, polymer-impregnated concrete (PIC), has also
been largely confined to experimental studies.
2.3 Specimen preparation
From each concrete mix, a series of slabs 600 x 300 x
150 mm in dimension were cast. All slabs cast from the
conventional and PIC mixes were moist-cured under
wet burlap over an initial period of 14 days. Slabs were
then tightly sealed in heavy polyethylene wrapping and
allowed to age for a period of 3 months.
Slabs cast from mixes LMC, ISC and PC were pro-
duced in accordance with procedures unique to each special
material. LMC slabs were moist-cured for only 1 day, fol-
lowed by continuous air drying. One set of ISC slabs was
given the initial 14-day moist cure, removed to air for an
additional 1 week of air curing, then surface treated with
heating blankets until the temperature reached 85 ~ C at 50
mm from the surface. A second set of ISC slabs (ISC-A)
was cured, but not subjected to surface heating. The slabs
were then polyethylene-wrapped as per the conventional
mixes. PC slabs were not given any moist curing after

478
Andrade, Whiting
Fig. 1 - Aspect of the cell used for AASHTO T 277.
casting, as no water is required for cure of the resin-based
binder. PIC slabs were given the initial 14-day cure, then
dried, soaked in monomer and polymerized.
After completion of specimen preparation and curing,
the plastic wrapping was removed and a series of 100-ram
diameter cores was extracted from one of the slabs in each
set for AASHTO T 277 testing. The companion slab was
prepared for AASHTO T 259 90-day ponding. Test pro-
cedures are described in the following section.
3. TEST PROCEDURES
3.1 AASHTO T 277
Test slices 50 mm thick were removed from the top
of each 100-mm diameter core taken from the concrete
slabs. The slices were allowed to air dry for i hour, then
were prepared for testing in accordance with the stan-
ii I I
I I I ||||
~ Y P )
-i :1
r ~
- ........................
\114"
dard AASHTO method [11]. Just prior to testing, the
electrical resistance of the specimen was measured
(P'qnitial) using a 100 Hz AC soil resistance meter applied
across the Screen electrodes within the test cell (Figs. 1
and 2). Upon conclusion of testing the resistance of each
specimen was once again measured using the AC meter
(P'-final). Each test specimen was then sealed in a thick
polyethylene bag and transferred to a freezer maintained
at - 18~ C in order to prevent further migration of chlo-
ride ions within the specimens until slices could be
obtained for the analysis of chloride gradients.
3.2 Determination of chloride
content in slices
Each 50 mm x 100 mm test specimen was rapidly
transferred to a water-cooled diamond saw, and a nomi-
nal 6-ram thick slice was obtained from the top surface.
Slices were removed until each specimen had been sec-
tioned into 5 slices. Slices were then fractured in a jaw
crusher, and ground to pass a 150-tim sieve. The result-
ing powder samples were analyzed for total chloride ion
content in accordance with AASHTO T 260.
3.3 AASHTO T 259 (90-day ponaing)
Slabs, companion to those from which the 100-mm
cores were obtained, were ponded with a 3-percent solu-
tion of sodium chloride for a period of 90 days. At the end
of this period, powder samples were obtained by drilling
at the following increments: 0-10 ram, 10-16 ram, 16-
22 mm, 22-29 mm and 29-41 mm. Powder samples were
then analyzed for total chloride ion content.
Two units req'd.
J---- 2" ~L~_4"
I
I-- r-IIIII
GLue join screen
3/" 1 i-JllL--
I
f
unit to cell
I
I
I
I
I
I
I
I
I
I Fig. 2 - Layout of the cell
I Mesh soldered of Fig. 1.
I
between shims
L1 5"~
479
Materials and Structures/Mat~riaux et Constructions, Vol. 29, October 1996

4. CALCULATION OF DIFFUSION Table 3 - Chloride contents of slices

COEFFICIENTS obtained from 90-day ponding specimens
Mixture Type Mid-point of Total
Three theoretical procedures have been used to cal- depth (mm) chloride(%)
culate diffusion coefficients: 1) by fitting equation (4) CON6 w/c=O.60 5 0.442
into the chloride profiles obtained either from the 13 0.293
AASHTO T 277 (60 V) test or from the 90-d ponding 19 0.179
test ; 2) by introducing resistivity values ; or 3) by intro- 25 0.107
ducing the charge passed (in coulombs) into the Nernst- 35 0.038
Einstein equation. CON4 w/c=0.40 5 0.503
The fitting of chloride profiles into equation (4) was 13 0.172
carried out by regression analysis. 19 0.083
25 0.025
From the Nerst-Einstein Equation (AC Resistivity), 35 0.012
effective diffusion coefficients, Deft, can be calculated, as
the equation only holds for ions diffusing under steady- CON32 w/c=0.32 5 0.261
13 0.054
state conditions with no reaction [24]. The equation 19 0.011
used is: 25 0.008
RT 1 to 35 0.007

Deft- nF 2 9 " cyZ (5) LMC latex-modified 5 0.303

13 0.044
In addition, the coulombs passed during the 6 h of 19 0.025
the AASHTO test may be converted into a "mean" 25 0.019
electrical current value by dividing the coulombs by the 35 0.011
time (21,600 seconds). The 60 V applied are then divid- ISC internally 5 0.052
ed by this mean-calculated current to obtain a mean sealed-heated 13 0.013
resistance. Finally, resistivity is measured using the cell 19 0.008
25 0.006
geometry parameters given in 4.2.II. 35 0.007
The resistivity value is then introduced into (5) in
order to calculate Deft. ISC internally 5 0.390
sealed-unheated 13 0.242
In addition to these three theoretical parameters, an 19 0.133
empirical approach suggested by Berke [26] has also been 25 0.057
used. Berke's equations are: 35 0.018

From coulombs: D = 0.0103 x 10-8 Q0.84 (6) PC polymer 5 0.058

13 0.022
From resistivity: D = 54.6 x 10-8 p -1.01 (7) 19 0.011
25 0.009
35 0.009
PIC polymer- 5 0.138
impregnated 13 0.043
Table 2 - Results of AASHTO T 277 19 0.013
testing on slices obtained from cores 25 0.009
35 0.000
Resistance
Mixture Type Charge Initial Final
passed (ohms) (ohms)
(coulombs) 5. RESULTS
CON6 w/c=O.60 4570 580 260
5.1 AASHTO T 277 results
CON4 w/c=O.40 1540 1000 675
CON32 w/c=0.32 1170 1200 945 Results ofAASHTO T 277 testing are shown in Table
LMC latex- 613 2600 1550 2. In addition to the amount of charge passed through the
modified slices over the 6-hour test period, the electrical resistance of
each specimen before and after testing was also recorded.
ISC internally 1330 1250 805
sealed-heated The highest values of charge passed (and lowest resistances)
were obtained for the high w/c ratio concrete (CON 6) and
ISC internally 4310 455 320 the ISC-A, which had not been surface heated. The charge
sealed-unheated
passed decreased for the remaining conventional concretes
PC polymer 0 > 106 5 x 105 with lower w/c ratios, and was much lower for LMC and
PIC polymer- 35 56000 23000 negligible for the PC and PlC. For the latter two concretes,
impregnated very high electrical resistances were recorded.

480
Andrade, Whiting

5.2 Chloride content of drill samples from Table 4 - Chloride contents of slices
90-day ponding specimens obtained from AASHTO T277 specimens
Chloride contents of the drill samples taken from the Mixture Type Mid-pointof Total
depth (mm) chloride (%)
90-day ponding slabs after completion of the test are
shown in Table 3. Significant amounts of chloride have CON6 w/c=0.60 4 0.192
diffused into the specimens over the 90-day period of test- 15 0.231
24 0.125
ing. In a number of the test concretes, chloride ions were 33 0.042
detected at depths of more than half-way through the test 45 0.008
slice. For all concretes, large amounts of chloride were
CON4 w/c=0.40 5 0.257
detected within the first 3 to 5 mm from the surface, indi- 17 0.110
cating that even highly-impermeable concretes are not 28 0.047
able to keep chloride from penetrating into the near-sur- 38 0.045
face skin under the conditions of the ponding test. 47 0.043
CON32 w/c=0.32 3 0.194
13 0.046
5.3 Chloride content of slices from 23 0.012
34 0.012
AASHTO T 277 test 46 0.011

Chloride contents of slices taken from the AASHTO LMC latex-modified 4 0.129
T 277 test specimens are shown in Table 4. No data 14 0.007
24 0.007
were obtained from the PC specimen. For comparative 34 0.005
46 0.005
%CL- total ISC internally 4 0.082
I
0.6 sealed-heated 14 0.045
1 o 90 days 22 0.050
0.5J - 9 60 Volts 31 0.052
43 0.056
04t k |
ISC internally 3 0.164
sealed-unheated 12 0.252
22 0.204
33 0.038
45 0.021
i
PIC polymer- 4 0.008
impregnated 14 0.008
25 0.008

~
34 0.007
O3 CON 3Z 46 0.007
O.Z
O.1 purposes, the chloride profiles resulting from 90-day
ponding and the 60 V test are shown in Fig. 3. For two

0-41
of the sets in Table 4 (CON6 and ISC-A), chloride con-
tent at the second sampling increment is greater than
from the first slice. This may be attributed to depletion
0.3 of the chloride concentration in the test cell reservoir as
S
l __CC the test proceeded, so that the amount of chloride enter-
O.Z
ing the cell was reduced over the testing period.
0.1 ~ In general, it can be seen from Fig. 3 that for ordi-
i J
nary concretes the profiles reached are of similar shapes
for both tests. This is especially true when the sampling
interval closest to the surface is disregarded. For poly-
meric concretes (LMC and ISC-A), agreement between

~
Pi._~c
P__q
chloride profiles for the two tests is reasonably good.
o.1 However, for the PIC mix there is a significant differ-
ence between the two profiles, with this arising from the
60 V test being anomalously "flat". For the PC, no pro-
files were obtained from the 60 V test specimens, thus
5 cm 1 2 3 4 5 cm
no comparisons can be drawn. Values of Cs, calculated
Fig.3 - Chloride profiles of the different concretes o f Table 1 from chloride profiles in both tests, are compared in Fig.
after 90-day ponding (Table 3) and 60V tests (Table 4). 4, which shows that the Cs achieved in the 60 V test is

481
Materials and Structures/Mat6riaux et Constructions, Vol. 29, October 1996

D x 10-ecm2/s
Cs% 60V g
/ 122.5 523.0
0.6- / ISC PIC
0.5-
line of
equality /
/
0.4- Y n 60Vdc
o Einstein in
/
/ CON4 9 Einstein fin /
/CON32 CON6
0.3-
=9 9
0 Berke Q
x Coulombs /
12000
0.2-
/ / ISC-A 9L M_..~C /
/ ISC-A
0.I - t I/_IS._..C.r=PI_..CC rl CON 6
/ o <>
' '
0.2 ' O14. . . 0.6
. 018 ' '
1.0 8000
Cs% PONDING
/
/ ~
Fig. 4 - Comparison of values of surface chloride s__.cc
i x
concentrations, Cs, obtained by curve fitting / CON 4 9
4000
.~QN 320 {~ X
Equation (4) into chloride profiles of Fig. 3 (90-day M._.._C,/~"
L O o
ponding and 60V tests).
/~ - t o

much smaller for ordinary, latex-modified and 2 4 6 8 10 12 14 16 18 2 2 2

internally-sealed concretes. That is, in spite of
the fact that the profiles seem similar, the more
rapid 60 V test apparently does not allow suffi-
cient time for a similar degree of chloride inter-
action with the concrete.
5.4 Calculated diffusion coefficients
The data developed in the original FHWA test pro-
gram [27] presented in Tables 3 and 4 were used to calcu-
late diffusion constants in accordance with the expressions
previously developed in Section 4 of this paper. Results are
PONDING Dap xlO~
Fig. 5 - Comparison of diffusion coefficients listed in Table 5.
presented in Table 5 and Fig. 5. Since no chloride concen-
tration profiles were obtained for the PC mix specimen
subsequent to the AASHTO T 277 test, no apparent dif-
fusion constants were calculated in this case.
It is evident from both Table 5 and Fig. 5 that D90 d is
always greater than D60 V, indicating that the 60 V test
does not absolutely reproduce the 90-day ponding test, as
was already seen in Fig. 4. However, in terms of relative
ranking, the comparison is more optimistic. Accordingly,

Table 5 - Values of resistivity, p,

surface concentration, Cs, and diffusivity, D, for the different test types
From CI profiles Einstein equation Berke equations
DappX10 -8 cm2/s DeffX 10.8 cm2/s Dappx 10s cm2/s
Ponding 60V Coulombs RINITIAL RFINAL FROM FROM
AASHTO p(KELCM) ILQ.CM Q RINT

CON6 Cs 0.552 0.258 4570 p 9.3 4.16

D 24.56 9 6.53 D 3.13 7.01 12 5.74

CON4 Cs 0.75 0.30 Q 1540 p 16.02 10.81

D 7.90 4.32 D 2.20 D 1.82 2.70 4.9 3.31

CON32 Cs 0.47 0.261 Q 1170 p 19.224 15.14

D 4.20 0.95 D 0.67 D 1.51 1.92 3.89 2.75

LMC Cs 0.59 0.233 613 p 41.65 24.83

D 3.44 0.3 0.87 D 0.7 1.17 2.26 1.26

ISC Cs 0.082 0.068 1330 p 20.02 12.89

D 6.26 122.5 1.37 D 1.45 2.26 4.33 2.64

iSC-A Cs 0.51 0.245 4310 p 7.29 5.12

D 18.34 13.1 4.40 D 4.00 5.70 11.63 7.34

PC Cs 0.079 p > 106 5x10s

D 10.74 D < 0.0001 0.00074

PIC Cs 0.22 0.008 35 p 897.1 368.46

D 6.46 523 0.036 D 0.032 0.079 0.204 0.057

482
Andrade, Whiting
rankings from 90-day D values compare favorably to those
from the rest of the derived diffusion coefficients shown in
Table 5, except in the case of those obtained from 60 V
profiles. For this last method of calculation, some anom-
alies are produced due to the flatness of the ISC and PIC
chloride profiles. For these two concretes, the Dapp values
calculated from the 60 V profiles are too high.
6. DISCUSSION
6.1 Comparison of different methods
of calculating D values
Several methods of calculating the D values have
been presented in Table 5. In order to compare them,
the differences between what have been termed Dapp
and Deft should be clarified.
An apparent (Dapp) value has been attributed [24[ [18]
to the value obtained in a non-steady state experiment
such as 90-day ponding, where chloride binding is occur-
ring simultaneously with diffusion. On the other hand, an
effective (Deft) value is obtained when the experiment is
performed under the steady-state condition in concretes
already saturated with chlorides ; therefore, no binding is
developed during diffusion. Usually, Dapp is smaller than
Deft. From the results shown in Table F, only D values
calculated from the Einstein equation (resistivity values)
yield Deft. In the other methods, Dapp is calculated.
Consequently, it does not appear reasonable that Deft
values are less than the Dapp values obtained from the
remaining methods. This willbe explained in 6.2.
The higher values of Deft obtained from R.fina1 result
from the fact that the resistivity of the concretes already
contaminated with chlorides during the test is less and
therefore, Deft final is greater than Deft initial. However,
Deft initial is probably more applicable to new construc-
tion, since it reflects the condition of a non-contaminated
concrete.
It is also apparent that D values obtained from resis-
tivity values (using AC methods) and those calculated
from coulombs passed are quite similar, confirming the
fact that the charge passed represents a measurement of
the concrete resistivity. In consequence, similar results
nlay be obtained by performing a resistivity test, in lieu
of the longer AASHTO T 277 procedure.
For any given concrete, the values obtained using
Berke's equations (from coulombs, Q, or resistivity,
Rinitial) are more similar to Dap~p (90 ,days) than. to Deft
(60 V). This is reasonable as Berke s equanons were
derived from long-term (two years or more) non-sta-
tionary chloride penetration.
6.2 Comparison of 90-day ponding
and 60 V tests
Natural diffusion and migration are effects controlled
by the same basic principles, and are both regulated by
the diffusivity or mobility of the ions. This means that if
483
electrolyte compositions are equal, movement of ions
will follow the same pattern [28-29] for natural diffusion
and for electrical migration.
This explains the similitude of chloride profiles
obtained from 90 d and 60 V tests. However, the fact
that (Cs, Dapp) 90 d are greater than (Cs, Dapp) 60 V indi-
cates that eitfier the 60 V test is too short or the voltage
too high to fully reproduce the 90-day test. In a previous
paper [19], it was found that a voltage drop of 12 V and a
testing time of one week were able to reproduce profiles
ofponding periods of one year.
In addition to the short duration of the 60 V test, two
other reasons may help explain the differences between
the profile shapes of the 90 d and 60 V tests:
1) If the testing time is too short, the binding or reac-
tion of chlorides with the cement matrix may be less
than in longer- term tests.
2) The D value may be an inverse function of the
chloride concentration, D = f (1/Ccl-). That is, D would
increase as CCl- decreases. This is demonstrated by the
flat shape of the profiles in the case of the impermeable
ISC and PIC concretes, as well as in the observation that
the penetration fronts (profiles beyond 1-2 cm where
the chloride concentration is smaller) are quite similar in
both types of tests. It appears that low chloride concen-
trations may allow more of a simulation of short-term
migration tests.
Therefore, if one wishes to obtain similar absolute D
values from 90-day and electrical migration tests, the test
duration and voltage have to be optimized in order to
minimize the development of other mechanisms, such as
absence of binding, or enhancement of the dependence
o l D values on chloride concentration.
This optimization is especially critical in concretes
made with polymers, as Table 5 demonstrates that they
may exhibit anomalous behaviour, which indicates dif-
ferent mechanisms of chloride penetration in these con-
cretes. Such differences may be due to "skin" effects or
non-constant D values.
7. CONCLUSIONS
The conclusions that can be drawn from the present
study include the following:
1. The acceleration of chloride penetration into con-
crete by the use of an electrical field is an important
advance, whose quantification will provide use in a vari-
ety of applications.
2. However, test conditions for the 60 V AASHTO
test have to be optimized if long-term concrete perfor-
mance is to be predicted.
3. For ordinary and latex-modified concretes, similar
chloride profiles are obtained for 90-day ponding and 60
V tests. For polymer-impregnated concretes, the differ-
ences in profiles between the two tests enable deducing
the occurrence of other mechanisms, such as lower chlo-
ride binding or a change in D value (D = f(Ccl-)) with
chloride concentration.
Materials and Structures/Mat~riaux et Constructions, Vol. 29, October1996
4. Among the different methods used for calculating
D values, those using initial resistivity or charge passed
(coulombs) yield similar results if the Einstein equation
is used. The concrete rankings obtained from these
methods are similar to those obtained from the 90-day
ponding test.
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