Magazine of Concrete Research, 1990, 42, No. 152, Sept.
, 177-185
Rapid estimation of chloride diffusion
coefficient in concrete
R. K. Dhir*, M. R. Jones*, H. E. H. Ahmed* and A. M. G. Seneviratne*
U N I V E R S I TOY
F DUNDEE
A simplepotentialdifference ( P D ) test is developed
thatcanrapidly(within 10 days) provide a chloride
dzffusion index. The test utilizes a small applied poten-
tialdzfference (10 V d c ) to acceleratethetransport
of chlorideionsthroughconcrete.Conventionalnon-
perturbative, concentration difference ( C D ) t e s t s have
been carried out in parallel, with typical test periods of
up to 12 months. Fick's First Lawof Dzffusion is applied
to calculate a dzffusion index from the PD test, andthe
coejicient of chloride dzffusion D from the C D t e s t . A
closerelationshipbetweenthesetwoparameters is
shown, allowing D to be estimated from the rapid P D
test.
Introduction
The ingress of chlorides into concrete can have a
major destructive effect on reinforcing steel, and is one
of the most serious problems encountered in concrete
structures worldwide. A recent report' for the Depart-
ment of Transport concluded that over 75% of con-
crete bridges in England and Wales may be affectedby
chloride attack, and that maintenance and repair costs
willhave to beincreased by 200% abovecurrent
spending levels. Methods of directly protecting rein-
forcement, e.g. by impressed cathodic currents, appear
tonot whollybe other
and indirect
methods, such as coatings on concrete or reinforce-
ment, have not been fully tested for a wide range of
structures.
For concrete to retain its reputation as a material
that is both economical and durable, particularly with
respect to maintenance, a greater understanding of the
*Concrete Technology Unit, University of Dundee, Dundee DD1
4HN, UK.
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kinetics of chloride ion transportation is necessary. A
fundamental parameter describing the resistance of a
particular concrete to the transport of chlorides is the
coefficientofdiffusion D , from which the depth of
penetration of chlorides over a period of time may be
estimated. The main problem is that the evaluation of
D using conventional concentration differencetype
tests is extremely slow, often taking up to a year to
complete. This type of test isnot, therefore, a practical
method for assessing the resistance of concrete to
chloride ingress.
Previous attempts to determine D more rapidly,
typicallywith paste systems,havemetwithlimited
success. Goto and Roy3 applied a potential difference
of up to 2 V (dc) across thin paste specimens ( < 5 mm
thick), assuming that this small perturbance did not
change the diffusionof chloride ions significantly.
Their solution to Fick's First Law was complex and
no attempt was made to relate the results to a non-
perturbative diffusiontestin order to validate the
method. Whiting4 carried out accelerated chloride
ingress testson bridge deckconcrete, in the laboratory
and in situ, using applied potential differences of 60-
80 V (dc). These results werenot correlated with D , as
it wasrecognized that thetransport ofchlorides
during the tests was not by diffusion. However, the
measured index values did appear to reflect the results
of the AASHTO chloride penetration test,5 also carried
out by Whiting.
This Paper reports the development ,of a simple,
rapid test that greatlyaccelerates the transport of
chlorides through concrete and provides a practical
basis for estimating the coefficient of diffusion. In
addition, a mathematical solution isprovidedof
Fick's First Law to evaluate the results of both the
rapid and conventional non-perturbative diffusion
tests. This solution also allows a check to assess the
validity of the experimental procedures.
177
 Dhir et al.

l
Aperture also used
for ISE electrode

10 V dc

l
Electrical supply

Clamp ,---k-l DIFFUS~ON U

stainless steel cathod,
Fig. 1. Dzffision cell used for CD and PD test (items in italics for PD test only)

Test equipment and procedures
The rapid test utilizes a perturbative application of
a small potential difference (PD) at a low current
across a concrete specimen in a diffusion cell. It has
been developed from a conventional, non-perturbative
concentration difference (CD) diffusion test, which
was used for purposes of calibration. Both tests utilize
the same basic apparatus; the PD test requires the
addition of electrodes and an electrical supply to the
diffusion cell.
Dgtrusion cells
The design of diffusion cells differs from the widely
used two-compartment type equipment, which suffers
from several disadvantages,includingthe riskof
chloride depletion in the upstream reservoir and an
inability to providemulticoncurrent tests. A single
178
sided diffusion cell was therefore developed (Fig. 1)
and placed in a large tank containing chloride solution
(Fig. 2).
The cells were manufactured from UPVC with an
endfitting to receive theconcrete specimens of
100mm dia. with thicknesses of 5-40mm. The cell
reservoir (downstream side) initially contains only
deionized water, i.e. chloride concentrationin C, = 0.
For the CD test, thecell reservoir water was saturated
with respect to Ca(OH), to preclude leaching of the
concrete specimen during the long test period. A cell
reservoir volume of 11 was chosen to ensure that a
steady state in the transport of chlorides could be
maintained over a reasonable periodof time, allowing
the use of Ficks First Law to define the diffusive flow
of ions from C, to C2 (Fig. 2(c)).
An ion selective electrode (ISE) system was used
to measure theconcentration of chloridesinthe
1990,42, Research,
Magazine of Concrete No. 152

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Amangement
Downstream side
chloride concentration
Cp. initially = 0 .
chloride conce
Tank size:
1000 x 800 x 500 mm deep
Fig. 2. Chloride immersion tanks used for PD and CD tests (item in italics for PD test only): ( a ) general arrangement;
(6) electrical supply for PD test; (c) detail of tank and diffusion cell, not to scale
reservoir.6 No attempt was made toestablish whether
other anions also increased in the cell reservoir, or
whether additional cations appeared in theimmersion
tanks. It was assumed that anyadditional ion transfer
did not significantly affect thetransportation of
chlorides.
Immersion tanks
The UPVC immersion tanks are shown in Fig. 2,
together with the electrical circuitry for the PD test
(Fig. 2(b)). Chloride solution is continuously recir-
culated throughthetankand piped to an outside
heater (stainless steel, 240V, 3 kW)via a plastic
impeller pump (240 V, 10 elmin), avoiding any local
temperature rises inside thetank.This allows the
solution tobe maintained at any required temperature
between 20 and 50" C, & 1 K,using a PID-type tem-
perature controller. A totalof four tankswere usedfor
both CD and PD tests, each of which could accom-
modate up to 40 cells, and had a hinged lidand
external insulationof 50 mm expanded polystyrene on
all sides, finished with 5 mm hardboard.
The tanks were filled with a 5 M sodium chloride
Magazine of Concrete Research, 1990,42, No. 152
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Rapid estimation of chloride diffusion coefficient
as shown in Fig. 1
55 mm polystyrene
3 mm hardboard
less steel cathode
(C)
solution (99.86% NaCl), i.e. 177 250 ppm of chloride
ion, and checked daily (PD test) or weekly (CD test)
using an XSE and maintaining a constant concentration.
This unsaturated chloride concentration was chosen
to preclude any precipitation of crystalline salt in the
concrete pores. For the CD test, the chloride solution
in theimmersion tanks was also saturated with respect
to Ca(OH), . All tests were carried out at 20" C.
Potential difference application
Anode. Materials tried were copper, galvanized steel,
stainless steel (316) and graphite. Only the graphite
electrodes were suitableasanodes, as the metals
quickly dissolved, producing a deposition of oxides
on the specimen surface (Fig. 3) whoseeffect on
the measured transport of chlorideions was not
quantifiable.
Cathode. A 3 mm stainless steel sheet was used as the
cathode, with the cells sitting on an openplastic mesh
platform 25 mm above (Fig. 2(c)).
Electrical supply. This was provided via a dc power
source (0-60 V, 0-3 A) (Fig. 2(b)). A rangeof potential
179
 Dhir et al.
Fig. 3. Deposition of corrosion products from various anode materials on concrete test specimens: ( a ) galvanized steel
anode; ( b ) stainless steel anode; ( c ) copper anode; ( d ) graphite anode; ( e ) original form of metallic anodes
differences(10,20, 40 and 60V), were tried at a
nominal supply current of up 0-5to A. Above 10 V the
cells emitted a strong smell of chlorine and caused
dissolution of even the graphite electrodes. Thus, the
applied potential difference was maintained at lOV,
giving a test period of 7-12 days, depending on the
quality of concrete. Although theelectric flux density
was not determined with all tests, the currentflowing
at steady state conditions was measured to be in the
order of 120-170mA.
Preparation of test specimens
The test specimens were obtainedfrom100mm
dia. x 300mmconcrete cylinders. Thetop lOmm
from the as-cast surface was discarded to minimize
variabilityassociated with surfaceconcrete.The
next 25mm slice was used, having been cut using a
diamond saw and lightly ground with silicon carbide
paste. Although thisspecimen preparation is likely to
produce some disturbance of the concrete microstruc-
ture, it was considered to be only a surface effect and
of minor importance to the whole test specimen. All
specimens were vacuumsaturated with deionized
water before testing to avoid any absorption effects.
The test specimen was sealed into the diffusion cell
by means of two O-rings, and additionallyby injection
of a silicon sealant around the circumferential space
between specimen and cell to prevent anypiping. This
gave an effective area of 70cm2 at steady state con-
ditions for chloride transportation.
Mathematical modelling of diffusion process
As steady state conditions are maintained in both
the PD and CD tests, Ficks First Law applies to the
180
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CD results anda similar equation to the PD test, with
electrical potential replacing chemical potential. The
same mathematical solution is used for both tests, as
follows:
J = -D-dC
dx
where J = flux (mole per cm2/s), D = coefficient of
diffusion (cm2/s) anddC/dx = chemical potential
(CD test) or electrical potential difference (PD test).
This equation can be rewritten in the form
where C , , C, = the concentration of chloride ions on
either side of the specimen of thickness e (see Figs 1
and 2).
Also, from a considerationof the kinetics of trans-
port of chlorides
where A = transmissionarea of theconcrete test
specimen of unit thickness, V = volume of the cell
reservoir containing C, concentration of chloride ions
(C, was maintained constant).
From equations (1) and (2)
Rearranging,
Magazine of Concrete
Research, 1990, 42, No. 152
 Rapid estimation of chloride dlffision coeficient

Assymtotic
to c2 = c,
Unsteady
state
/--p

Steady
state
I
I
Projection to
I
--
C2 = 0 at f
---
Unsteady
I state
b
O b 1.
Time
Fig. 4. Ideal form of chloride ion transmission through test specimens for CD and P D tests

Integrating, cement (OPC) (to BS 12) and two pulverized fuel ashes
(PFAs) (to BS 3892 : Part 1) used are given in Table 1.
Ash P3 1P differs from P28P in having lowamorphous
glass and high mullite contents. Notwithstanding any
where to = the time corresponding to the projection effects on durability, this difference has been shown
of the abscissa at C, = 0 of the linear portion of the not to affect the engineering properties of concrete.'
time versus C, graph, asshown for example in Fig. 4; The coarse aggregate was a natural gravel in two size
r, = the time at the conclusion of the experiment a t a fractions, lOmm and 20 mm combined in the ratio
concentration in thecell reservoir of (C,),, (see Fig. 4). I :2, and the natural sandwas of medium grading; all
Solving, complied with BS 882. Concrete mixes were
to cover therange of strengths and workabilities
DA
- (t,, - t o ) =
VI!
In
1 generally used in various structures (Table 2).
The concrete cylinders were demoulded after 24 h
= In [Cl
c,
-
-
c
2
c,
+
c, - c, 1 under wet hessian and cured as detailed in
Table 3. Two test specimens were prepared from each
cylinder, as described above, and mounted in the dif-
= In [ Cl - c
2
1 fusion cells. Of each pair of cells, one was placed in
the CD immersion tanks and the other, fitted with
agraphite electrode, in the PD immersion tanks.
Rearranging, The chloride concentration (C,) in each of the cell
reservoirs wasmeasuredusing theISE, at weekly
intervals for the CD test and daily for the PD tests.
This was continued until steady state conditionswere
Equation (4) isin the formof a straightline-a regres- achieved.
sion analysis willyield the slope (DAlVI!) and the
intercept value (In C, ). Thus, the coefficient ofdiffusion Test results
D maybe calculated. Comparison of the projected Typical results for the OPC concrete and two PFA
intercept value (elnC')with thetrue valueof C, concretes (C40 grade, El cured) showing the marked
provides a check that the assumptions made (steady difference intime takento reachsteady statecon-
flow conditions, etc.) and the experimental procedure ditions for the C D and PD tests are plotted in Fig. 5 .
are correct. It can also be seen from Fig. 5 that approximately ten
times as many chloride ions are passed through the
Materials and test results specimen in the PD test as in theC D test. This shows
that asmall applied potentialdifference is sufficient to
Materials producea very rapidtransportation of chlorides
The main characteristics of the ordinary Portland through concrete.
Magazine of Concrete Research, 1990, 42, No. 152 181

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 Dhir et al.

Table 1. Characteristics of OPC and PFAs used

Major oxides: YO Mineralogical Physical properties
composition: YO

OPC

63.3 CaO Setting times: min

19.1 SiO, initial 86
A', 0, 4.8 final 110
Fe, 0, 3.2 Compressive strength: N/mm2
Loss onignition 1.9 1 day 11.5
7 day 28.5
28 day 40.0

PFAs*: P31P (P28P)

SiO, 46.8 (48.1) Glass (80.2)

57.9 Fineness: % ret. 45pm sieve 5.7(7,0)
4 0, (26.4)
33.3 Mullite (8.0)
29.3
Fe, 0, 7.5 (1 1.8) Quartz 5.7 (1.8) Water
requirementt: YO 9 l(90)
CaO 3.7 (1.5) Hematite (1.7)
2.3 Pozzolanic
activity
index?: YO 101(101)
Loss on ignition 2.3(3.6) Magnetite 2.5
(4.7)
*Both PFAs comply with BS 3892 : Part 1.
?With respect to control OPC.

There is a change in juxtaposition between the
CD and PD test results for the two PFA concretes
in Fig. 5, but it is not clear whether or not this is
significant-further investigation is under way. To
give a typical example, the coefficient of diffusion D
for the OPC concrete (40N/mm2, 75 mm slump) was
calculated from Fig. 5 and equation (4) to be 26.91 x
cm2/s, which contrasts markedly with the PD
indexvalueof2.19 x cm2/s.The order ofmagni-
tude differencebetweenthese two values further
demonstrates that the results obtained with thePD test
cannot be taken directly as coefficients of diffusion.
The check of the intercept value of the In (C, - C,)
versus timeplots showed that elnc' was generally within
lOOppmof the true C , value of 177250ppm for
the CD method; for the PD test the valueswere
within 250ppm. This validates, in
principle, the
useof Fick's First Law and a similar equation for

Table 2. Mix proportions of concrete

28 day Slump T Mix constituents: kg/m'
cube strength* mm
N/mmz OPC PFA Water Aggregates?

OPC concrete
20 25 200 165 2035
75 225 185 1960
125 235 I95 1925
40 25 285 165 1950
75 320 185 1865
125 340 1951 1820
60 25 385 145 1850
75 430 165 1755
125 455 1951 1705

PFA concrete P3 IP
and P28P
20 25 150 145 2015
75 170 165 1945
125 180 175 1905
40 25 210 145 1905
75 235 165 1830
125 250 175 1785
60 25 305 145 1820
75 345 1651 1730
125 365 1751 1680
*Standard test to BS 1881 : Part 116.
?Gravel coarse aggregate (10 and 20mm sizes) and natural sand (Zone M, BS882).
tInclusive of plasticizer at dosage 0.32% weight of total cement content.

182 Magazine of Concrete Research, 1990, 42, No. 152

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 Rapid estimation of chloride diffusion coefficient

Table 3. Curing conditions for concrete test specimens index are comparedin Fig. 7. This shows that a reduc-
Code I Curing conditions* tion in D and PD index, noted for the PFA concrete
as compared to the corresponding OPC concrete, is
El 20C water for 28 days also present when the test specimens receive no addi-
E2 20C water for 3 days followed by air curing
tional moist curing (E3) before testing.
E3 Air curing for 28 days
E4 El then 3 months air curing Figures 6 and 7 show that the coefficients of diffu-
sion are closelyreflectedby the PD index values,
*Including initial 24 h under damp hessian after casting as is demonstrated in Fig 8. The relationship between
D and the PD index is not linear, probably due to
both tests, even though simple diffusion may not the effects of continued OPC hydration and/or PFA
be thedominantchloridetransport process in the reactions during the prolonged water-submerged test
PD test. periods of the CD test.' This also explains the outlier
Values of the measured coefficient of diffusion D shown in Fig. 8, which represents the E3 cured PFA
from the CD test and the corresponding PD index concrete. The 9 month soaking of these specimens in
values for the El cured concretesare shown in Fig. 6. the immersion tanks during the CD test allows the
Varying the workability of concrete from slump25 to pozzolanic reaction to restartand contribute to reduc-
125 mm had little effect on either D or PD index. ing chloride diffusion. On the other hand, the short
However, increasing theconcretegrade oradding period in the immersion tanks of the corresponding
PFA produced a marked reduction in the movement specimen in the PD test is not sufficient to restart the
of chlorides. The performances of the two PFA con- pozzolanic reaction and thereby influence chloride
cretes were essentially similar, andfurtherwork is transportation.
under way to establish the influence of various PFA The PD test has been used for a number of mixes,
qualities on chloride ion diffusion. featuring concrete design strengths of 20-60 N/mm2,
The effect of different curing regimes on D and PD and the use of plasticizers and PFAs of varying fine-

E
!?
0"
800

700

600
1
PFAP28P
./
A A
L

32 30 28 26
Time: weeks
(a)
8000 F
E 7000
e
'&
V
6000
/

1 40 o o5 L L
' -P"
&
7-
I I
PFAP28P

I l 1

6 7 8 9 10 11
Time: days
(W
Fig. 5. Comparison of periods required to achieve steady-state conditions for ( a ) C D
and (b) PD tests (C40 grade, cured E l )
Magazine of Concrete Research, 1990, 42, No. 152 183

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 Dhir et al.

100 1 OPC

12575 2512575 2512575 25

20 N/mm2 40 N/mm2
Concrete strength
- 60 Nlmm2
mm Slump

Fig. 6. Influence of PFA, concrete grade and workability on chloride diffusion and
corresponding PD index value (curing E l )

ness and loss on ignition obtained from various sources.
The curing conditions were also varied in the range
from E l to E4 (Table 3). The results obtained with the
CD and PD tests are shown in Fig. 9. This confirms
that the coefficient of chloride diffusion can be esti-
mated rapidly from the results of the PD test, with
an accuracy of k 4 x cm2/s at a 5% level of
significance.
Conclusions
1. The PD test method developed can greatly acceler-
ate the transport of chloride ions through concrete
specimens by the application of a small perturba-
tive potential difference. This results in a PD index.
2 . A wide range of OPC and PFA concrete mixes
and applied curing processeshavebeen studied.
184
For thesemixes the PD indexis shown to be
related to the coefficientof chloride diffusion;
this permits a rapid estimation of the coefficient
of diffusion.
3. The relationship between D and PD index is shown
to vary with the introduction of PFA, but there is
a suggestion that the influence of PFA quality, for
example its fineness and loss on ignition, may be
disregarded in estimating thecoefficient of dif-
fusion. This requires verification;appropriate work
is in progress.
4. A solution to Ficks First Law is derived whichcan
be used to calculate the coefficient of diffusion and
PD index. This solution can also be usedto confirm
that steady-state conditions were achieved during
the test, and that the assumptions made in usingthe
Fickean model were valid.
Magazine of Concrete Research, 1990, 42, No. I52

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 Rapid estimation of chloride dlffision coeficient

50
X

a
G
U

c significance

Coefficient of
correlation r = 0.99

/
I
O K ' '
0 10 20 30 40 50
Estimated value of D: cm% X io-'
Fig. 9. Accuracy of estimation of D from the proposed
rapid test

Acknowledgement
The authors gratefullyacknowledgetheresearch
El E2 E3 E4 grant provided by the South of Scotland Electricity
Curing
Board in support of this work.
Fig. 7 . Effect of curing on coeficient of diffusion and P D
index values
References

i'
1. DEPARTMENT OF TRANSPORT.The performance of concrete in
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2. ANON.Crumbling concrete closed flyover. New Civil Engin-
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3. GOTOS. and ROYD. M. Diffusion of ions through hardened
cement paste. Cem. Concr. Res., 1981, 11, No. 5/6, 751-757.
4. WHITING D. Rapid measurement of the chloride permeability
of concrete. Public Roads, 1981, 45, No. 3, 101-112.
5 . AMERICAN ASSOCIATION OF STATE HIGHWAY AND TRANSPOR-
TATION OFFICIALS. Standard method of test for resistance of
concrete to chloride ion penetration. Washington, DC, 1980,
AASHTO T-259801.
6 . DHIR R.K . et al. Determination of total andsoluble chlorides
in concrete. Cem. Concr. Res. (to be published).
7. DHIR R.K . et al. Contribution of PFA to concrete workability
and strengthdevelopment. Cem. Concr. Res.,1988,18, No. 2,
277-289.
8. TEYCHENNE D. C. etal.Design of normal concrete mixes.
Department of the Environment, Watford, 1988.
9. MUNDAY J. G . L. et al. Mix proportioning of concrete with
pulverized-fuel ash: acriticalreview. ACI, Detroit, 1983, ACI
publication SP-79, pp. 267-288.

PD index: cm% x
Fig. 8.Relationship of PD test index and D f o r OPC and
PFA concretes (item in brackets not included in regression Discussion contributions on this Paper should reach the Editorby
analysis) 29 March 1991

Magazine of Concrete Research, 1990, 42, No. 152 185

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