Magazine of Concrete Research, 1991, 43, No. 154, Mar.
, 37-44
Concrete durability: estimation of chloride
concentration during design life
R. K. Dhir*, M. R. Jones* and H. E. H. Ahmed*
U N I V E R S I TOF
Y DUNDEE
Valuesofthe coeficient of chloride dzflusion D, as
measured by the classical diffusion test and by a pen-
etration test, are compared. isItshown that D cannot be
determined reliably from penetration tests. Two setsof
nomograms are developed for the design of concrete
structures in chloride environments.
Theproposed
nomograms can copewithawiderange of concrete
variables:abasis is providedfor their extension
to include parametersnotstudied in thepresent
investigation.
Introduction
Adequate provisions for durability arevery import-
ant to engineers in the design of concrete structures.
For achloride-containingenvironment, these will
entail estimation of the rate of increase in chloride
concentration within concrete and the period taken to
reach a critical value at the level of reinforcement.
At present, adequatedurability is provided by
specifying a set of concrete and construction require-
ments. While durability is related to these parameters
individually, the variations caused by on-site work-
manship and curing cangreatly change concrete qual-
ity and lower its durability response. Moreover, the
use of different cementitious materials may produce
large variations inconcrete durability while comply-
ing with an overall specification, e.g. of minimum
cement content, workability or strength.
Durability can be better provided for by specifying
in terms of measured performance. Indeed, there is a
move in this direction in the development of European
codes and harmonized standards. In terms of resis-
tance of structural concrete to chloride attack, the
coefficient of chloride diffusion D provides afun-
*Concrete TechnologyUnit, Department of CivilEngineering,
University of Dundee, Dundee DD1 4HN, UK.
Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
damental parameter which can be used in specifying
durability. This Paper describes the development of a
methodfor estimating therateat which chlorides
build up in concrete, using the value of D. Such
amethodcan provide a basis for performance
specifications.
Review
The diffusion of chlorides in cement pastes and
mortars has been studied widely;-5various methods
of measuring D have been ~uggested.~. Although there
has been a move towards testing concrete, such inves-
tigations have been limited to comparisons of different
mixes.-
Several studies have attempted to calculate D from
the penetration of chlorides into mortar andconcrete
Collepardi etal.13 calculated D from
laboratory-basedpenetration tests using Ficks
Second Law for various mixes with and without a
natural pozzolana.Midgley and IllstonI4examined the
effects of surface chloride concentrations and water/
cement ratios at various ages. West and Hime tested
concrete in existing structures with different durations
of exposure. A recent reportI6 prepared by Taywood
Engineering for the Department of Energy and Off-
shore Industry found that for concrete penetration
specimens ina simulated marineenvironment, D
varied with the period of exposure even up to23 years.
The problems with calculating D from penetration
tests are that achieving a steady-state condition takes
a very long time, and establishing that such a con-
dition has in fact been reached is virtually impossible.
Thus, values of D from such atest could normally be
expected to vary with time as reported in Refs 14 and
16, and cannot be reliably used to estimate chloride
movement in concrete for design purposes.
Lawrence provided a theoretical consideration of
37
 Dhir et al.

a penetration test using Crank's relationship to Fick's Table 2. Curing conditions for concrete test Specimens
Second Law. From this work, the concrete chloride Curing conditions
Code
content C, could be estimated at a particular depth of
concrete x from aknown surface chloride concen- El 20C water for 28 days
tration C,. The main problem of this approach lies in E2 20C water for 3 days, then air curing to 28 days
E3 Air curing for 28 days
interpreting the value of C,, as it must be measured
E4 2OoC water curing for 6 months
in parts per million (ppm). Brownel' developed a E5 Water-based curing membrane for 28 days
design nomogram which could be used to estimate the
time taken to reach a particular C,, provided that D
and C, can be established. It is difficult, however, to
determinethe value of C, in the required units of A solutionto this equationcan be represented
percentage of weight of cement. Thus, the method is according to Crank's relationship"
only applicable to existing structures.

Determination of coefficient of chloride

The diffusion coefficients obtained using equation (2)
diffusion are given in Table 1, as are the corresponding values
A series of tests were carried out on concrete cube of D determined directly from diffusion tests2' also
specimens exposed at 28 days to unidirectional started at the age of 28 days. The curing conditions
chloride penetration in a 5 M NaCl solution applied tothe specimens before immersion in the
(l77 250 ppm Cl- ion) at 20C. Profiles of both the chloride solution are given in Table 2.
totaland water-soluble chlorides were determined Table 1 shows that the diffusion coefficients cal-
after 3, 6 and 12 months of exposure, using incre- culated from the penetration tests decrease between 3
mentally drilled powder samples. The methodsused to and 12 months,and begin toapproachthe values
measure the total andwater-soluble chloride contents obtained from the diffusion tests. A reduction with
are described in Ref 19. The data were used to cal- time in the value of D calculated from penetration
culatethe coefficients of chloride diffusion using tests is also reported in Ref. 16. As there is clearly a
Fick's Second Law, as follows. problem in interpreting such data, the values of D
Fick's Second Law statesthatfor diffusion in a determined from the penetration tests are referred to
semi-infinite, homogeneous medium as chloride penetration indices in Table 1.
This reduction in the index value with increasing
exposure time suggests that steady-state conditions
were not achieved in the test periods used. Table 1 also
given the boundary conditions shows that total and water-soluble chloride contents
give different chloride penetration indices. It is
C, = 0 at t = 0 when0 x < CO
therefore considered that thevalue of D for estimating
C, = C, at x = 0 when 0 < t < CO chloride movement in concrete should be determined

Table 1. Demonstration that steady-state conditions were not achieved during the laboratory penetration tests

Concrete Standard 28 day Curing Chloride penetration index: cm2/s x D determined from
type strength: N/mm2 regime diffusion test:2'
Exposure period cm2/s x

3 months 6 months 12 months

Total Water Water Total Water Total

soluble soluble soluble

OPC 20 El 146.2 108.0 133.3 96.5 125.6 89.0 82.5

40 El 46.9 41.2 39.1 33.8 35.5 30.2 26.9
40 E2 58.4 56.1 54.2 50.1 52.1 46.3 38.0
40 E3 81.9 72.2 72.1 62.5 66.6 57.2 48.2
60 El Nil Nil Nil Nil 13.5 11.5 IO. 1

PFA 20 El 92.3 74.2 82.1 63.8 76.0 56.8 51.3

40 El Nil Nil 18.5 16.3 15.8 13.5 12.1
40 E2 41.8 37.0 36.931.1 33.4 27.8 24.2
40 E3 61.2 52.1 43.2 53.1 48.2 38.2 35.4
60 El Nil Nil Nil Nil Nil Nil 5.5

Nil = no chloride penetration detected.

38 Magazine of Concrete Research, 1991, 43, No. 154

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
 Estimation of chloride concentration

from all the constituent materials to 0.1-0.4wt % of

from a diffusion test. In addition, thediffusion test is
relatively simple to performandcan be completed cement content, depending on the type of reinforce-
within 14 days using a rapid test method.2 Although ment, cement and concrete used. For site-produced
reinforced concrete, the Building Research Establish-
curing is specified, it can vary widely on site, causing
concretequalitytovary,particularly in thecovermentZ6hasestablisheda maximum tolerabletotal
zone.Therefore, D is best measuredon chloride content of 0.4wt YO of cement content. In
in situ
concrete. contrast, the American Concrete Institute specifies a
maximum water-soluble chloride content0.1 of5 wt o/o
of cement content.
Estimation of chloride concentration For a given concrete,the ingress of chlorides is
Durability in thiscontext is defined as the time dependent on exposure conditions,which can be vari-
fora specific chlorideconcentration to reachthe able.Although D maybe considered an intrinsic
reinforcement/concreteinterface. The British Stan- property, concrete normally degrades during service,
dard Codes of Practice and major specifications22-2s and so thevalue of D may change. However, to
limit the maximum concentration of chlorides arising develop an estimation method in this case a uniform

Fig. 1. Nomogram for estimating time to reach a chosen total chloride concentration in concrete: (a) for 50mm cover,
C, = 0.5 M and Cxi= 0 wt % cement; ( b ) effect of cover x; ( c ) effect of surface concentration C,; effect of initial chloride
content Cxi

Magazine of Concrete Research, 1991, 43, No. 154 39

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
 Dhir et al.

set of environmentalconditions were chosen in terms The values of C, were obtainedfrompenetration

of surface chlorideconcentration and temperature.
Similarly, D was assumed to be constant.
Proposedmethod of estimatingtimeto reach a
spec@ chloride content
The method developed for estimating the time to
reach a specific total chloride concentration (Fig. 1) is
essentially based on Cranks solutionto Ficks Second
Law (Equation (2)). In the first instance, this equation
has been used to give relationships of D and t, for a
specific value of x (50mm), with C, ranging up to
0.8 wt Yo of cement content. As there is no single
. ~ ~ of C,
agreed critical chloride c ~ n t e n t , ~a*range
values have been chosen to allow the design engineer
to select suitable figures for different structures.
tests, carried out in the laboratory, by projecting the
chloride profile back to the surface. This allowed the
value of C, to be expressed in terms of wt% of cement
content in orderto satisfy the requirement for similar
units
to C, in equation (2). Thus, the time t , to reach
a specific chlorideconcentrationforaparticular
measured D can be obtained.
Figure l(a) was constructed with an initial C, value
of 0.5 M, as this represents the upper chloride con-
centrationsencountered in marine environments.
Fig. l(b) allows the cover depth to be varied from
x = 25mm to lOOmm, and accordingly modifies the
time t2 to reach the specific chloride concentration.
Fig. l(c) allows the surface chloride concentration C,
to be varied from 0.1 to 5.0M. In orderthat the

Selected water-soluble
chloride content

0.8
U

Fig. 2. Nomogram for estimating time to reach a chosen water-soluble chloride concentrated in concrete: (a) fan 50mm
cover, C, = 0 . 5 m and C,, = 0 wt % cement: ( b ) effect of cover x; ( c ) effect of surface concentration C,: ( d ) e f e c t of
initial chloride content C,,

40 Magazine
Research,of Concrete 1991, 43,No. 154

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.

engineer may easily measure theambient surface
chloride concentration,C, in Fig. l(c) is given in units
of molarity. To achieve this, Crank's solution has been
used as follows. For any surface concentration C,
equation ( 2 ) becomes
cm --
_ 1 - erf X
Cm 2(Dt,,,)'/2
Dividing equation (2) by equation (3)
, . x
. x
Using equation (4), relationships between C,, and t,,
can be obtained.
FigureI(a) is based on theassumption thatno
chlorides are present in the concrete at the time D
is established. However, in reality chlorides may be
present. Indeed, for new structures the codes of prac-
tice22-25 specify tolerances for chlorides from the con-
stituent materials up to a total of 0.4 wt YOof cement
content. Where chlorides are already present in the
concrete, the rate of penetration of chlorides from
external sources will vary. Fig. l(d) allows various
initial concrete chloride contents and their effect on
penetration to be taken into accountby modifying the
estimated time.
Some organizations have shown preference for speci-
fications in terms of water-soluble chlorides. Some
authors have also suggested that thequantity of
water-soluble chlorides provides more a realistic
assessment of the risk of corrosion to reinforce-
ment.'9.30A nomogram (Fig.2) for estimating the time
taken to reach a specific water-soluble chloride con-
centration has been developed in a similar manner to
Fig. 1.
Example l
To illustrate the use of the proposed methods, the
following example has been chosen for estimating the has been chosen.
time taken toreach a particular total chloride content. Step 2. Starting with Fig. 3(a), determine C,, . For
The steps shownare similar fora water-soluble D = 15 x lop9cm2/s and t, = 40 years, C,, =
chloride content.
Step I . Establish the concrete parameters
( a ) concrete coefficient of chloride diffusion D (cm'ls) Step 4 . Using Fig. 3(c), determine Cx,. For
(b) cover thickness x (mm)
(c) initial concrete total chloride content CXi(wt % of
cement content)
( d ) specific total chloride content C, (wt O/' of cement tent of 0.1 wt % of cement content, theestimated total
content)
and the ambient environmental parameter
(e) Surface chloride concentration C, (moles)
In this example the following values are assumed
(a) D = 15 x lop9
Magazine of Concrete Research, 1991, 43, NO.154
Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
Estimation of chloride concentration
(b) x = 75
(c) cxi= 0.1
( d ) C, = 0.4
(e) C, = 0-3
Step 2. Starting with Fig. l(a), determine t , . For
D = 15 x 10p9cm2/s andC, = 0.4wt % of cement
content, t2 = 15 years.
If the concrete and ambient environment param-
eters are the same as those used in Fig. l(a), then t ,
becomes the overall estimated time and Fig. l(b)-(d)
is not used.
Step 3. Using Fig. I(b), determine t , . For
x = 75mm, t, = 33 years.
Step 4 . Using Fig. l(c), determine t , . For
C, = 0.3 M, t , = 48 years.
Step 5. Using Fig. I(d), determine the factorF. Mul-
tiply t, by F to determine theoverall estimated period
to reach a specific concrete chloride content of 0.4 wt YO
of cement content. For CXi= 0.1 wt % of cement
content, F = 0.83. The overall estimated time to
reach the chosen chloride content for this concrete =
0.83 x 48 = 40 years.
Proposed method of estimatingchloride content for a
given exposure period
In certain cases, engineers may wish to estimate the
chloride content that builds up in the concrete after a
given exposure period. To enable this, two further
nomograms have been developed, as shown in Figs 3
and 4, for the total and water-soluble chloride con-
tents respectively. The nomograms have again been
developed using Crank's relationship, but C, rather
than t, is calculated. Inthis case, any existing chlorides
in the concrete are added to the estimated chlorides
that will ingress during theperiod under consideration.
Example 2
Step I . The parameters used here are as in Example 1,
except that in ( d ) the engineer decides on the exposure
period (t, years). In this example a period of 40 years
1.38 wt% of cement content.
Step 3. Using Fig. 3(b), determine C,,. For
C, = 0.3 M, C, = 0.30 wt Yo of cement content.
CS = 0.3 M, C,, = 0.30 wt Yo of cement content.
Step 5. Addthequantity of existing concrete
chlorides to C,, . For an initial concrete chloride con-
contentafter 40 years exposure is 0.10 0.30 = +
0.4 wt % of cement content.
Discussion
The effect of curing on the resistance of an OPC
concrete andaPFA concrete onthe ingress of
41
 Dhir et al.

\
Fig. 3. Nomogram f o r estimating the total chloride concentration in concrete after a chosen period of exposure: ( a ) f o r
S0mm cover and C, = 0 . S M ; ( b ) effect of cover x; (c) effectof surface concentration C,

Table 3. Variation of D within a single concrete grade

Concrete Water Total Curing 28 day D: cm2/s x Time take to reach 0.4% chloride
type cementitious cementitious measured content:t years (c, = 0.5 M)
ratio* strength: N/mm2 content:
kg/m3

OPC 0.55 325 El 26.9 40.0 8.5

0.55 325 E2 38.0 29.0 6.5
0.55 325 E3 48.2 20.5 5.0
0.55 325 E4 44.0$ 9.5 24.0
0.55 325 E5 33.5 33.5 7.0

PFA 0.45 365 El 40.0 12.1 18.1

365 0.45 E2 9.5 24.2 28.5
0.45 365 E3 35.4 20.5 7.0
365 0.45 E4 60.5$ 32.0 6.0
0.45 365 E5 14.2 37.0 16.5

*Either w/c or w/c + f.

?Total chloride concentration as weight of cement content.
$At 6 months.

42 Magazine of Concrete Research, 1991, 43, No. 154

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
 Estimation of chloride concentration

(a) /
Selected exposure

/ O/ years

Overall estimated water-soluble Cl ~ Cx3:wt% cement

\\ Water-soluble Cl ~ C,,: wt% cement

Fig. 4 . Nomogram for estimating the water-soluble chloride concentration in concrete after a chosen period of exposure:
(a) ,for50 mm cover and C, = 0.5 M ; ( b ) effect of cover x; ( c ) eflect of surface concentration C,

chlorides can be inferred from Table 3. From the
values of D it is clear that water/cementratio or
cement content alone cannot be used to define the
quality of concrete in situ.
Although, for a given cement type and source, in
situ strength may provide an estimate of the potential
durability of concrete, difficulties could arise with this
approach. This is due to the fact that strength is not
likely to reflect the influence of concrete microstruc-
ture on the transportation of chlorides in sufficient
detail. Moreover, strength alone does not account for
the chloride binding capacity of different cement
types: the effect of PFA in this regard is shown,
although in this instance account must be taken of
different total cement content (c + f) and w/c + f
ratio.Therefore, as suggested above, D is amore
realistic parameter on which to base estimates of the
Magazine of Concrete Research, 1991, 43, No. 154
rate of ingress of chlorides into concrete. The times to
reach a critical total chloride content of 0-4wt % of
cement content estimated from Fig. 1 are alsogiven in
Table 3.
The proposed methods have the potential to cope
with variations in the materials, curing, cover, initial
concrete chloride content and surface chloride con-
centration. However, the scope of the experimental
work precluded consideration of the effects of, for
example, ambient temperature, wetting and drying,
structural cracks and variations in surface chloride
concentration. All of these should be considered
in anyestimation of therate of chloride ingress.
The form of the proposed methods, however, can be
extended to include such additional parameters; this
work is under way using methods recently established
by the A ~ t h o r s . ' ~ , ~ '
43

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.
 Dhir et al.

Conclusions 7. DIAB H.et al. The diffusion of Cl- ions through Portland
cement and Portland-polymer-~ pastes. Cem.Concr.Res.,
1 . Concrete specifications give no guidance as to the 1988, 18, NO. 5 , 715-722.
likely durability of concrete; specifying by strength, 8. OST B. and MONFORE G. E. Penetration of chlorides
intoconcrete. Journal of PCA Research and Development
cement content or w/c ratio alone cannot ensure Laboratories, 1986, No. I, 46-52.
adequate
durability in chloride-containing 9. G J ~ 0. V E. and VENNESLAND 0. Diffusion of chloride ions
environments. from sea water into concrete.Cem. Concr. Res.,1979,9, No.2,
2. The coefficient ofchloride diffusion D characterizes pp. 229-238.
the resistance of concrete to chloride ingress and 10. LUKAS W. Chloride penetration in standard concrete, water-
reduced concrete and superplasticizedconcrete. American
can take intoaccount the material, production and Concrete Institute, Detroit, 1981, special publication 68-14,
curing characteristics.D should therefore be deter- pp. 253-257.
mined from site concrete. 11. MARUSIN S. L. and PFEIFER D. W. Chloride penetration into
3. D cannot be determined reliably from penetration concrete madewith various admixtures.Proc. American Con-
crete Institue Symposium 85, RILEM, 1985, pp. 291-312.
tests: these are extremely slow, and itis not possible
12. MOUKWA M. Penetrationof chloride ions fromsea water into
to check that steadystateconditions have been mortarsunderdifferentexposureconditions. Cem.Concr.
reached. D should therefore be measured using a Res. 1989, 14, No. 6, 894-904.
diffusion test. 13. COLLEPARDIM.etal. Penetration of chlorideionsinto
4. Cranksrelationship to Ficks Second Law has cementpastes and concretes. J.Am.Ceram.Soc., 1972,
been used to develop a series of nomograms, based No. 55, 534-535.
14. MIDGLEY H. G . and ILLSTON J. M.Thepenetrationof
on laboratory diffusion and penetration tests and chlorides into hardenedcementpastes. Cem.Concr.Res.,
designed to allow practical estimation of chloride 1984, 14, NO. 4, 546-558.
ingress rates into the concrete. 15. WESTR. E. and HIMEW. G. Chloride profiles in salty con-
5 . Two sets of nomograms have been developed. One crete. Materials Performance, 1985, No. 7,29-36.
estimates the time taken to reach a critical chloride 16. FIDJESTOL P. et al., Factors affecting the design for corrosion
protection in concrete offshore and marine structures. Offshore
content, chosen in terms of total or water-soluble technology report, HMSO, London. 1987.
chlorides; the second estimates the concrete

17. LAWRENCE C. D. Durability of concrete: molecular transport
chloride content that is likely to have built up at a processes and testmethods. CementandConcrete Associ-
chosen depth of cover aftera specific exposure ation, 1981, technical report 544.
period, either as a total or water-soluble propor- 18. BROWNER. D. Design prediction of the life for reinforced
concrete in marine and other chloride environments. Durabil-
tion. ity of Building Materials, 1982, No. I, 113-125.
6 . The nomograms can cope with variations in con- 19. DHIRR.K. etal. Determination of totalandsoluble
crete
materials,
curing, cover, initial concrete chlorides in concrete. Cem.Concr.Res., 1990, 20, No.4,
chloridecontent and surface chloride concen- Sept., 579-590.
tration.Theform of themethods allows their 20. CRANK J. The mathematics of drffision. Oxford University
Press, 1975, 2nd edn.
extension to include effects from other exposure 21. DHIRR. K. et al. Rapidestimation of chloride diffusion
conditions, such as temperature, wetting and drying, coefficient in concrete. Mag. Concr. Res., 1990, 42, No. 152,
cracks and effects not considered in this paper. Sept., 177-185.
22. BRITISH STANDARDS INSITUTION. Structural use of concrete.
BS8IlO:Part 1, 1985.
Acknowledgements 23. BRITISHSTANDARDSINSTITUTION. Design of concrete struc-
turesfor retaining aqueous liquids. BS 8007, 1987.
The Authors gratefully acknowledge the research 24. BRITISHSTANDARDS INSTITUTION.Speclfication for materials
grant provided by Scottish Power plc in support of and workmanship, concretereinforcement andprestressing ten-
this work. dons. BS5400: Part 7, 1978.
25. DEPARTMENT OF TRANSPORT. Specification for highway works.
Part 5, 1986.
26. BUILDINGRESEARCH ESTABLISHMENT. Deterioration due to
References corrosion in reinforced concrete. BRE, Watford, 1980, Infor-
I. PAGEC. L. etal. Diffusionofchlorideions in hardened mation paper IP12/80.
cement pastes. Cem. Concr. Res., 1981, 11, No. 3, 395406. 27. AMERICANCONCRETEINSTITUTE. Building codeACI 318-83,
2. GOTOS . and ROYD. M. Diffusion of ions through hardened Detroit, 1983.
cement pastes. Cem. Concr. Res., 1981, 11, No. 51, 751-757. 28. TUUTTII K. Service life of structures with regard to corrosion
3. HANSSON C. M. et al. The effect of cement type on the dif- of embedded steel. Proc. 9th CIB Congress, Stockholm, 1983,
fusion of chloride. Nordic Concr. Res., 1985, No. 4, 70-80. Vol. 2, pp. 233-243.
4. BUENFELDN. R. and NEWMAN J.B. Permeabilityof marine 29. HOPE B. B. and IP A. K. C. Chloride corrosion threshold in
concrete1986. Proceedingsofinternationalconferenceon concrete. J. Am. Concr. Inst., 1987, 84, No. 4, 306-314.
concrete in the marine environment, London,1986, The Con- 30. DHIRR.K. AND JONESM. R. Influence of pfa on proportion
crete Society, pp. 165-173. of free chlorides in salt contaminated concrete.Proc. 3rd Int.
5. BYFORSK. Influence of silica fume and pulverized fly ash on Symp. on corrosion of reinforcement in concrete construction,
chloride diffusionand pH levels in cement paste. Cem. Concr. Wishaw, 1990,Society of the Chemical Industry, pp. 227-236.
Res., 1987, 17, No. I, 115-130.
6 . KUMARA. et al. Diffusion through concrete. Concrete, 1987, Discussioncontributions on thisPapershouldreach theEditor by
21, No. 1, Jan., 31-32. 30 September 1991

44 Magazine of Concrete Research, 1991, 43, No. 154

Downloaded by [ Indian Institute Of Technology - Bombay] on [18/09/17]. Copyright ICE Publishing, all rights reserved.