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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 damental parameter which can be used in specifying
measured by the classical diffusion test and by a pen- durability. This Paper describes the development of a
etration test, are compared. isItshown that D cannot be methodfor estimating therateat which chlorides
determined reliably from penetration tests. Two setsof build up in concrete, using the value of D. Such
nomograms are developed for the design of concrete amethodcan provide a basis for performance
structures in chloride environments.
Theproposed specifications.
nomograms can copewithawiderange of concrete
variables:abasis is providedfor their extension
to include parametersnotstudied in thepresent
Review
investigation. The diffusion of chlorides in cement pastes and
mortars has been studied widely;-5various methods
of measuring D have been ~uggested.~. Although there
Introduction has been a move towards testing concrete, such inves-
Adequate provisions for durability arevery import- tigations have been limited to comparisons of different
ant to engineers in the design of concrete structures. mixes.-
For achloride-containingenvironment, these will Several studies have attempted to calculate D from
entail estimation of the rate of increase in chloride the penetration of chlorides into mortar andconcrete
concentration within concrete and the period taken to Collepardi etal.13 calculated D from
reach a critical value at the level of reinforcement. laboratory-basedpenetration tests using Ficks
At present, adequatedurability is provided by Second Law for various mixes with and without a
specifying a set of concrete and construction require- natural pozzolana.Midgley and IllstonI4examined the
ments. While durability is related to these parameters effects of surface chloride concentrations and water/
individually, the variations caused by on-site work- cement ratios at various ages. West and Hime tested
manship and curing cangreatly change concrete qual- concrete in existing structures with different durations
ity and lower its durability response. Moreover, the of exposure. A recent reportI6 prepared by Taywood
use of different cementitious materials may produce Engineering for the Department of Energy and Off-
large variations inconcrete durability while comply- shore Industry found that for concrete penetration
ing with an overall specification, e.g. of minimum specimens ina simulated marineenvironment, D
cement content, workability or strength. varied with the period of exposure even up to23 years.
Durability can be better provided for by specifying The problems with calculating D from penetration
in terms of measured performance. Indeed, there is a tests are that achieving a steady-state condition takes
move in this direction in the development of European a very long time, and establishing that such a con-
codes and harmonized standards. In terms of resis- dition has in fact been reached is virtually impossible.
tance of structural concrete to chloride attack, the Thus, values of D from such atest could normally be
coefficient of chloride diffusion D provides afun- expected to vary with time as reported in Refs 14 and
16, and cannot be reliably used to estimate chloride
*Concrete TechnologyUnit, Department of CivilEngineering, movement in concrete for design purposes.
University of Dundee, Dundee DD1 4HN, UK. Lawrence provided a theoretical consideration of
37

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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

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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

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Dhir et al.

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


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

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Estimation of chloride concentration

engineer may easily measure theambient surface (b) x = 75


chloride concentration,C, in Fig. l(c) is given in units (c) cxi= 0.1
of molarity. To achieve this, Crank's solution has been ( d ) C, = 0.4
used as follows. For any surface concentration C, (e) C, = 0-3
equation ( 2 ) becomes Step 2. Starting with Fig. l(a), determine t , . For
cm -- D = 15 x 10p9cm2/s andC, = 0.4wt % of cement
_ 1 - erf X
content, t2 = 15 years.
Cm 2(Dt,,,)'/2
If the concrete and ambient environment param-
Dividing equation (2) by equation (3) eters are the same as those used in Fig. l(a), then t ,
becomes the overall estimated time and Fig. l(b)-(d)
, . x
is not used.
Step 3. Using Fig. I(b), determine t , . For
. x
x = 75mm, t, = 33 years.
Step 4 . Using Fig. l(c), determine t , . For
Using equation (4), relationships between C,, and t,, C, = 0.3 M, t , = 48 years.
can be obtained. Step 5. Using Fig. I(d), determine the factorF. Mul-
FigureI(a) is based on theassumption thatno tiply t, by F to determine theoverall estimated period
chlorides are present in the concrete at the time D to reach a specific concrete chloride content of 0.4 wt YO
is established. However, in reality chlorides may be of cement content. For CXi= 0.1 wt % of cement
present. Indeed, for new structures the codes of prac- content, F = 0.83. The overall estimated time to
tice22-25 specify tolerances for chlorides from the con- reach the chosen chloride content for this concrete =
stituent materials up to a total of 0.4 wt YOof cement 0.83 x 48 = 40 years.
content. Where chlorides are already present in the Proposed method of estimatingchloride content for a
concrete, the rate of penetration of chlorides from given exposure period
external sources will vary. Fig. l(d) allows various
In certain cases, engineers may wish to estimate the
initial concrete chloride contents and their effect on
chloride content that builds up in the concrete after a
penetration to be taken into accountby modifying the
given exposure period. To enable this, two further
estimated time.
nomograms have been developed, as shown in Figs 3
Some organizations have shown preference for speci-
and 4, for the total and water-soluble chloride con-
fications in terms of water-soluble chlorides. Some
tents respectively. The nomograms have again been
authors have also suggested that thequantity of
developed using Crank's relationship, but C, rather
water-soluble chlorides provides more a realistic
than t, is calculated. Inthis case, any existing chlorides
assessment of the risk of corrosion to reinforce-
in the concrete are added to the estimated chlorides
ment.'9.30A nomogram (Fig.2) for estimating the time
that will ingress during theperiod under consideration.
taken to reach a specific water-soluble chloride con-
centration has been developed in a similar manner to Example 2
Fig. 1.
Step I . The parameters used here are as in Example 1,
Example l except that in ( d ) the engineer decides on the exposure
To illustrate the use of the proposed methods, the period (t, years). In this example a period of 40 years
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. 1.38 wt% of cement content.
Step 3. Using Fig. 3(b), determine C,,. For
Step I . Establish the concrete parameters
C, = 0.3 M, C, = 0.30 wt Yo of cement content.
( a ) concrete coefficient of chloride diffusion D (cm'ls) Step 4 . Using Fig. 3(c), determine Cx,. For
(b) cover thickness x (mm) CS = 0.3 M, C,, = 0.30 wt Yo of cement content.
(c) initial concrete total chloride content CXi(wt % of Step 5. Addthequantity of existing concrete
cement content) chlorides to C,, . For an initial concrete chloride con-
( d ) specific total chloride content C, (wt O/' of cement tent of 0.1 wt % of cement content, theestimated total
content) contentafter 40 years exposure is 0.10 0.30 = +
and the ambient environmental parameter 0.4 wt % of cement content.

(e) Surface chloride concentration C, (moles) Discussion


In this example the following values are assumed The effect of curing on the resistance of an OPC
(a) D = 15 x lop9 concrete andaPFA concrete onthe ingress of
Magazine of Concrete Research, 1991, 43, NO.154 41

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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

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

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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,
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22. BRITISH STANDARDS INSITUTION. Structural use of concrete.
BS8IlO:Part 1, 1985.
Acknowledgements 23. BRITISHSTANDARDSINSTITUTION. Design of concrete struc-
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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
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21, No. 1, Jan., 31-32. 30 September 1991

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