Construction and Building Materials 123 (2016) 27–34

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Experimental study on chloride permeability in concrete by non-contact

electrical resistivity measurement and RCM
Lianzhen Xiao a,b,⇑, Zheng Ren a, Wenchong Shi a, Xiaosheng Wei c
a
School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430073, China
b
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, China
c
School of Civil Engineering and Mechanics, Huazhong University of Science and Technology, Wuhan 430074, China

h i g h l i g h t s

A new technique (NC-ER) was proposed to test chloride diffusion coefficient.

There is a linear relationship between the results of pastes by NC-ER and RCM.

There are no errors caused by electrodes and about 5 min was taken to complete a test.

a r t i c l e i n f o a b s t r a c t

Article history: A new non-contact electrical resistivity (NC-ER) measurement technique was proposed to measure the
Received 9 April 2016 chloride diffusion coefficient of cement-based materials, and the results from testing were compared
Received in revised form 18 June 2016 with the rapid chloride migration test, traditionally called RCM. Cement pastes with water cement ratios
Accepted 21 June 2016
of 0.30, 0.35 and 0.40, and concrete with a water cement ratio of 0.4 were prepared for the chloride dif-
fusion coefficient measurement by the two methods.
The chloride diffusion coefficient results obtained by both approaches show a reasonable decrease with
Keywords:
hydration age and increase with the increase of water cement ratio. The results for the pastes from the
Electrical resistivity
Slice
RCM test are in range of (0.693.15)  107 cm2/s at 3d80d, and the results from the NC-ER test are
Ion migration in the range of (0.531.71)  107 cm2/s., which are of the same order of magnitude and follow a linear
Chloride diffusion coefficient relationship DRCM = 1.8821DNC-ER  0.3506 (R2 = 0.9205).
From the NC-ER test, the chloride diffusion coefficient of concrete C0.4 is lower than that of paste P0.3
at the same ages and was verified by the porosity and formation factor analysis, while the RCM test
obtained opposite trends. A better linear correlation between the chloride diffusion coefficient of the con-
crete and paste samples was obtained based on the NC-ER test. It can be deduced that the NC-ER set-up
has advantages over the RCM set-up in measuring the chloride diffusion coefficient of concrete, such as
there being no electrodes in the NC-ER setup which eliminates errors, and taking a much shorter time
(about 5 min) to complete a test.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction chloride migration test (RCM) [5] and resistivity techniques [6,7].
The electrical methods are considered as rapid tests for evaluating
The chloride diffusion coefficient is an index of concrete dura- concrete permeability [8].
bility. The methods to measure the diffusion of chloride ions for Concrete is considered to be a solid electrolyte, and the trans-
determining concrete permeability include standard methods, port of ionic species i in the pore solution of the solid electrolyte
such as the test for the resistance of concrete to chloride ion pen- follows Nernst-Plank equation as Eq. (1) [9].
etration (Salt Ponding Test) [1,2], the electrical indication of the
@C i Z i F @E
ability of concrete to resist chloride ion penetration [3,4], the rapid
J i ¼ Di þ Di C i  Civ i ð1Þ
@x RT @x

⇑ Corresponding author at: School of Materials Science and Engineering, Wuhan where Ji is the ionic flux of species I (mol/cm2/s), Di is the diffusion
Institute of Technology, Wuhan 430073, China. coefficient of species i in the concrete (cm2/s), Ci is the concentra-
E-mail address: xiaolz@gmail.com (L. Xiao). tion of species i in the pore solution as a function of location x

http://dx.doi.org/10.1016/j.conbuildmat.2016.06.110
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
28 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34
(mol/cm3), Zi is the valence and vi is the convection velocity of the
ionic species I (cm/s). F is Faraday’s constant (96487 C/mol), R is
the universal gas constant (8.314 J/mol.K), T is the absolute temper-
ature (K), and E is the applied electrical potential (V).
The each item of ion migration in Eq. (1) has a specific trans-
portation mechanism, in which are the ionic movement under a
concentration gradient is controlled by Fick’s first law, the ionic
movement driven by electrical potential, and convection from
the pressure gradient. If the pressure gradient is negligible, and
the ion concentration in the concrete pore solution is constant in
a steady state condition, and the ion migration is controlled only
by electrical field as in Eq. (2), and the chloride diffusion coefficient
can be obtained by Eq. (3), which is called the Nernst-Einstein
equation.
Zi F @E
J i ¼ Di C i
RT @x
RT ri
Di ¼
Z 2i F 2 C i
where ri is the partial conductivity of species i in the solution (S/
cm). The ri can be determined by the apparent conductivity of con-
crete and transfer number of species i in Eq. (4).
ri ¼ t i r
where r is apparent conductivity of concrete (S/cm) and ti is trans-
fer number of species i.
The diffusion coefficient of chloride in concrete can be found by
measuring the electrical conductivity of the concrete and the trans-
fer number of chloride ti in the pore solution according to Eq. (5).
RTt i r
Di ¼
Z 2i F 2 C i
Test methods based on the Nernst-Einstein equation were pro-
posed [6,10], and although great interest was aroused and many
efforts have been made on electrical testing, the methods have
not been widely accepted in the field yet. The experiments on chlo-
ride permeability were conventionally undertaken with electrode
measurements, using either alternating current or direct current,
where the polarization reaction on the electrodes consumes the
ions in the solution, resulting in the ion concentration and the
transfer number to vary during testing. The results and models
presented by different researchers were not fully consistent due
to the error caused by the electrodes, various measurement factors
and the assumptions were not fully satisfied in regard to the theo-
retical equations used.
A non-contact electrical resistivity method (NC-ER) [11–13]
using alternating current (AC) is developed and used in this study
to measure the electrical resistivity of the concrete mixtures satu-
rated by NaCl solution, and hence to obtain the diffusion coefficient
of chloride. The NC-ER eliminates the problems caused by the elec-
trodes in conventional set-ups since there are no electrodes in this
setup. In the non-contact electrical resistivity setup, there is no
contact resistance between the test sample and the electrodes.
No ions are consumed in the electrodes reaction and the total
transfer number is truly equal to 1.0, compared to values smaller
than 1.0 in the conventional electrode measurement method
[14], and the transfer number of Cl (ti) in the used sodium chlo-
ride solution can be determined according to reference [15] as
0.604, and the chloride concentration Ci is equal to the saturated
pore solution concentration. These parameters were used to calcu-
late the diffusivity of the ions in the concrete according to Nernst-
Einstein equation. Additionally, the RCM test was taken to measure
the chloride diffusion coefficient of the same samples at the same
ages for comparison, and the results from the two methods were
analyzed.
2. Raw materials and mixture preparation
All tests were carried out using Ordinary Portland cement
P.O42.5, meeting Chinese standard GB175-2007, and quartz sand
of size 0.6 mm5 mm and crushed granite of size 5 mm10 mm
were used in the concrete samples. The density and the
Blaine specific surface area of the cement were 3.15 g/cm3 and
356 m2/kg, respectively. The chemical composition of the cement
is shown in Table 1.
Three paste samples were prepared with water cement ratios
(W/C) of 0.30, 0.35 and 0.4, marked as P0.30, P0.35 and P0.40,
respectively. A concrete sample was prepared with a sand/coarse
ð2Þ aggregate weight ratio of 0.5 and a total aggregate volume fraction
(Va) of 65%, at a W/C ratio of 0.40 marked as C0.40.
Each sample was mixed for 2 min in a planetary-type mixer at
ð3Þ 45 rpm and for a further 2 min at 90 rpm. The mixtures were
respectively cast in a ring mould (1.67 L) for the NC-ER test and
in a cylinder mould (diameter 100 mm  height 100 mm) for the
RCM test. All the tests were conducted at 22 ± 2 °C.
3. Test methods
ð4Þ
3.1. Slice sample preparation and non-contact electrical resistivity in
AC field
Slice samples were prepared by cutting the ring samples at the
designated ages according to the dimensional requirement from
the hardened mixtures for the chloride diffusion test. Each slice
sample was vacuumed for 1 h and saturated with 10% (1.724 M)
NaCl solution for 1 h using a vacuum pump.
ð5Þ
The electrical resistivity of each saturated slice sample was
measured by a non-contact electrical resistivity setup (NC-ER) in
alternating current (AC) field, as shown in Fig. 1(a) and (b), based
on the transformer principle with 1 kHz frequency used. A trans-
former consists of two coils of wire wound on the same core. The
primary coil is the input coil of the transformer and the secondary
coil is the output coil. The ring sample acts as the secondary coil of
the transformer in this setup. When an AC voltage is applied to the
primary coil, a toroidal voltage (V) in Fig. 1(b) will be induced in
the secondary coil. Subsequently, a toroidal current (I) will be gen-
erated inside the ring mould. There are two parts in the ring mould,
a saturated slice sample inserted with sealant and the NaCl solu-
tion with the concentration of 10% (1.724 M) poured then.
The saturated slice sample and the 1.724 M NaCl solution form
a series model as secondary coil of the transformer in Fig. 1(b). The
solution resistance Rsolution and the slice sample resistance Rslice can
be calculated based on Ohm’s law in Eq. (6).
V
Rsolution þ Rslice ¼ ð6Þ
I
The original pore solution inside the slice sample was fully
replaced by the 1.724 M NaCl solution, and the conductivity of a
slice sample results from the movement of conductive ions Cl
and Na+ through the pore paths inside the slice sample under the
electrical field to form current. The electrical resistivity of the
slice sample (qslice) was then calculated by obtaining the electrical
Table 1
The chemical composition of cement (wt%).
CaO SiO2 Al2O3 Fe2O3 MgO SO3 K2O Na2O LOI
63.93 21.17 6.08 3.21 0.82 2.39 0.42 0.17 1.81
 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34 29

Fig. 1. The set-up for non-contact electrical resistivity measurement of the slice sample.

resistance of the solution and the bulk electrical resistance of the The disc sample was removed and axially split after the mea-
setup, when the slice sample size and the height of the solution surement was done. 0.1 M AgNO3 solution was sprayed on to one
in the ring mould are known. The chloride diffusion coefficient of the fresh split sections and the area containing chloride ions
(DNC-ER) can be calculated by Eq. (7), derived from Eq. (5). appeared to be white due to the AgCl formation. The chloride pen-
etration depth inside a sample was measured by a vernier caliper
RTt Cl 9:22 and the depth of the sample was determined by the average depth
DNC-ER ¼ ¼ ð7Þ
Z 2Cl F 2 C Cl qslice qslice of ten points. The other parameters, such as the initial and final
temperature, the specimen thickness, the voltage and time were
where DNC-ER: steady state chloride diffusion coefficient, recorded and the chloride diffusion coefficient was calculated by
107 cm2/s; Eq. (8) [5,16].

qslice: the electrical resistivity of the slice sample, Ohm.m;

C Cl : chloride concentration, 1.724 M;
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!

t Cl : the transfer number of Cl in the NaCl solution, 0.604; 00:0239ðT þ 273ÞL ðT þ 273ÞLX d

Z Cl : the valency of Cl, 1.0. DRCM ¼ X d  0:0238 ð8Þ
ðU  2Þt U2

3.2. Disc sample preparation and rapid chloride migration test (RCM)
where
Disc samples were prepared by cutting the cylinders into
DRCM: non-steady-state chloride diffusion coefficient,
50 mm thick sections at the designated ages from the hardened 1012m2/s;
mixtures for chloride diffusion testing. Each disc sample was vac-
U: absolute value of the applied voltage, V;
uumed for 3 h and saturated with saturated Ca(OH)2 solution for
T: average value of the initial and final temperatures in the ano-
1 h, then kept at the atmospheric pressure for more 18 h in the vac- lyte solution, °C;
uum chamber.
L: thickness of the concrete specimen, mm;
The electrical resistivity of each disc sample was measured by a
Xd: average value of the penetration depths, mm;
rapid chloride migration setup (RCM), as shown in Fig. 2.
t: test duration, hour.
In the RCM setup, 0.3 M NaOH solution was added in the anode
chamber, and 10% NaCl solution was poured in the cathode cham- Three discs from each mixture, at each age, were measured in
ber. The test period was set according to the electrical current in order to calculate the chloride diffusion coefficient, and the aver-
the first minute, and the voltage ranged 060 V. age value of the three discs was taken as the test result of DRCM.
30 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34

Fig. 2. The set-up for RCM of hardened concrete disc.

3.3. Thermal analysis (TGA) and porosity
Thermal gravimetric analysis (TGA) using TGA/DTA 92 (room
temperature to 1000 °C, with increments of 10 °C/min, in N2) was
performed for the quantification of the cement hydration products
for calculating the degree of hydration [13]. The porosity of cement
paste can be calculated by the hydration degree of the cement in
the paste, according to Power’s law [17].
4. Experimental results and discussion
4.1. The electrical resistivity and the chloride diffusion coefficient of the
slice samples by the NC-ER test
The electrical resistivity development during the first 12mins of
the slice samples P0.30, P0.35 and P0.40 at 3d are shown in Fig. 3 as
examples. Two slices from each mixture at each age were mea-
sured at intervals of 30 s and the average value of the electrical
resistivity of the two slices was taken as the test result for
calculating the chloride diffusion coefficient by Eq. (7). The electri-
cal resistivity of the slices for pastes P0.30, P0.35, P0.40 and con-
crete C0.40 at each age was measured and the results were
obtained in the same way.
It can be seen in Fig. 3 that the electrical resistivity does not
change with time during the testing period, indicating that the
slice samples have been fully saturated by the NaCl solution. The
results of two slices from each mixture are very close, showing that
this setup has high repeatability in measuring the resistivity. Addi-
tionally, the electrical resistivity of paste P0.30 is the highest, and
decreases with increase of water cement ratio, which is reasonable
due to the higher porosity in a higher water cement ratio paste for
the same pore solution.
The chloride diffusion coefficient (DNC-ER) of samples P0.30,
P0.35, P0.40 and C0.40 was calculated from the measured electrical
resistivity of the slice samples using Eq. (7) and the DNC-ER vs. ln(t)
results at 1d, 2d, 3d, 14d, 28d and 80d are shown in Fig. 4, where
the unit of time t is hours.
It can be seen in Fig. 4 that the chloride diffusion coefficient
(DNC-ER) of each sample decreases with age. The DNC-ER values of

10.0
9.0 P0.3
Electrical resistivity of slices

Chloride diffusion coefficient

8.0 8.0
P0.4
7.0 7.0
P0.35 6.0 P0.35
(Ohm.m)

6.0
(×10-7cm2/s)

P0.4 5.0
5.0 P0.3
4.0
4.0
3.0 C0.4
3.0
2.0
2.0
1.0
1.0 0.0
0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 ln(t) (hour)
Time (min)
Fig. 4. The chloride diffusion coefficient (DNC-ER) of samples P0.30, P0.35, P0.40 and
Fig. 3. Repeatability of the electrical resistivity of the slice samples. C0.40 at 1d, 2d, 3d, 14d, 28d and 80d.
 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34
the pastes reasonably increase with W/C at each age. The chloride
diffusion coefficient of concrete C0.40 is clearly lower than that of
paste P0.40 with the same W/C, and is the lowest of all the sam-
ples. Additionally, the chloride diffusion coefficient of the pastes
or the concrete appears to have a higher slope before 3d and a
lower slope after 3d. This is consistent with the cement hydration
rate, which developed faster in earlier period. Additionally, the per-
meability of the samples decreases 812 times from 1d to 80d, and
the concrete decreases more in this range.
The DNC-ER values of sample C0.40 is much lower than that of
sample P0.40 at each age. It is attributed to the aggregate without
open pores in concrete sample C0.40, taking porous space by the
volume fraction of 65%, greatly decreasing the ion migration path,
which considerably exceeds the ITZ effect on ion diffusion.
4.2. The chloride diffusion coefficient of the disc samples by RCM test
The Cl migration depth, seen as the white region in the split
disc sample P0.35 at 3d, 7d and 28d in Fig. 5(a) is used, for calcu-
lating the chloride diffusion coefficient by Eq. (8). The chloride dif-
fusion coefficient (DRCM) vs. ln(t) results are shown in Fig. 5(b).
It can be seen in Fig. 5(b) that the chloride diffusion coefficient
(DRCM) of the pastes with various W/C or concrete reasonably
decrease with hydration age due to the hydration products filling
the pore spaces, the DRCM value of the paste samples increases with
W/C at each age, and the chloride diffusion coefficient of concrete
C0.40 is clearly lower than that of paste P0.40.
Chloride diffusion coefficient
4.0
3.0
(h10-7cm2/s)
2.0
1.0
0.0
0.0
Fig. 5. The chloride diffusion coefficient (DRCM) of samples P0.30, P0.35, P0.40 and C0.40 at 3d, 7d, 14d, 28d, 56d and 80d.
31
4.3. The comparison of the chloride diffusion coefficient from the two
measurements
4.3.1. The relationship of the chloride diffusion coefficient results (the
DNC-ER vs. the DRCM)
The chloride diffusion coefficient results from the two methods
are of the same order of magnitude as mentioned earlier, however,
the DRCM values in Fig. 5(b) are higher than the DNC-EM values in
Fig. 4 by 1.072.54 times for the paste samples, and 3.405.52
times for the concrete sample at the same ages (3d, 14d, 28d and
80d). Additionally, the DRCM values of concrete C0.40 are clearly
higher than that of paste P0.3 before 28d, higher than that of paste
P0.35 at 3d and 7d as well, which differ from the results of the DNC-
ER in Fig. 4.
The relationship of the chloride diffusion coefficient of samples
P0.3, P0.35, P0.4 and C0.4 obtained from the two measurements at
3d, 14d, 28d and 80d is shown in Fig. 6.
It can be seen in Fig. 6 that there is a linear relationship between
the chloride diffusion coefficient results from the RCM and the NC-
EM tests on the same mixture samples at the same ages, which has
a similar development trend caused by either the water cement
ratio or the hydration time. Both the RCM and the NC-ER are essen-
tially based on chloride ions movement in an electrical field
through the pores of the samples. It should be recognized that
the electrical migration of chlorides in concrete and the rate of
chloride diffusion both depend on the porosity, pore connectivity
and tortuosity [18,19], which explains the correlation. The linear
trend for all the samples is also shown in Eq. (9), however, a better
Higher W/C paste has a
P0.4 higher DRCM
P0.35
C0.4
P0.3
2.0 4.0 6.0 8.0
ln(t) (hour)
(b)
32 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34

3.5 The linear correlation in Eq. (12) shows that the chloride diffu-
Chloride diffusion coefficient

3.0 Paste DRCM = 1.8821DNC-ER - 0.3506 sion coefficient of a concrete with an aggregate volume fraction of
R² = 0.920 65% is a function of the chloride diffusion coefficient of the paste
DRCM (×10-7cm2/s)

Concrete
2.5
2.0
1.5
1.0
0.5
0.0
0.0 0.5
Chloride diffusion coefficient DNC-EM (×10-7cm2/s)
Fig. 6. The relationship of the chloride diffusion coefficient of the samples at 3d,
14d, 28d and 80d from the RCM test and the NC-EM test.
linear correlation, excluding concrete C0.4 can be obtained, as
shown in Eq. (10).
For paste and concrete samples,
DRCM ¼ 1:1935DNCER þ 0:4381; R2 ¼ 0:5581
For paste samples,
DRCM ¼ 1:8821DNCER  0:3506; R2 ¼ 0:9205
A poor linear trend in Eq. (9) from all the samples is due to that
a higher contradiction of the two test methods arises in concrete
C0.4. The DRCM values of concrete C0.40 are higher than these of
paste P0.3 at the same ages, while the DNC-ER values of concrete
C0.40 are lowest in all the samples, as mentioned earlier. It can
be analyzed from the pore structure investigation and the forma-
tion factor, as described later.
4.3.2. The correlation between the chloride diffusion coefficient of
concrete and paste
The correlation between the chloride diffusion coefficient of
concrete and paste from the two test methods are shown in Fig. 7.
Two separate linear trends corresponding to the two test meth-
ods are observed in Fig. 7, the one from the RCM test is the upper
line and a higher correlation coefficient (R2 = 0.9923) is obtained
from the NC-ER test. The correlations between concrete C0.40
and paste P0.40 are shown in Eqs. (11), (12).
From the RCM test,
DRCM ðC0:40Þ ¼ 0:6614DRCM ðP0:40Þ; R2 ¼ 0:9042
From the NC-ER test,
DNCER ðC0:40Þ ¼ 0:3074DNCER ðP0:40Þ; R2 ¼ 0:9923
DRCM = 1.1935DNC-ER + 0.4381 with the same W/C and paste matrix volume fraction of 35% inside
R² = 0.5581
the concrete.
In the RCM test, a sample was saturated with Ca(OH)2 solution,
and the Cl ions migrated inside the sample from the outside by
the electrical driving force. The chloride diffusion coefficient
(DRCM) was calculated by Eq. (8), ignoring ionic diffusion by the
concentration gradient and convection migration in the concrete.
1.0 1.5 2.0 2.5 3.0 3.5
However, the concrete at an early age probably has macropores
or connected capillary channels, and there were additional Cl ions
suction by capillary action, and concentration gradient as well,
besides the electrical driving force. Therefore, the DRCM results cal-
culated by Eq. (8) are over-estimated due to the height of the Cl
migration from the combining effect of the electrical driving force
and the capillary action.
In the NC-EM setup, a sample was saturated with NaCl solution,
the type and concentration of the pore solution inside the sample
ð9Þ being the same as outside the sample in the electrical circuit,
avoiding ionic diffusion driven by the concentration gradient and
convection migration, really following the Nernst-Einstein equa-
tion. Moreover, the smaller sample size make a good saturation
ð10Þ
effect, and high accuracy can be reached.
Additionally, each test takes 696 h to be completed, after sam-
ple preparation, in the RCM method. The electrodes reaction can
change the solution concentration and the current was partially
consumed in the electrodes reaction with the voltage of 060 V,
not fully on Cl migration, which may cause the DRCM results vari-
ation. The NC-EM is newly proposed to measure the chloride diffu-
sion coefficient, and there are no electrodes in this setup and the
test can be completed in 5 min, with consistent results and better
correlation, as in Fig. 7, then being obtained.
4.3.3. The porosity analysis by TGA and the formation factor by the NC-
ER test
The TGA results of pastes P0.3 and P0.4 at 3d are shown in Fig. 8.
The non-evaporating water content in the hydrated pastes, as
chemical bonded water, was obtained in the range 105 °C950 °C
by TGA, considering the ignition loss of the original cement (LC).
The hydration degree of the cement (a) in the pastes can be calcu-
lated by the equation [13] shown in Fig. 8, where W105 and W950
ð11Þ
are the sample weights at temperatures 105 °C and 950 °C, respec-
tively, and Wn/Ccomp. is chemical bounded water per gram com-
pletely hydrated cement.
ð12Þ

Temperature (oC)
0 100 200 300 400 500 600 700 800 900 1000
0
Chloride diffusion coefficient of C0.4

2.5 DRCM(C0.4)=0.6614DRCM(P0.4) -2
R² = 0.9042
-4
2.0
-6
from the NC-ER
TG (mg)
(×10-7cm2/s)

1.5 -8

-10
1.0 DNC-ER(C0.4) = 0.3074DNC-ER(P0.4)
R² = 0.99 -12
0.5 -14 P0.4
P0.3
0.0 -16
0.0 2.0 4.0 6.0 8.0
-18
Chloride diffusion coefficient of P0.4 (×10-7cm2/s)
-20
Fig. 7. The correlation of the chloride diffusion coefficient of paste P0.4 and
concrete C0.4 from the RCM and the NC-EM tests. Fig. 8. The TGA results of pastes P0.3 and P0.4 at 3d.
 L. Xiao et al. / Construction and Building Materials 123 (2016) 27–34 33

The porosity (u) is determined by the ratio of the capillary vol-
ume (Vcapillary) to the total volume of water and cement in the paste
(Vtotal), as shown in Eq. (13).
  
V capillary W=C a a
u¼ ¼   V total
V total Dw Dh Dc
where Dw, Dc, Dh represent the density of the pore solution, cement
and hydrates, respectively.
For Dw = 1.01 g/cm3, Dc = 3.15 g/cm3, Dh = 1.529 g/cm3 (based on
assuming that one unit volume of cement produces 2.06 unit vol-
umes of gel) [17].
The porosity of pastes P0.3 and P0.4 at 3d were 0.351 and 0.432
by Eq. (13), respectively. The porosity of sample C0.4 can be calcu-
lated by the porosity of sample P0.4 and the ITZ volume fraction in
sample C40 according to the aggregate volume faction and the ITZ
thickness. The aggregate volume faction of 65% was used in con-
crete C0.4, and the ITZ thickness of 0.05 mm is taken which is
the highest value in the reference [20,21], the ITZ volume fraction
of 17.6% can be obtained by the calculation [21], the possible total
porosity of concrete C0.4 provided by the paste matrix (u of the
matrix = 0.432  (1–65%) = 0.151) and the ITZ (u of the
ITZ = 0.176) is 0.327, which is obviously lower than that of paste
P0.3 (u = 0.351). It can be derived from the porosity values of sam-
ples P0.30 and C0.40 in that the chloride diffusion coefficient of
sample C0.4 should be lower than that of paste P0.3 at the same
ages.
The formation factor (FF) as a global parameter characterizing
the pore structure of concrete or paste materials is used to analyze
chloride migration. The formation factor of the concrete and paste
samples can be calculated by Eq. (14), and is equal to the electrical
resistivity of a slice sample to the electrical resistivity of the solu-
tion inside the slice sample, as shown in Fig. 9.
qslice
FF ¼
qsolution
In the paste samples, sample P0.3 with the lowest W/C has the
least free water space, resulting in the lowest connected pore net-
work and the highest tortuous pore network highlighted by the
highest formation factor values at each age. The concrete sample
C0.4 has the highest formation factor in all the samples, indicating
the lowest connected pore network and the most tortuous paths
for ion migration. The formation factor results are consistent with
the results of the chloride diffusion coefficient DNC-ER, confirming
that the DNC-ER results are more reasonable, while the DRCM results
appear to have clear errors, especially for the low permeability
samples, such as concrete C0.40 and P0.30.
Therefore, the porosity and the formation factor analysis veri-
fies the reasonable order of the chloride diffusion coefficient
results from the NC-ER test.
350
Formation factor, FF
It can be concluded that the newly proposed measurement
technique NC-ER has advantages in several aspects: (1) no elec-
trode reaction consuming ions and no contact resistance causing
error, (2) a smaller specimen is more easily saturated with solu-
tion, with the test completed in minutes, (3) using a higher concen-
ð13Þ
tration solution to saturate concrete specimen, preventing
interference from the original ions in the concrete, (4) steady state
chloride migration, avoiding interference from capillary action,
concentration gradient and convection, which are hard to be
exactly accounted for.
5. Conclusions
(1) A new non-contact electrical method (NC-EM) is proposed to
obtain the chloride diffusion coefficient of hardened con-
crete and paste by measuring the electrical resistivity of slice
samples being saturated with 10% concentration NaCl solu-
tion. This technique eliminates the errors and problems
caused in the traditional setups with electrodes.
(2) The chloride diffusion coefficient results from the NC-EM
test were compared with that from a rapid chloride migra-
tion test (RCM). Both measurements show that the chloride
diffusion coefficient of the paste or concrete samples reason-
ably decrease with hydration age, and increases with
increase of water cement ratio.
(3) The chloride diffusion coefficient results of the paste sam-
ples at 3d80d by the RCM and the NC-ER tests are in range
of (0.694.35)  107 cm2/s and (0.531.71)  107 cm2/s,
respectively, there being linear relationships. All the results
from the RCM tests are higher than from the NC-ER tests
for the same samples at the same ages, due to the effect of
the chloride migration into the samples in the RCM setup,
possibly not only just by the electrical driving force which
is only considered in the equation used.
ð14Þ
(4) There is better linear correlation between the chloride diffu-
sion coefficient of the concrete and paste samples from the
NC-ER test, and the chloride diffusion coefficient of concrete
C0.4 is lower than that of paste P0.3 at the same ages from
the NC-ER, which were verified by the porosity and forma-
tion factor analysis, while the RCM test showed an opposite
trend.
Acknowledgements
The authors gratefully acknowledge Funding by the National
Natural Science Foundation of China (51348001 and 51478202),
and the State Key Laboratory of Silicate Materials for Architectures
(Wuhan University of Technology) (SYSJJ2015-01).
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