crystals
Article
Standardized Procedure of Measuring the pH Value of Cement
Matrix Material by Ex-Situ Leaching Method (ESL)
Wei-Chien Wang *, Wei-Hsing Huang, Ming-Yu Lee, Hoang Trung Hieu Duong






Citation: Wang, W.-C.; Huang,
W.-H.; Lee, M.-Y.; Duong, H.T.H.;
Chang, Y.-H. Standardized Procedure
of Measuring the pH Value of Cement
Matrix Material by Ex-Situ Leaching
Method (ESL). Crystals 2021, 11, 436.
https://doi.org/10.3390/cryst11040436
Academic Editor: Nima Farzadnia
Received: 13 March 2021
Accepted: 14 April 2021
Published: 17 April 2021
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Copyright: © 2021 by the authors.
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This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Crystals 2021, 11, 436. https://doi.org/10.3390/cryst11040436
and Ya-Hui Chang
Department of Civil Engineering, National Central University, Zhongli District, Taoyuan City 32001, Taiwan;
t321655@ncu.edu.tw (W.-H.H.); 108322057@cc.ncu.edu.tw (M.-Y.L.); trhieu.ncu@g.ncu.edu.tw (H.T.H.D.);
a0928434179@gmail.com (Y.-H.C.)
* Correspondence: weichien@ncu.edu.tw; Tel.: +886-3-422-7151 (ext. 34135)
Abstract: According to the Spanish National Research Council (CSIC) report, the ex-situ leaching
method (ESL) is more appropriate and accurate than other methods for measuring pH value in
terms of repeatability and reproducibility. In this study, the ESL method was used to measure the
pH value of cement matrix materials. The design test process aimed to avoid underestimating the
variation in pH during the process of solution stirring and pH measurement without using both
argon and nitrogen to block the specimen contact with air, with good repeatability and reproducibility.
This study also considered the influence of the dryness of the specimen before crushing, the size
of the powder, the air-exposed specimen, the air-exposed solution, the temperature of the solution,
etc. After testing and analysis, a standard procedure for detecting the pH value of cement matrix
materials was established which is known as the S-ESL method.
Keywords: ESL method; pH measurement; cement; mortar; concrete
1. Introduction
To measure the pH value of concrete, Larbi et al. [1] compressed the fresh concrete to
squeeze the pore solution, and then vacuum filtered it for chemical composition analysis
and pH measurement. Nowadays, it is typical to measure the pH value of fresh concrete
using hydroxide titration methodology.
However, Behnood et al. [2] mention that many countries have not developed a set of
standardized test procedures for pH measurement in concrete; therefore, they categorized
the pH measurement methods of hardened concrete into destructive methods and non-
destructive methods. Destructive methods include the expression method, the in-situ
leaching method (ISL), and the ex-situ leaching method (ESL). Non-destructive methods
include embedded potentiometric electrodes and optical fiber sensors.
In the extraction method, Taylor [3] obtained the pore solution of hardened concrete
pieces through a hydraulic press machine, then measured the pH value of the pore solution.
Taylor used this method to extract the pore solution of cement slag paste (water-cement
ratio: 0.5); after two years of curing, the pore solution was squeezed with a maximum
hydraulic pressure of 343 MPa. To obtain more pore solution of mortar, Barneyback et al. [4]
increased the pressure to 550 MPa. After extracting the concrete pore solution, the pH value
could be measured by the commercial electrode pH measurement equipment or could be
calculated from the hydroxide ion concentration by titration.
Then, Sagues et al. [5] developed an in-situ leaching method by drilling holes in
concrete specimens with a diameter of nearly 5 mm and a depth of 25 mm. After holes
are drilled, the concrete powder is removed. Then 0.4 mL of deionized water is poured
into the hole, and MI-405 glass pH microelectrode and Ag/AgCl electrode are used to
measure the pH value. Stojanović [6] also used the ISL method to measure the pH level
of powdered concrete samples and in suspension. However, Li [7] and Cyr [8] claimed
that the ISL method has a variety of limitations such as require moisture saturation, the
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Crystals 2021, 11, 436 2 of 13

constituent assumption, and a long testing period. In addition, Paudel [9] developed a
modified in situ leaching method to achieve a more accurate method using for measuring
pH value of fly-ash geopolymer concrete.
Another pH measurement method which is called ex situ leaching methods (ESL) is
well-known for faster and easier due to its simple procedures and no special or expensive
equipment required [10]. The ex situ leaching method (ESL) is conducted by taking the
sample to the laboratory and sealing it in a bag during transportation to prevent it from
evaporation and exposure to carbon dioxide in the air. In the laboratory, the specimen is
crushed and passed through a #200 (0.074 mm) sieve. After that, 10 g of the specimen is
mixed with 10 g of deionized water, with continuous stirring on a magnetic stirrer for 5 min,
and then pH is measured. This method is based on the ASTM D4972 for soil pH value
measurement, which is typically used to measure the pH value of soil. Behnood et al. [2]
compiled the results of the ex-situ leaching method to determine the pH of concrete under
different study conditions. However, there is still no standardized test procedure for
measuring the pH of concrete using the ESL method. According to Plusquellec et al. [11],
a majority of ESL methods should include the following steps: (1) ground concrete is
powdered, (2) leaching of the powder with a known amount of deionized water in a set
time, (3) the solution is filtered, (4) the extracted solution is analyzed. In recent years, the
ESL method was used widely for measuring the pH level of the mortar and concrete [12]
For the pH measurement method for the pore solution of low alkaline cementitious
materials, the Spanish National Research Council (CSIC) [10], mentioned that the repeata-
bility and reproducibility of the ESL method can be more applicable and more accurate
than other pH measurement methods. Besides, Xia [13] stated that the applicability to
high performance concretes and short experimentation period are the advantages of the
ESL method compared to in situ leaching (ISL) method and pore water expression (PWE)
method. However, the accuracy of the ESL method when measurement concretes contain-
ing pozzolans or highly soluble inorganic salts should be determined.
Since the pH plays an important role in the durability of the concrete used in the final
storage site of radioactive nuclear waste, it is essential to develop a set of specific standard
test methods for high accuracy, repeatability, and reproducibility in measuring the pH of
the concrete. The current ESL method has two problems. Firstly, the specimen treatment
method before crushing is not clear enough, such as whether air-drying or oven-drying is
required; the second is that the stirring of solution and the pH measurement need to be in
an environment of N2 gas.
In this study, the experiments used the ordinary Portland cement (OPC) paste and
OPC mixing with the silica fume (SF) and propose an S-ESL method to measure a pH
value. The first consideration is to understand the impact of the processing method of the
specimen before crushing on the results of the pH measurement; the second consideration
is to understand the influence of the pH measurement process if it is not under the N2 gas
protection environment. S-ESL method is according to the above test results, by improving
the standard procedures of ESL to simplify the equipment required of test, but still achieve
the accuracy of pH measurement.

2. Experimental Methods
2.1. The Experimental Procedure
Extensive experiments were conducted to examine the S-ESL method for a standard
testing procedure using various combinations of the pure cement paste (OPC) as well
as 40% silica fume as cement paste replacement (C60-SF40), with a water-binder (W/B)
ratio of 0.5, and curing at room temperature for 1 day, 7 days, and 28 days. Due to the
characteristics of continuous hydration of the short curing age specimens, the variation of
the test results can be amplified. Thus, the S-ESL method can achieve reliable results.
The preliminary test procedure refers to the standard pH test method for the soil
ASTM D4972 as in a related report, wherein, the specimen was not dried, and the ground
powder was quenched with cold water [7,10,14–19]. Alonso [10] recommended that the
Crystals 2021, 11, x FOR PEER REVIEW 3 of 15

Crystals 2021, 11, 436 3 of 13

The preliminary test procedure refers to the standard pH test method for the soil
ASTM D4972 as in a related report, wherein, the specimen was not dried, and the ground
powder was quenched
typical experiment’s with cold
parameters waterbe
should [7,10,14–19].
considered,Alonso [10]specimen’s
including recommended thatwith
powder the
typical experiment’s parameters should be considered, including specimen’s powder with
particle size less than 80 µm, the liquid-to-solid ratio of 1, followed by specimen stirring
particle
and size lessinthan
quenching 80 ESL
5 min. μm, process
the liquid-to-solid
is shown inratio of 1.
Figure 1, followed by specimen stirring
and quenching in 5 min. ESL process is shown in Figure 1.

Prepare the specimen The particle diameter of around 80 μm

(powdering) < 15 min (without using a sieve)

By a minimum of three pH buffer solutions that

Calibration the pH electrode bracket the expected pH of the samples and are
ideally three pH units or more apart.

pH 4.00 pH 7.00 pH 10.00

Preparation of the suspension: mix

10 g of powdered and 10 mL of
the CO2-free deionised water < 5

Stirring: continuously and

vigorously stir the suspension for
5 min

Filtering (when it is made) < 5 min

pH measurement, just after stirring:

 To measure the pH of the suspension directly with the
combination pH electrode, stirring continuously during The filtration of the suspension and the pH
the measurement until the pH value is stable and record measurement must be made under an inert
the value obtained. atmosphere by bubbling/flushing with N2 gas.
 To pass the suspension through a 0.45 μm filter and
measure the pH of the filtered solution.

Figure
Figure 1. Ex-situ leaching
1. Ex-situ leaching (ESL)
(ESL) method
method process
process chart.
chart.

S-ESL
S-ESL method
method is
is designed
designedfor
forhard-dissolved
hard-dissolvedsolid
solidmaterials.
materials.The
Thepreliminary
preliminaryoperat-
oper-
ing procedures of the experiment are described here. The specimen was taken out from the
ating procedures of the experiment are described here. The specimen was taken out from
curing room, the surface water was wiped, the specimen was crushed with a hydraulic
the curing room, the surface water was wiped, the specimen was crushed with a hydraulic
punch, the specimen’s pieces were collected and ground within 15 min. The specimen
punch, the specimen’s pieces were collected and ground within 15 min. The specimen
powder was passed through a #200 sieve (0.074 mm) and kept in a zipper bag containing
powder was passed through a #200 sieve (0.074 mm) and kept in a zipper bag containing
soda lime. Then, 10 g of powder was taken out from the zipper bag and put kept in a beaker,
soda lime. Then, 10 g of powder was taken out from the zipper bag and put kept in a
mixed with 10 g of deionized water within 5 min, stirred for 5 min on a magnetic stirrer,
beaker, mixed with 10 g of deionized water within 5 min, stirred for 5 min on a magnetic
and then the pH was measured just after stirring, without stirring continuously during the
stirrer, and then the pH was measured just after stirring, without stirring continuously
measurement until the pH value is stable and record the value obtained. The temperature
during the measurement until the pH value is stable and record the value obtained. The
of the solution in the experiment should match the room temperature environment. S-ESL
temperature of the solution in the experiment should match the room temperature envi-
process is shown in Figure 2.
ronment. S-ESL process is shown in Figure 2.
With an aim to evaluate the standard operating procedures of the S-ESL method,
variation in various factors were investigated which comprise the specimen, the curing
time, the dryness of the specimen before crushing or the drying of the specimen in general,
the size of the powder, the air-exposure periods of the powder as well as the solution, and
the temperature of solution. The effects of those factors on the pH of the specimen were an-
alyzed to understand the influence of those factors, then the standard operating procedure
of the S-ESL method was established for measuring the pH of cement matrix materials.
Crystals2021,
Crystals 2021,11,
11,436
x FOR PEER REVIEW 44 of
of 13
15

 Specimen should be crushed without air-drying or oven-

drying, the specimen were collected and powdering
Prepare the specimen within 15 min.
 Specimen after powdering passed through a #200 sieve
(0.074 mm) and kept in a zipper bag containg soda lime.

By a minimum of three pH buffer solutions that

Calibration the pH electrode bracket the expected pH of the samples and are
ideally three pH units or more apart.

pH 4.00 pH 7.00 pH 10.00

Preparation of the suspension: mix

10g of powdered and 10 mL of
deionised water < 5 min

Stirring: continuously and

vigorously stir the suspension for
5 min

pH measurement: to measure the pH of the

suspension directly with the combination pH
electrode just after stirring, without stirring
continuously during the measurement until the pH
value is stable and record the value obtained.

Figure 2.
Figure 2. Modified
Modified Ex-situ
Ex-situ leaching
leaching (S-ESL)
(S-ESL) method
method process
process chart.
chart.

Withexperimental
The an aim to evaluate the standard
procedures operating
for the tests procedures
designed in this of the S-ESL
study method,
are described
variation
as follows:in various factors were investigated which comprise the specimen, the curing
time,
1. the dryness
The influenceofofthe specimenbefore
air-drying beforecrushing
crushing onorpH
thevalue.
drying Theof the specimen
cement paste in
wasgeneral,
cured
the size
for 28 days. After that, the specimen was taken out of the curing room, and and
of the powder, the air-exposure periods of the powder as well as the solution, the
the temperature
surface water of of
solution. The effects
the specimen was of those After
wiped. factors0, on
0.25, the0.5,
pH0.75,
of the specimen
1, 2, 3, 4, andwere
5 h,
analyzed to understand
the specimen the influence
was crushed of those factors,
by a hydraulic punch. thenThethe standard operating
experiment proce-
was conducted
dure according
of the S-ESL method
to the standardwas S-ESL
established for measuring the pH of cement matrix mate-
procedure.
rials. The influence of oven-drying on the pH value before crushing. The cement paste
2.
The
was experimental
cured for 28 days. procedures for the
After that, thetests designed
specimen was in takenthis out
study are curing
of the described
room,as
follows:
the surface water of the specimen was wiped, and the specimen was kept in an oven
at 105 ◦ C for 0, 1, 3, and 6 h. Then, the specimen was taken out of the oven and
1. The influence of air-drying before crushing on pH value.
cooled
The for 1 paste
cement h, thenwas crushed
curedwith a hydraulic
for 28 days. After punch.
that, The experiment
the specimen wastaken
was conducted
out of
according to the standard S-ESL procedure.
the curing room, and the surface water of the specimen was wiped. After 0, 0.25, 0.5,
3. 0.75,
The influence
1, 2, 3, 4, of
and the 5 air-exposure
h, the specimen timewasof powder
crushedon bythe pH valuepunch.
a hydraulic Both the OPC
The and
experi-
C60-SF40 cement paste were cured for 28 days.
ment was conducted according to the standard S-ESL procedure. After that, the specimen was taken
2. The out of the curing
influence room, the surface
of oven-drying on thewater
pH valueof the specimen
before crushing. wiped, and the specimen
was cement
The crushedpaste
and ground
was cured withfor
a hydraulic
28 days. Afterpunch. Then,
that, the the powderwas
specimen wastaken
exposed
out to
of
the air for 0, 1, 5, 10, 20, 30, 60, and 120 min before mixing
the curing room, the surface water of the specimen was wiped, and the specimen was with deionized water. The
experiment
kept wasat
in an oven conducted
105 °C foraccording
0, 1, 3, and to6the standard
h. Then, the S-ESL
specimen procedure.
was taken out of the
4. ovenThe influence of the air-exposure time of solution
and cooled for 1 h, then crushed with a hydraulic punch. on the pH value
The The experiment
experiment was
was divided into two parts and the difference
conducted according to the standard S-ESL procedure. of the results was observed between
3. The 1 and 28 daysof
influence ofthespecimen curingtime
air-exposure time. In the first
of powder on part,
the pH thevalue
OPC paste was cured
Both the OPC and C60-SF40 cement paste were cured for 28 days. S-ESL
for one day, and the powder was obtained according to the standard method.
After that, the
The powder
specimen waswastaken divided
out of into six solution
the curing room, parts at thewater
the surface same of time
the which
specimencontained
wiped,
10 g of powder each in six separate beakers. Then, the solutions in these six beakers
and the specimen was crushed and ground with a hydraulic punch. Then, the pow-
were exposed to the air for 0, 5, 12, 20, 30, and 60 min before conducting the pH
der was exposed to the air for 0, 1, 5, 10, 20, 30, 60, and 120 min before mixing with
measurements. In the second part, both of the OPC and C60-SF40 pastes were cured
Crystals 2021, 11, 436 5 of 13

for 28 days and then divided into eight solution parts at the same time. These eight
beakers of solutions were exposed to the air for 1, 5, 10, 20, 30, 45, 60, and 120 min
before measuring the pH.
5. The pH of multiple beaker solutions from the same source were compared. The
OPC paste was cured for seven days, then the powder was obtained according to the
standard S-ESL method, then, eight beakers were taken to make eight parts of the
solution, and the test was carried out according to the standard S-ESL procedure.
6. The pH result of the same cup of solution at different measurement time intervals.
The OPC paste was cured for seven days, then the powder was obtained according to
the standard S-ESL method. After making one beaker of the solution as an experiment
specimen, it was exposed to air and the pH was measured every 5 min for a total of
eight times.
7. Influence of the particle size of the powder on the results of pH value. OPC and C60-
SF40 pastes were cured for 28 days, then the powder was obtained according to the
standard S-ESL method. The powder was tested in 4 sizes: #30~#50 (0.595–0.297 mm),
#50~#100 (0.297–0.149 mm), #100~#200 (0.149–0.074 mm); <#200 (0.074 mm).
8. The influence of the solution’s temperature on the pH. OPC and C60-SF40 pastes were
cured for 28 days, and the powder was obtained according to the standard S-ESL
method. The temperature of the solution was adjusted to 24 ◦ C, 25 ◦ C, 30 ◦ C, 35 ◦ C,
40 ◦ C, and 45 ◦ C using a magnet heater.

2.2. Materials
The experiment used Portland cement type 1 (Taiwan Cement Company, Taipei,
Taiwan), and Microsilica Grade 951-U silica fume (ELKEM, Oslo, Norway). The chemical
composition of the cement is mentioned in Table 1. In addition, the silica fume used was a
gray powder with a particle size of 0.1~0.2 µm, a specific gravity of 2.2, the specific surface
area variation between 2200 and 2600 m2 /kg and passed through No. 325 sieve > 90%.

Table 1. The chemical composition analysis of the cement and silica fume.

Composition SiO2 CaO Al2 O3 Fe2 O3 MgO SO3 I.L. * Ca/Si

Cement 22.1% 64.6% 5.4% 3.1% 1.4% - 1.06% 2.92
Silica fume 95.0% 0.4% 0.6% <0.05% 0.3% <0.2% - 0.004
* I.L. is the abbreviation for loss on ignition. Source: The materials in Table 1 are provided by Taiwan Cement
Company which is measured by the XRF method.

2.3. The Experimental Instrument

The experimental equipment were: (1) a pH measurements from the S-ESL method
using combination of pH electrode with a resolution of 0.01 pH, accuracy of ±0.1 pH,
and automatic temperature compensation (ATC) (Bland: DGWater, model: G59U10-10000,
made in Poland), (2) Electronic scale with ±0.1 g accuracy, (3) a magnetic stirrer (model:
PC-420D, LED digital display, the heating temperature control ranger is 5~550 ◦ C, and the
speed is 60~1150 rmp, Corning, Glendale, AZ, USA), (4) beakers and plastic flasks or cups
(can be capped or sealed), and (5) a grinding equipment (working mechanism: pressure,
impact and friction, fineness < 0.04 mm (depending on the material), grinding chamber
volume: max. 250 mL, input: broken glass < 15 mm).
To calibrate the pH electrode, at least three standard buffer solutions were required.
The expected range of pH should be 10.5–12.5 for the low-pH cement material. Ideally,
the standard buffer solution should be separated into three pH ranges, for example, pH 7,
10 ± 0.8, and 13–14. All standard buffer solutions for temperature correction and calibration
were included, and the pore solution was tested at the same temperature.
 As shown in Figure 3, when the OPC-28D’s air-drying time is under 5 h, the mean
and standard deviation (SD) of the measured pH value is 12.82 ± 0.02, the repeatability
Crystals 2021, 11, 436 6 of 13
error Sr = 0.013, the value of repeatability r = 0.038, and repeatability variability Vr =
0.101%. The result shows that the repeatability (r) of the pH measurement is acceptable.
The repeatability (r) obtained is lower than ±0.1, which can be assigned to the pH elec-
trode. However,
3. Results when the C60-SF-28D’s air-drying time is under 5 h, the mean and stand-
and Discussions
ard
3.1. deviation of Air-Drying
The Effect of the measured pHCrushing
before value ison
12.14 ± 0.16, the repeatability error Sr = 0.114,
the pH
valueFigure
of repeatability r = 0.323, and repeatability variability
3 shows that for OPC and C60-SF40 pastes, after Vr =28
0.939%.
days ofThe resultsthe
curing, showpH
that the repeatability (r) of the pH measurement is unacceptable, which is about
value of the S-ESL test decreased as the air-drying duration before crushing increased. In 3 times
higher than
addition, thethe
pHerror
valueofofthe
thepH electrode
C60-SF40 (±0.1). reduced
specimen Therefore, the pH measurement
at approximately 0.096 perresults
hour.
will be affected by the air-drying time before the specimen is crushed. In the S-ESL
In contrast, a decrease in pH of the OPC specimen was slower at about 0.012 per hour. The proce-
dure,
reasonthe
forspecimen should
the decrease in pHbe crushed without
was related to theair drying. of the specimen still.
hydration

Figure
Figure 3.
3. The
Theeffect
effectofofthe
theair-drying
air-dryingtime
timeononthe pH
the value
pH of of
value OPC and
OPC C60-SF40
and after
C60-SF40 curing
after for for
curing 28
days.
28 days.

3.2. The
ForEffect of Oven-Drying
the C60-SF40 cement before Crushing
paste, on the pH Value
the hydration rate was slower than that of OPC
cement paste due to the additional silica
Figure 4 shows that for OPC and C60-SF40 pastes,fume in the C60-SF40
after 28component. As athe
days of curing, result,
pH
the hydration
value percentage
of the specimen of the C60-SF40
decreased specimeninafter
with the increase the 28 days was
the oven-drying lower than
duration. the
In addi-
hydration percentage of the OPC specimen. Thus, changing the specimen’s
tion, the pH value of the C60-SF40 specimen reduced more at the rate of about 0.093 per air-drying
duration
hour. Thehad a significant
explanation for effect on the reduction
this reduction pHtovalue
is related of C60-SF40.
the continued Therefore,
hydration when
of paste.
the specimen reaches the curing age, it is suggested that the subsequent
The hydration percentage of C60-SF40 paste after 28 days curing was lower than that ofprocedure such as
crushing be carried out immediately after air-drying, so as not to underestimate
the OPC paste after 28 days curing. Thus, oven-drying the specimen before crushing has the pH of
the concrete.
a significant impact on the reduction of the C60-SF40 pH. Therefore, when the specimen
reachesThethe
pHcuring
of OPCage,
anditC60-SF40 specimens
is suggested that theafter 28 days ofprocedure
subsequent curing was 12.84
such asand 12.35,
crushing
respectively, indicating that adding silica fume to the cement could reduce the pH of the
should be carried out immediately after oven-drying so that the measured pH value of
paste. In addition, we also carried out the pH test of C60-SF40 paste after curing for seven
the concrete is not underestimated.
days and 28 days, and the results were 13.07 and 12.35, respectively. This indicates that
Using Equations (1)–(3), the result is shown in Figure 4. When the OPC-28D is put
when silica fume is used to replace the cement, silica fume consumes the alkalinity in the
under oven-drying within 6 h, the mean and standard deviation of the measured pH value
cement admixture and reduces the pH of concrete. This is the method used for designing
is 12.77 ± 0.06, the repeatability error Sr = 0.046, the value of repeatability r = 0.129, and
low alkaline cement by adding Pozzolan materials to achieve low alkali properties.
repeatability variability Vr = 0.360%. For C60-SF-28D, the mean and standard deviation of
In addition, observation by statistical analysis, the statistical analysis method of the
the measured pH value is 12.06 ± 0.25, the repeatability error Sr = 0.176, the value of re-
Spanish National Research Council (CSIC) [10] was used to estimate the variance of the
peatability r = 0.499, and repeatability variability Vr = 1.459%. The repeatability (r) of two
statistical analysis (S2r ), based on the equation:
specimens uses oven-drying before crushing is higher than two specimens using air-dry-
ing before crushing. Therefore, for incomplete s hydration’s specimen, the pH results will
SSr
be affected by the oven-drying period Sbefore r = the specimen is crushed. Therefore, the spec- (1)
N−p
imen should be crushed without oven-drying.
r = 2.83Sr (2)
Sr
Vr = (3)
m
where:
SSr is the residual, i.e., the sum of the variance of the statistical analysis value in the laboratory;
N is the total number of data points;
Crystals 2021, 11, 436 7 of 13

p is the number of laboratories;

r is value of repeatability. The uncertainty of between measurements is equal to the
confidence√interval of differences. By convention, the confidence interval is taken to be
95%, r = 2 2Sr = 2.83Sr [10].
Vr is repeatability variablility;
and m is the gross average value.
As shown in Figure 3, when the OPC-28D’s air-drying time is under 5 h, the mean and
standard deviation (SD) of the measured pH value is 12.82 ± 0.02, the repeatability error
Sr = 0.013, the value of repeatability r = 0.038, and repeatability variability Vr = 0.101%.
The result shows that the repeatability (r) of the pH measurement is acceptable. The
repeatability (r) obtained is lower than ±0.1, which can be assigned to the pH electrode.
However, when the C60-SF-28D’s air-drying time is under 5 h, the mean and standard
deviation of the measured pH value is 12.14 ± 0.16, the repeatability error Sr = 0.114, value
of repeatability r = 0.323, and repeatability variability Vr = 0.939%. The results show that
the repeatability (r) of the pH measurement is unacceptable, which is about 3 times higher
than the error of the pH electrode (±0.1). Therefore, the pH measurement results will be
affected by the air-drying time before the specimen is crushed. In the S-ESL procedure, the
specimen should be crushed without air drying.

3.2. The Effect of Oven-Drying before Crushing on the pH Value

Figure 4 shows that for OPC and C60-SF40 pastes, after 28 days of curing, the pH
value of the specimen decreased with the increase in the oven-drying duration. In addition,
the pH value of the C60-SF40 specimen reduced more at the rate of about 0.093 per hour.
The explanation for this reduction is related to the continued hydration of paste. The
hydration percentage of C60-SF40 paste after 28 days curing was lower than that of the
OPC paste after 28 days curing. Thus, oven-drying the specimen before crushing has a
significant impact on the reduction of the C60-SF40 pH. Therefore, when the specimen
reaches the curing age, it is suggested that the subsequent procedure such as crushing
Crystals 2021, 11, x FOR PEER REVIEW 8 of 15
should be carried out immediately after oven-drying so that the measured pH value of the
concrete is not underestimated.

Figure
Figure 4.
4. The
The effect
effect of the oven-drying
oven-drying time
time on
onthe
thepH
pHof
ofOPC
OPCand
andC60-SF40
C60-SF40after
aftercuring
curingfor
for2828days.
days.
Using Equations (1)–(3), the result is shown in Figure 4. When the OPC-28D is put
3.3. Theoven-drying
under Effect of Air-Exposure
within 6 h,Time
the of the Specimen
mean Powder
and standard on the pH
deviation of Value
the measured pH value
is 12.77 ±
The experiment was conducted using OPC and C60-SF40 paste after 28r =
0.06, the repeatability error S r = 0.046, the value of repeatability 0.129,
days and
of cur-
repeatability variability V = 0.360%. For C60-SF-28D, the mean and standard
ing. According to the resultr shown in Figure 5, the pH of the specimen decreased with the deviation
of the measured
increase pH value
in air exposure duration. In±
is 12.06 0.25, thethe
addition, repeatability
pH value oferror Sr = 0.176,
the C60-SF40 the value
reduced of
faster
repeatability r = 0.499, and repeatability variability
than that of the OPC paste. The pH reduction of the C60-SF40 V r = 1.459%. The repeatability (r) of
was approximately 0.11 per two
hour. In contrast, the pH reduction rate of the OPC specimenspecimens
specimens uses oven-drying before crushing is higher than two was smallerusing air-drying
and the rate
was approximately 0.04 per hour. The reason for the pH value reduction is continuous
hydration. For C60-SF40 paste, the hydration degree of curing for 28 days was lower than
that of OPC. Therefore, the contact time between cement powder and the air has a signif-
icant impact on the reduction in C60-SF40 pH. Thus, after the specimen reaches the curing
Crystals 2021, 11, 436 8 of 13

before crushing. Therefore, for incomplete hydration’s specimen, the pH results will be
affected by the oven-drying period before the specimen is crushed. Therefore, the specimen
should be crushed without oven-drying.

3.3. The Effect of Air-Exposure Time of the Specimen Powder on the pH Value
The experiment was conducted using OPC and C60-SF40 paste after 28 days of curing.
According to the result shown in Figure 5, the pH of the specimen decreased with the
increase in air exposure duration. In addition, the pH value of the C60-SF40 reduced faster
than that of the OPC paste. The pH reduction of the C60-SF40 was approximately 0.11 per
hour. In contrast, the pH reduction rate of the OPC specimen was smaller and the rate
was approximately 0.04 per hour. The reason for the pH value reduction is continuous
hydration. For C60-SF40 paste, the hydration degree of curing for 28 days was lower
than that of OPC. Therefore, the contact time between cement powder and the air has a
significant impact on the reduction in C60-SF40 pH. Thus, after the specimen reaches the
Crystals 2021, 11, x FOR PEER REVIEW 9 of 15
curing age, the subsequent procedure of pH testing should be carried out immediately
after grinding, so as not to underestimate the pH of the concrete.

Figure
Figure 5.
5. The
ThepH
pHof
ofOPC
OPC and
and C60-SF40
C60-SF40 paste
paste powder
powder exposed
exposed to
to air.
air.

Using
3.4. The Equations
Effect (1)–(3),Duration
of Air-Exposed the resultof is
theshown in Figure
Solution on pH 5, when the exposure time of the
OPC-28D’s powder is under 120 min, the mean and standard deviation of the measured pH
The pH value in the first stage of the air exposure is shown in Figure 6, the one-day
value is 12.84 ± 0.03, the repeatability error Sr = 0.019, the value of repeatability r = 0.054,
OPC specimen curing has the mean and standard deviation of the measured pH value is
and repeatability variability V = 0.148%. For C60-SF-28D, the mean and standard deviation
12.84 ± 0.03, the repeatability rerror Sr = 0.019, the value of repeatability r = 0.054, and re-
of the measured pH value is 12.22 ± 0.08, the repeatability error Sr = 0.055, the value of
peatability variability Vr = 0.148%. The numerical variation was small, which indicates
repeatability r = 0.157, and repeatability variability Vr = 0.450%. The result shows that
that in the context of typical operating procedures, the cement paste solution which is air-
the repeatability (r) of the OPC-28D is satisfied with the error of the pH electrode (±0.1).
exposed for 60 min, has an insignificant pH deviation.
Besides, the repeatability (r) of the C60-SF-28D is acceptable, the values obtained are close
In the second stage of air exposure, pH measurement of 28-days curing of OPC and
to the instrument’s error of the pH electrode (±0.1). Although the statistical analysis results
C60-SF40 was conducted, and the results are mentioned in Figure 7, which showed that
of the experiment showed that the specimen powder contacting with air under 120 min
the 28-day curing OPC had the mean and standard deviation of the measured pH value
did not have a significant effect on the results, the S-ESL procedure is still required to mix
is 12.79 ± 0.00, the repeatability error Sr = 0.003, the value of repeatability r = 0.007, and
with deionized water within 5 min for safety issues.
repeatability variability Vr = 0.023%. The result showed that the repeatability (r) of the pH
measurement
3.4. The Effect is
of satisfied
Air-Exposed with the error
Duration of of
thethe pH electrode
Solution on pH (±0.1). The 28-day curing C60-
SF40 The
had pH
the value
mean in and standard deviation of the measured
the first stage of the air exposure is shown pH value is 12.31
in Figure ± 0.01,
6, the the
one-day
repeatability error S r = 0.010, the value of repeatability r = 0.028, and repeatability varia-
OPC specimen curing has the mean and standard deviation of the measured pH value
bility Vr ±
is 12.84 = 0.081%.
0.03, theThe result shows
repeatability errorthat
Sr =the repeatability
0.019, the value (r) of the pH measurement
of repeatability r = 0.054, and is
satisfied with the error of the pH electrode (±0.1). Thus, these results prove
repeatability variability Vr = 0.148%. The numerical variation was small, which indicates that in the
cement paste
that in the operating
context procedures,
of typical within
operating 120 min ofthe
procedures, air-exposure,
cement pastethesolution
cement paste
whichso-is
lution has no significant deviation in pH of the
air-exposed for 60 min, has an insignificant pH deviation. samples measured.
In conclusion, this stage of experiment is aimed to investigate whether the pH of the
cement paste solution is affected by environmental components such as CO2 in the air and
found that the effect of the environment on the cement paste solution is not significant.
Crystals 2021, 11, 436
x FOR PEER REVIEW 109 of 13
15

Crystals 2021, 11, x FOR PEER REVIEW 10 of 15

Figure 6.
Figure pH value
6. pH value of
of 1-day
1-daycuring
curingof
ofair-exposed
air-exposedOPC
OPCwithin
within6060
min of of
min air-exposure time
air-exposure of solution.
time of solu-
tion.
In the second stage of air exposure, pH measurement of 28-days curing of OPC and
C60-SF40 was conducted, and the results are mentioned in Figure 7, which showed that
the 28-day curing OPC had the mean and standard deviation of the measured pH value
is 12.79 ± 0.00, the repeatability error Sr = 0.003, the value of repeatability r = 0.007, and
repeatability variability Vr = 0.023%. The result showed that the repeatability (r) of the
pH measurement is satisfied with the error of the pH electrode (±0.1). The 28-day curing
C60-SF40 had the mean and standard deviation of the measured pH value is 12.31 ± 0.01,
the repeatability error Sr = 0.010, the value of repeatability r = 0.028, and repeatability
variability Vr = 0.081%. The result shows that the repeatability (r) of the pH measurement
is satisfied with the error of the pH electrode (±0.1). Thus, these results prove that in
Figure 6. pH value
the cement paste of 1-day curing
operating of air-exposed
procedures, OPC
within within
120 60 air-exposure,
min of min of air-exposure time of solu-
the cement paste
tion.
solution has no significant deviation in pH of the samples measured.

Figure 7. pH value of 28-days cured OPC, and 28-days cured C60-SF40 within 120 min of air expo-
sure time of solution.

3.5. Comparison of the pH Value of Multiple Beaker Solutions from the Same Source
According to the results in Figure 8, the mean and standard deviation of the meas-
ured pH value is 12.56 ± 0.01, the repeatability error Sr = 0.010, the value of repeatability r
= 0.028, and repeatability variability Vr = 0.080%. The result shows that the repeatability
(r) of the pH measurement is satisfied to the error of the pH electrode (±0.1). Measuring
the pH value of eight beaker’s solutions from the same source, using the S-ESL method to
measure pH value achieved acceptable repeatability results (SD < 0.1).

Figure7.
Figure pH value
7. pH value of 28-days cured
curedOPC,
OPC,and
and28-days
28-dayscured
curedC60-SF40
C60-SF40within
within120 min
120 of of
min airair
exposure
expo-
sure
timetime of solution.
of solution.

In conclusion,
3.5. Comparison of thethis
pHstage
Valueofof experiment is aimed
Multiple Beaker to investigate
Solutions whether
from the Same Sourcethe pH of the
cement paste solution
According to the is affected
results by environmental
in Figure 8, the meancomponents
and standard such as CO2 in
deviation of the
theair and
meas-
found that the effect of the environment on the cement paste solution is not significant.
ured pH value is 12.56 ± 0.01, the repeatability error Sr = 0.010, the value of repeatability r
= 0.028, and repeatability variability Vr = 0.080%. The result shows that the repeatability
(r) of the pH measurement is satisfied to the error of the pH electrode (±0.1). Measuring
the pH value of eight beaker’s solutions from the same source, using the S-ESL method to
measure pH value achieved acceptable repeatability results (SD < 0.1).
Crystals 2021, 11, 436 10 of 13

3.5. Comparison of the pH Value of Multiple Beaker Solutions from the Same Source
According to the results in Figure 8, the mean and standard deviation of the measured
pH value is 12.56 ± 0.01, the repeatability error Sr = 0.010, the value of repeatability
r = 0.028, and repeatability variability Vr = 0.080%. The result shows that the repeatability
(r) of the pH measurement is satisfied to the error of the pH electrode (±0.1). Measuring
Crystals 2021, 11, x FOR PEER REVIEW
the pH value of eight beaker’s solutions from the same source, using the S-ESL 11 of 15
method to
measure pH value achieved acceptable repeatability results (SD < 0.1).

ThepH
Figure8.8.The
Figure pHvalue
valueofofeight
eight beakers
beakers with
with thethe same
same source
source of solution.
of solution.
3.6. The Effect of pH Measurement in the Same Cup of Solution at Equal Time Interval
3.6. The Effect of pH Measurement in the Same Cup of Solution at Equal Time Interval
According to the results shown in Figure 9, the mean and standard deviation of
According to the results shown in Figure 9, the mean and standard deviation of the
the measured pH value is 12.53 ± 0.01, the repeatability error Sr = 0.004, the value of
measured pH value is 12.53 ± 0.01, the repeatability error Sr = 0.004, the value of repeata-
repeatability r = 0.010, and repeatability variability Vr = 0.032%. The result shows that
bility r = 0.010, and repeatability variability Vr = 0.032%. The result shows that the repeat-
the repeatability (r) of the pH measurement is satisfied with the error of the pH electrode
ability (r) of the pH measurement is satisfied with the error of the pH electrode (±0.1). The
(±0.1). The pH measurement of the same cup of the solution at an equal time interval,
pH measurement of the same cup of the solution at an equal time interval, using the S-
using
ESL the S-ESL
method methodpH
to measure tovalue
measure
has pH
good value has goodresults
repeatability repeatability results (SD < 0.1).
(SD < 0.1).

Figure 9. The effect of placing one cup of cement paste solution for air-exposure at different periods
Figure 9. The effect of placing one cup of cement paste solution for air-exposure at different peri-
on the
ods pH.pH.
on the
3.7. The Influence of Particle Sizes on the pH
3.7. The Influence of Particle Sizes on the pH
The effect of particle sizes on pH was as shown in Figure 10. For the OPC-28D, the
The effect of particle sizes on pH was as shown in Figure 10. For the OPC-28D, the
mean and standard deviation of the measured pH value is 12.75 ± 0.03, the repeatability
mean and standard deviation of the measured pH value is 12.75 ± 0.03, the repeatability
error S = 0.019, the value of repeatability r = 0.05, and repeatability variability Vr = 0.149%.
error Srr= 0.019, the value of repeatability r = 0.05, and repeatability variability Vr = 0.149%.
The result shows that the repeatability (r) of the pH measurement is satisfied with the
The result shows that the repeatability (r) of the pH measurement is satisfied with the
error
error ofof the
the pH
pHelectrode (±0.1).
electrode(±0.1). However,
However, forfor
thethe C60-SF-28D,
C60-SF-28D, the the
meanmean
and and standard
standard
deviation of the measured pH value is 12.16 ±
deviation of the measured pH value is 12.16 ± 0.10, the repeatability error Sr = 0.071, valuevalue
0.10, the repeatability error S r = 0.071,
of repeatability r = 0.202, and repeatability variability Vr = 0.584%. The results show that
the repeatability (r) of the pH measurement is unacceptable. The repeatability (r) is two
times higher than the error of the pH electrode (±0.1).
If the concrete is used as a tank for the final disposal site of high-level radioactive
Crystals 2021, 11, 436 11 of 13
Crystals 2021, 11, x FOR PEER REVIEW 12 of 15

of repeatability
show that for ther C60-SF-28D,
= 0.202, and the
repeatability variabilitysize,
larger the specimen Vr =the
0.584%. ThepH
measured results
valueshow
will that
thelower.
be repeatability
Therefore,(r)using
of thethe
pHS-ESL
measurement
method withis unacceptable. The
the particle size repeatability
smaller than the (r) is two
#200
times(0.074
sieve higher
mm)than themeasure
can error ofthe
thepHpHvalue
electrode (±0.1).
of concrete more accurate.

Crystals 2021, 11, x FOR PEER REVIEW 12 of 15

show that for the C60-SF-28D, the larger the specimen size, the measured pH value will
be lower. Therefore, using the S-ESL method with the particle size smaller than the #200
sieve (0.074 mm) can measure the pH value of concrete more accurate.

Figure10.
Figure Theeffect
10.The effectofofparticle
particle sizes
sizes onon pH.
pH.

If the
3.8. The concrete
Effect is used Temperature
of the Solution’s as a tank foron the final
the pH disposal
of the Cementsite of Solution
Paste high-level radioactive
nuclear waste, concrete is required to use low-alkaline cement.
The effect of the temperature on the solution’s pH is shown in Figure The results
11. Thein pH
Figure
of 10
28-days cured OPC solution at 25 °C has the maximum pH value. The mean and standard be
show that for the C60-SF-28D, the larger the specimen size, the measured pH value will
lower. Therefore,
deviation using thepH
of the measured S-ESL
valuemethod
is 12.76with thethe
± 0.03, particle size smaller
repeatability errorthan
Sr = the #200
0.050, thesieve
(0.074 mm) can measure the pH value of concrete more accurate.
value of repeatability r = 0.140, and repeatability variability Vr = 0.392%. The result shows
Figure 10.repeatability
that the The effect of particle
(r) of sizes on pH.
the pH measurement is satisfied with the error of the pH elec-
3.8. The
trode Effect
(±0.1). of the Solution’s
However, Temperature on
for the C60-SF-28D, thethe
pHpH
atof25the
°CCement
has thePaste Solution
maximum value, the
3.8. The Effect of the ofSolution’s Temperature on thesolution’s
pH of the Cement Paste Solution
meanThe andeffect
standard the temperature
deviation of the on the
measured pH value pHisis12.18
shown in Figure
± 0.10, 11. The pH of
the repeatability
error The
Sr =effect
28-days cured
0.071, ofOPCthe temperature
value solution on ◦the
at 25
of repeatability solution’s
C rhas pH repeatability
the maximum
= 0.200, and is shownpH in Figure
value. The11.mean
variability TheVrpH=and of standard
0.583%.
28-days
deviation
The cured
resultsof OPC
showthe thatsolution
measured at 25 °C has
pH value (r)
the repeatability the maximum
of the ±
is 12.76 pH
pH0.03, value. The mean
the repeatability
measurement and standard
error Sr The
is unacceptable. = 0.050,
deviation
the valueofofthe
repeatability (r) measured
is two times
repeatability pH higher
r=value isthan
0.140,12.76
andthe ± 0.03,
errortheof repeatability
repeatability the variability error S
pH electrode =r =0.392%.
0.050,
Vr (±0.1). Thethe results
The result
value of repeatability r = 0.140, and repeatability variability Vr = 0.392%. The result shows
above
showssuggest
that thethat the suitable
repeatability (r)curing
of thetemperature
pH measurement shouldisbesatisfied
set to room
withtemperature
the error of(25 the pH
that the repeatability (r) of the pH measurement is satisfied with the◦error of the pH elec-
°C). Besides,
electrode ( ± while
0.1). using air conditioning,
However, for the the temperature
C60-SF-28D, the pH should
at 25 C behascontrolled
the maximumat 25 °C value,
trode (±0.1). However, for the C60-SF-28D, the pH at 25 °C has the maximum value, the
±the
2°C.
mean and standard deviation of the measured pH value is 12.18 ± 0.10, the repeatability
mean and standard deviation of the measured pH value is 12.18 ± 0.10, the repeatability
errorSSr r= =0.071,
error 0.071, value
value of repeatability
of repeatability r = 0.200,
r = 0.200, and repeatability
and repeatability variability
variability Vr = 0.583%.
Vr = 0.583%.
Theresults
The resultsshow show that
that thethe repeatability
repeatability (r) of(r) ofpH
the themeasurement
pH measurement is unacceptable.
is unacceptable. The The
repeatability(r)(r)
repeatability is is
two two times
times higher
higher thanthan the error
the error of theofpH the pH electrode
electrode (±0.1).
(±0.1). The The results
results
abovesuggest
above suggest thatthatthe the suitable
suitable curing curing temperature
temperature should be should be set
set to room to room temperature
temperature (25
°C). ◦ C). Besides,
(25 Besides, while usingwhileair conditioning,
using the temperature
air conditioning, should be controlled
the temperature should at be25 °C
controlled at
±25 ◦ C ± 2◦ C.
2°C.

Figure 11. The effect of the temperature on the pH of the cement paste solution.

Figure
Figure11.
11.The
Theeffect of the
effect temperature
of the on the
temperature onpH
theofpH
the of
cement paste solution.
the cement paste solution.
Crystals 2021, 11, 436 12 of 13

3.9. The S-ESL Method Goals

The S-ESL procedure proposed in this research hopes that the entire procedure can be
operated under normal environmental condition instead of under N2 requirement condi-
tion, the protocol becomes simpler and using more popular instruments, which will benefit
a variety of laboratories lacking N2 equipment. On the other hand, by researching the
variation of results produced by each different operation step, more reasonable operation
steps are proposed, and the requirements of accuracy and repeatability can be achieved.
Variations explored in this study include: air-drying time and oven-drying time before
specimen crushing, air exposure time of powder or solution, the multiple beaker solutions
from the same source, measuring the same cup of solution at equal time intervals, the
particle size of the specimen, and the solution’s temperature. According to the repeatability
statistical analysis results, it is found that if the test conditions are not restricted properly,
factors such as air-drying time and oven-drying time before specimen crushing, the particle
size of the specimen, and the solution’s temperature can make the measurement result
become inaccurate. Therefore, these test conditions need to be strictly controlled in the
S-ESL procedure.
Increasing the air-drying time and oven-drying time before crushing will increase the
value of repeatability (r) of the test. The reason can be related to the continuous hydration
of cement during the pH measurement process. Therefore, in the S-ESL procedure, after
grinding, the specimen’s powder needs to be placed in a zipper bag with soda lime to stop
hydration.
Increasing the particle size of the specimen will increase the value of repeatability (r)
of the test. The reason can because the particle size increases, which lead to the decreasing
of the amount of alkali dissolution in the specimen during the mixing and stirring process.
Therefore, in the S-ESL procedure, the specimen needs to pass the #200 sieve (0.074 mm),
so the alkali in the specimen can be dissolved into the deionized water.
In addition, increasing the temperature of the test solution will reduce the measured
pH value. Therefore, the temperature of the solution should be controlled during the
measurement process, at least the same as room temperature, and this study suggest that it
is best to be able to control it at 25 ◦ C ± 2 ◦ C.

4. Conclusions
This study reviews the revised standard operating procedure, which is called the S-ESL
method. Variations explored in this study include: air-drying time and oven-drying time
before specimen crushing, air exposure time of powder or solution, the multiple beaker
solutions from the same source, measuring the same cup of solution at equal time intervals,
the particle size of the specimen, and the solution’s temperature. We conclude that:
1. According to the repeatability statistical analysis results, it is found that factors such
as air-drying time and oven-drying time before specimen crushing, the particle size
of the specimen, and the solution’s temperature can affect the pH measurement result.
This effect occurs higher in the C60-SF-28D specimen.
2. The pH of the specimen reduces if the sample is air-drying or oven-drying before
being crushed. Moreover, increasing air-drying time or oven-drying time reduces the
pH value of the measurement.
3. The pH of the specimen increases due to the decrease in the specimen particle size. In
contrast, the pH of the specimen reduces due to the increase in the temperature of
the solution.
4. The standard procedure for measuring the pH of cement substation materials by the
S-ESL method is: take out the specimen from the curing room, wipe the surface water,
then crush the specimen with a hydraulic punch. Collect the concrete pieces, then
grind the pieces within 15 min. After that, take the specimen powder which has
been passed through the #200 (0.074 mm) sieve and keep the powder in a zipper bag
containing soda lime. If the specimen is concrete, the collected specimen’s pieces are
mortar. Take out 10 g specimen powder from the zipper bag and put it into a beaker,
Crystals 2021, 11, 436 13 of 13

then add 10 g deionized water within 5 min. Use a magnetic stirrer to stir the solution
compound for 5 min. The unfiltered solution should conduct the pH measurement
within 5 min. The solution’s temperature at the time of the experiment should be the
same as the room temperature (25 ◦ C ± 2 ◦ C).

Author Contributions: Data curation, W.-C.W., M.-Y.L. and Y.-H.C.; methodology, W.-C.W., M.-Y.L.
and H.T.H.D.; resources, W.-C.W., W.-H.H., H.T.H.D. and Y.-H.C. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by Fuel Cycle and Materials Administration, Atomic Energy
Council, Executive Yuan, grant number 107FCMA003.
Data Availability Statement: The data presented in this study are available within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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