materials
Article
Investigation of the Behavior and Mechanism of Action of
Ether-Based Polycarboxylate Superplasticizers Adsorption on
Large Bibulous Stone Powder
Zuiliang Deng 1,2 , Guimin Lu 1, *, Lefeng Fu 2,3 , Weishan Wang 2,3 and Baicun Zheng 2,3






Citation: Deng, Z.; Lu, G.; Fu, L.;
Wang, W.; Zheng, B. Investigation of
the Behavior and Mechanism of
Action of Ether-Based
Polycarboxylate Superplasticizers
Adsorption on Large Bibulous Stone
Powder. Materials 2021, 14, 2736.
https://doi.org/10.3390/ma14112736
Academic Editors: Patryk Rozylo,
Hubert Debski and
Katarzyna Falkowicz
Received: 7 April 2021
Accepted: 17 May 2021
Published: 22 May 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
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4.0/).
Materials 2021, 14, 2736. https://doi.org/10.3390/ma14112736
1 School of Resources and Environmental Engineering, East China University of Science and Technology,
Shanghai 200237, China; dengzl@sunrisechem.com.cn
2 Technical Center, Shanghai Sunrise Polymer Material Co., Ltd., Shanghai 200231, China;
lefeng@sunrisechem.com.cn (L.F.); weishan@sunrisechem.com.cn (W.W.); baicun@sunrisechem.com.cn (B.Z.)
3 Shanghai Engineering Research Center of Construction Admixtures, Shanghai 200231, China
* Correspondence: gmlu@ecust.edu.cn
Abstract: The aim of this paper is to study the adsorption behavior of polycarboxylate superplasticiz-
ers (PCE) on coarse aggregates with a property of high water consumption (above 2%). The coarse
aggregates were ground into a powder to create large bibulous stone powder, and it was observed
that significant amounts of the ether-based PCE were absorbed onto large bibulous stone powder.
The adsorption rate immediately reached a maximum after 5 min and then gradually decreased until
an equilibrium absorption was established after 30 min. Zeta potential, infrared spectroscopy, and
thermogravimetric analysis (TGA) measurements confirmed that the polycarboxylate superplasti-
cizer adsorbed on the surface of the stone powder. Hydrodynamic diameter measurements showed
that the polycarboxylate superplasticizer molecules were smaller than pore size, and the surface area
and pore volume were reduced by the polymer incorporation in the pores.
Keywords: large bibulous stone powder; polycarboxylate (PCE); adsorption; pore size
1. Introduction
The travel time between Maputo to Kosi Bay in Africa was drastically reduced from
6 h to 90 min when the Maputo Katembe Bridge project was finished. However, during
construction, it was found that the physical and chemical properties of the local raw
materials were incompatible with the ordinary admixtures used in other areas. In fact, the
water absorption of coarse aggregate of the coarse stone aggregates from Mozambique was
(2–5%) higher than other standard construction materials (<2%) [1].
It was surprising that the high water consumption was due to the presence of these coarse
aggregates in Mozambique instead of clays from the sand, such as bentonite and kaolinite [2].
These clays are considered harmful contaminants since they significantly reduce the effective-
ness of admixtures, such as water-reducing agents. One of the most popular water-reducer
agents used in construction materials is polycarboxylate (PCE) which has several advantages
including better dispersion, greater slump retention ability, and lower required dosages than
other lignosulfonate-based, melamine-based and naphthalene-based superplasticizers, even
if it possesses corrosion-inhibiting ability [3–5]. This overall better dispersion from PCE
can be attributed to the effects of the steric hindrance from its side chains [6]. However,
PCEs are adsorbed more strongly by clays than polycondensates since PCE can interact
with clays by not only physisorption (surface adsorption) vis hydrogen bonding from
polymers’ side chains or electrostatic adsorption from the anchoring group of polymers
but also by chemisorption (intercalation) while polycondensates are only consumed by
surface interactions [7–10]. In all of different types of clay, montmorillonite shows the
most deleterious influence on the adsorption of PCE onto cement particles as compared
with kaolinite, feldspar and mica. As such, Lei et al., Chen et al., Liu et al., and Li et al.,
https://www.mdpi.com/journal/materials
Materials 2021, 14, 2736 2 of 12

have designed and synthesized several novel polymer structures to prevent physisorp-
tion and chemisorption onto montmorillonite, such as modifying the side chain structure,
replacing it with short side chains, designing star-shaped PCE and using a zwitterionic
functional group [11–15]. Moreover, a general trend was observed from Werani et al. that a
copolymer of poly(methacrylic acid) (PMAA) and methoxy polyethylene glycols (MPEG)
macromonomer with a shorter nEO of 10 could provide better anti-clay dispersing ability
in the cement paste contained 1% (by weight of cement) of montmorillonite [16].
Interestingly several research works show promising results on using limestone pow-
der as a supplementary cementitious materials replacement. For instance, Felekoglu
reported that a substitution of 10% of cement with quarry limestone powder (QLP) could
not only improve the 28 days compressive strength of self-compacting concrete (SCCs)
but also slightly reduce the required dosage of superplasticizer [17]. Moreover, Ahmadi
et al. also showed that the concrete produced from partial replacement of natural zeolite
could present better compressive strength but suffered from a higher dosage of superplasti-
cizer [18]. In addition, Shi et al. also studied the mechanism of limestone powder blended
with cement by researching the nucleation effect, filler effect, dilution effect and chemical
effect of limestone powder. Furthermore, Li et al. presented a study that lithological stone
powders (limestone and tuff) could shorten the setting time of cement paste [19]. However,
insufficient studies have investigated the adsorption of PCE on to stone powders beside Lei
Feng et al. and Hui Feng et al. In the study of Lei Feng et al., they measured the adsorption
capacity of PCE on the surface of tuff powder with quartz, albite and potash feldspar with
two methods, ultraviolet (UV) and total organic carbon (TOC) [20]. Similarly, Hui Feng et al.
analyzed the impact of PCEs’ molecular structure in the presence of Ledong stone powder
and Haikou stone powder. Their studies also showed that aggregates with a stratified
structure and containing mica significantly increased their intercalation with PCEs and thus
decreased the workability of the resulting pastes [21]. However, PCEs possessing shorter
side chains could prevent such intercalation. Limited study could provide a reasonable
explanation for such high water demand from large bibulous stone powder (LBSP) as in
coarse aggregates used in the Maputo Katembe Bridge project in Mozambique since this
specific coarse aggregate does not contain stratified structures. Here, this paper studied the
PCE interactions with the coarse aggregates. First, the coarse aggregate was ground into
stone powder to obtain LBSP. Then, the adsorption behavior of the ether-based PCE onto
the stone powder was analyzed by the TOC method and by measuring the zeta potential
in different pH and PCE concentration solutions. Finally, the adsorption mechanism of
action between the stone powder and the PCE was determined by pore size distribution,
Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA)
measurements. Overall, this paper provides insights into the interactions between PCEs
and coarse aggregates with high water contents.

2. Materials and Methods

2.1. Materials
A coarse aggregate with a relatively high water consumption of 3.1% was provided
from the Hipermaquinas quarry in Boane District, Mozambique. The coarse aggregate
was ground and sifted through a 200 mesh sieve to obtain the LBSP, as displayed in
Figure 1. Then, the stone powder was dried in an oven at 105 ◦ C for two hours, and the
chemical composition was characterized using X-ray fluorescence analysis (D/MAX 2550
VB/PC diffractometer of Rigaku, Tokyo, Japan) and phase identification of such sample
was measured via X-ray powder diffraction (18KW/D/max2550VB/PC, manufactured by
Rigaku, Japan). As shown in Table 1 and Figure 2, the stone powder contains quartz sand,
sanidine (K, Na)(Si3 Al)O8 ), and orthoclase (KAlSi3 O8 ). The orthoclase was mainly from
magmatite, gneiss, and migmatite and could become kaolinite after weathering.
 composition was characterized using X-ray fluorescence analysis (D/MAX 2550 VB/PC
diffractometer of Rigaku, Tokyo, Japan) and phase identification of such sample was
measured via X-ray powder diffraction (18KW/D/max2550VB/PC, manufactured by
Materials 2021, 14, 2736 3 of 12
Rigaku, Japan). As shown in Table 1 and Figure 2, the stone powder contains quartz sand,
sanidine (K,Na)(Si3Al)O8), and orthoclase (KAlSi3O8). The orthoclase was mainly from
magmatite, gneiss, and migmatite and could become kaolinite after weathering.

(a) (b)

Figure 1. Optical photographs of coarse aggregate (a) and large bibulous stone powder (LBSP) (b).
Figure 1. Optical photographs of coarse aggregate (a) and large bibulous stone powder (LBSP) (b).

Table 1.
Table Chemicalcomposition
1.Chemical compositionofoflarge
largebibulous
bibulousstone
stonepowder.
powder.
Materials 2021, 14, x FOR PEER REVIEW 4 of 14
Chemical
Chemical Composition Composition (wt%)
(wt%)
SiO2 Al2 O3 Fe2 O3 Na2 O CaO TiO2 BaO ZrO2 SO3 Br MgO MnO P2 O5
SiO2 Al2O3 Fe2O3 Na2O CaO TiO2 BaO ZrO2 SO3 Br MgO MnO P2O5
67.22 13.25 5.17 2.18 1.20 0.33 0.14 0.13 0.12 0.08 0.06 0.06 0.04
67.22 13.25 5.17 2.18 1.20 0.33 0.14 0.13 0.12 0.08 0.06 0.06 0.04

25,000
♦ SiO2(Quartz)

20,000 Orthoclase
KAlSi3O8
sanidine
15,000 (K,Na)(Si3Al)O8
Intensity (CPS)

10,000
♦ ♦
5,000 ♦♦ ♦ ♦

10 20 30 40 50 60 70 80
2 - Theta (°)
Figure 2. X-ray diffraction (XRD) patterns of stone powder.
Figure 2. X-ray diffraction (XRD) patterns of stone powder.
Polycarboxylate, PCE-1, was provided by Shanghai Sunrise Polymer Material Co., Ltd.,
Polycarboxylate,
Shanghai, China. ItsPCE-1, wascomposition
chemical provided by Shanghai in
is presented Sunrise
FigurePolymer
3, and itsMaterial Co.,
characterization
Ltd., Shanghai,
and China.
solid content is Its chemical
shown composition
in Table 2. is presented in Figure 3, and its charac-
terization and solid content is shown in Table 2.
 2 - Theta (°)

Figure 2. X-ray diffraction (XRD) patterns of stone powder.

Materials 2021, 14, 2736 Polycarboxylate, PCE-1, was provided by Shanghai Sunrise Polymer Material4 of Co.,
12
Ltd., Shanghai, China. Its chemical composition is presented in Figure 3, and its charac-
terization and solid content is shown in Table 2.

Figure 3. Molecular
Figure 3. Molecular structure
structure of
of the
the ether-based
ether-basedpolycarboxylate
polycarboxylate(PCE)
(PCE)used
usedin
inthis
thisstudy.
study.

Table2.2.Characteristic
Table Characteristicmolecular
molecularparameters
parametersof
ofPCE-1.
PCE-1.

Length of Side Side Chain Den- Mn Mw Polydispersity Index

Polydispersity Solid Content
Sample Length of Side Side Chain Mn Mw Solid Content
Sample Chain (nEO) Index
(a:b) (a:b) (g/mol)
Chain (nEO ) sityDensity (g/mol) (g/mol) (g/mol) (Mw/Mn) (wt%)
(wt%)
(Mw /Mn )
PCE-1
PCE-1 54 54 3.2:1 3.2:1 18,60018,600 34,800 34,800 1.87 1.87 50.0
50.0

Materials 2021, 14, x FOR PEER REVIEW Deionized

Deionized (DI) water
waterwas
wasobtained
obtainedfrom
from a laboratory
a laboratory scale
scale DI-water
DI-water 5instrument
instrument
of 14 pro-
produced
duced by Shanghai Miaokang CD3400, Shanghai, China. The conductivity of theof
by Shanghai Miaokang CD3400, Shanghai, China. The conductivity DIthe DI
water
water wasμs/cm.
was 0.30 0.30 µs/cm.

To2.2.
2.2. Polycarboxylate
Polycarboxylate
ascertain (PCE)
(PCE) Adsorption
the interactions betweenvia
Adsorption theTotal
via Total Organic
and Carbon
Organic
PCE-1 (TOC)
Carbonpowder,
stone (TOC) the absorbed
To ascertain the interactions between the PCE-1 and
amounts of PCE were determined via the TOC method using a TG-WS instrumentstone powder, the absorbed
man-
ufactured by Shanghai Lu Xiangyi Centrifuge Instrument, Shanghai, China. The standard manu-
amounts of PCE were determined via the TOC method using a TG-WS instrument
factured
curve for by organic
the total Shanghai Lu Xiangyi
carbon Centrifuge
with different Instrument,ofShanghai,
concentrations China.
PCE is shown in The standard
Figure
4. curve for the total organic carbon with different concentrations of PCE is shown in Figure 4.

400
y = 304.17x + 12.791
350
2
R = 0.9922
300

250
TOC (mg/L)

200

150

100

50

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2

Concentration of PCE-1 (g/L)

Figure 4. The adsorption standard curve of PCE-1.
Figure 4. The adsorption standard curve of PCE-1.
In a typical experiment, 5 g of stone powder was added to four separated Erlenmeyer
Inflasks
a typical
thatexperiment,
contained a5 stir
g ofbar
stone
andpowder
50 mLwas added
of PCE to fourwith
solution separated Erlenmeyer
different concentrations
flasks that contained
ranging from 0.1a stir bar0.5
g/L, and 50 1.0
g/L, mLg/L,
of PCE
andsolution
2.5 g/L.with different
Then, concentrations
the Erlenmeyer flasks were
ranging from 0.1
sealed, g/L, 0.5
placed in ag/L, 1.0 bath,
water g/L, and
and2.5 g/L. Then,
stirred. Next,the
15 Erlenmeyer flasks were
mL of the mixture sealed, and
was collected
placedcentrifuged
in a water bath,
for 10and
minstirred. Next,
at 10,000 rpm.15 Moreover,
mL of the mixture was collected
a blank sample, and PCE
replacing centri-
solution
fuged for 10 min at 10,000 rpm. Moreover, a blank sample, replacing PCE solution with a
DI water, was also prepared in order to subtract the free carbon in the background. After-
wards, the supernatant was extracted and the TOC was measured on a TOC-L CPN In-
strument manufactured by Shimadzu, Kyoto, Japan.
Materials 2021, 14, 2736 5 of 12

with a DI water, was also prepared in order to subtract the free carbon in the background.
Afterwards, the supernatant was extracted and the TOC was measured on a TOC-L CPN
Instrument manufactured by Shimadzu, Kyoto, Japan.
The PCE adsorption was calculated according to:

(C0 − Ce )V
qe = (1)
m
where qe (unit = mg/g) is the amount of adsorbed material; C0 and Ce (unit = mg/L) are the
concentration of PCE solution before and after the stone powder was added, respectively;
V (unit = L) is the volume of sample collected for the centrifuge; and m (unit = g) is the
mass of stone powder.
To study the adsorption kinetics, the TOC values were measured at different time
points (5 min, 15 min, 30 min, 60 min, and 120 min) while for the isothermal adsorption
measurements, the TOC values were measured at different temperatures (293 K, 303 K,
313 K).

2.3. Characterization
Supernatant from Section 2.2 with a concentration of 20 g/L was extracted and filtered
by suction filtration with a filter paper. During this step, 500 mL of DI water was washed
through the filter paper to remove the polymer on the surface of stone powder. Then, the
filter paper was dried at 80 ◦ C in an oven for 24 h. The collected compound, named the
PCE/stone compound, was stored in desiccators for further characterizations, such as pore
size distribution, FTIR, and TGA.

2.3.1. Pore Size Distribution

The pore size distribution and the Brunauer-Emmett-Teller (BET) surface area of the
stone powder and compound were measured using a High-Speed Automated Surface Area
and Pore Size Analyzer, ASAP2010N, manufactured by Micromeritics, Norcross, GA, USA.

2.3.2. Fourier-Transform Infrared Spectroscopy (FTIR)

In order to determine the C–H group, the PCE, LBSP, and PCE/stone compound
were analyzed by FTIR (6700, Nicolet, Madison, WI, USA) over a wavelength range 400 to
4000 cm−1 with a resolution of 2 cm−1 and averaged over 32 scans.

2.3.3. Thermogravimetric Analysis (TGA)

To determine the derivative thermogravimetry (DTG) and the weight loss of the
PCE/stone compound, approximately 8~12 mg of compound was placed under an N2
environment in a TGA device “STD Q600” from TA instrument. Test conditions: nitro-
gen atmosphere (100 mL/min), temperature range was 25–800 ◦ C, and heating rate was
20 ◦ C/min

2.4. Zeta Potential Measurements

The zeta potential of the suspension was measured on a Zetasizer “ZEN3600” manu-
factured by Malvern, Malvern, UK. The LBSP suspensions were prepared by dispersing
5.0 g of LBSP in 50 mL of PCE solutions from 0.1 g/L, 0.5 g/L, 1.0 g/L, and 2.5 g/L with
the original pH value of 6.7. The suspensions were ultrasonic dispersed after 30 min, then
the zeta potential measurements were conducted. The pH value of the dispersion was
adjusted carefully between 2.1 and 11.0 by adding 0.1 mol/L HCl or NaOH solutions to
test zeta potential with PCE concentration of 2.0 g/L.

2.5. Hydrodynamic Diameter Distribution

The hydrodynamic diameter distribution of PCE-1 in solution with concentration of
2.0 g/L was measured using a Zeta 90 Plus instrument [22]. A simulated cement pore
solution (SCPS) was prepared using 1.72 g/L CaSO4 ·2H2 O, 6.96 g/L Na2 SO4 , 4.76 g/L
Materials 2021, 14, 2736 6 of 12

K2 SO4 and 7.12 g/L KOH, the pH value of SCPS was 12.4 [23]. The measurements of PCE-1
were made in two types of solvent: DI water and SCPS.

3. Results and Discussion

Materials 2021, 14, x FOR PEER REVIEW
3.1.
Adsorption Kinetics of PCE-1 on Stone Powder 7 of 14

The adsorption kinetics of four different PCE-1 concentrations (0.1 g/L, 0.5 g/L,
1.0 g/L, and 2.5 g/L) onto LBSP at a temperature of 303 K are shown in Figure 5.

0.20

0.1 g/L
0.5 g/L
0.15
1.0 g/L
Adsorption amount (mg/g)

2.5 g/L

0.10

0.05

0.00

0 20 40 60 80 100 120
Time (min)
Figure
Figure5.5.Adsorption
Adsorptionbehavior of of
behavior four different
four PCE-1
different concentrations
PCE-1 in the
concentrations in stone powder
the stone over over
powder 120
min.
120 min.

Thehighest
The highestadsorbed
adsorbedamounts
amountsofofPCE PCEwerewereobserved
observedatat55min,
min,then
thenthey
theygradually
gradually
decreased and equilibrated after 30 min. This interesting adsorption behavior can can
decreased and equilibrated after 30 min. This interesting adsorption behavior be
be at-
attributed to the chemical composition of LBSP and described by
tributed to the chemical composition of LBSP and described by diffusion theory. First,diffusion theory. First,
LBSPisisan
LBSP anacidic
acidicrock
rock and
and isis hydrophilic
hydrophilic because
because itit contains
contains 67.2%
67.2% ofof SiO
SiO22,,aarelatively
relatively
high content. Consequently, PCE, which is a strong hydrophile surfactant,
high content. Consequently, PCE, which is a strong hydrophile surfactant, easily wetted easily wetted
theLBSP
the LBSP surface.
surface. Secondly,
Secondly,the thestone
stonepowder
powderhas hasaa porous
porous structure
structure which
which provides
provides
many absorption sites for the PCE polymers. However, once the
many absorption sites for the PCE polymers. However, once the diffusion equilibrium diffusion equilibrium
(equilibrium state)
(equilibrium state) was
was reached,
reached, some
somePCE PCEpolymers
polymerspermeated
permeatedback into
back thethe
into bulk
bulksolution.
solu-
tion. Hence, the adsorbed polymer amount and rate remained stable after the 30mark.
Hence, the adsorbed polymer amount and rate remained stable after the 30 min min
BasedBased
mark. on thisonfinding, the reaction
this finding, time for
the reaction all for
time subsequent experiments
all subsequent was fixed
experiments wastofixed
30 min.
to
A min.
30 similar measurement
A similar was taken
measurement by Hui
was taken by Feng et al.etThere,
Hui Feng with
al. There, thethe
with PCEPCEsolution
solutionof
2.5 g/L, the adsorbed PCE amount was 4.24 mg/g and 0.79 mg/g for Ledong stone powder
of 2.5 g/L, the adsorbed PCE amount was 4.24 mg/g and 0.79 mg/g for Ledong stone pow-
(LDSP) and Ledong stone powder (LDSP), respectively [21]. Similarly, Feng Lei et al.
der (LDSP) and Ledong stone powder (LDSP), respectively [21]. Similarly, Feng Lei et al.
tested the adsorption of polycarboxylate superplasticizer on the surface of tuff powder
tested the adsorption of polycarboxylate superplasticizer on the surface of tuff powder
with quartz, albite and potash feldspar as main components by the TOC method, and the
with quartz, albite and potash feldspar as main components by the TOC method, and the
adsorption capacity was 4.7 to 5.0 mg [20]. Here, the adsorbed amount of PCE ono stone
adsorption capacity was 4.7 to 5.0 mg [20]. Here, the adsorbed amount of PCE ono stone
powder (LBSP) with a PCE concentration of 2.5 g/L at 5 min mark was nearly 0.2 mg/g.
powder (LBSP) with a PCE concentration of 2.5 g/L at 5 min mark was nearly 0.2 mg/g.
Based on these results, it can be concluded that the adsorbed amount of PCE can be varied
Based on these results, it can be concluded that the adsorbed amount of PCE can be varied
depending on the types of stone powder.
depending on the types of stone powder.
Nevertheless, this adsorption trend from this study can be explained by diffusion
Nevertheless, this adsorption trend from this study can be explained by diffusion
theory. The steeper the concentration gradient, the faster rate of diffusion, and thus the
theory. The steeper the concentration gradient, the faster rate of diffusion, and thus the
higher the adsorption amount and the saturation capacity for PCE-1 concentrations of
higher
0.1 g/Lthe
and adsorption
2.5 g/L are amount and the
0.051 mg/g saturation
to 0.114 mg/g,capacity for PCE-1
respectively. concentrations
Similar of 0.1
adsorption kinetics
g/L and 2.5 g/L are 0.051 mg/g to 0.114 mg/g, respectively. Similar adsorption
were also seen in studies by Wang et al., Bulut et al., and Karagozoglu et al. where they kinetics
were alsoabsorption
studied seen in studies by (sepiolite
on clays Wang et al., Bulut et al.,
or bentonite) and Karagozoglu
instead of stone powderet al.[24–26].
where they
studied absorption on clays (sepiolite or bentonite) instead of stone powder [24–26].

3.2. Isothermal Adsorption of PCE onto Large Bibulous Stone Powder (LBSP)
In addition to the concentration gradient, temperature also plays a significant role in
Materials 2021, 14, 2736 7 of 12

3.2. Isothermal Adsorption of PCE onto Large Bibulous Stone Powder (LBSP)
Materials 2021, 14, x FOR PEER REVIEW In addition to the concentration gradient, temperature also plays a significant8 role of 14
in the adsorption kinetics and thermodynamics. As presented in Figure 6, the amount of
sorbed PCE increased as the temperature rose, which indicated that lower temperatures
did not promote polymer adsorption. Furthermore, the movement of molecules per unit
time is enhanced at higher temperature, according to the so-called collision model. Thus,
polymers
polymers were
weresorbed
sorbedmore
moreeffectively
effectivelyonto
ontothe free
the adsorption
free sites
adsorption of the
sites porous
of the structure
porous struc-
at higher
ture temperatures.
at higher temperatures.

0.16

0.14

0.12

0.10
qe (mg/g)

0.08

0.06

293 K
0.04 303 K
313 K
0.02
0.0 0.5 1.0 1.5 2.0 2.5
ce (g/L)

Figure 6. Adsorption isotherms

isotherms ofof PCE-1
PCE-1on
onLBSP
LBSPatatthree
threedifferent
differenttemperatures.
temperatures.(293
(293K,K,303
303K,K,and
and K)
313 313asK) as indicated
indicated in theinlegend.
the legend.

The following
followingequations
equationspresent
presentthe
thecalculation of of
calculation thethe
change of Gibbs
change freefree
of Gibbs energy ∆G
energy
(kJ/mol), enthalpy
ΔG (kJ/mol), ∆HΔH
enthalpy (kJ/mol), and
(kJ/mol), entropy
and entropy∆SΔS
(kJ/(K ·mol)):
(kJ/(K·mol)):

Cads
KC = 𝐶 (2)
𝐾 =Csol (2)
𝐶
∆G = − RT ln Kc (3)
∆𝐺 = −𝑅𝑇 ln 𝐾 (3)
∆S ∆H
ln Kc = ∆𝑆 − ∆𝐻 (4)
R RT
ln 𝐾 = − (4)
where KC is the thermodynamic equilibrium constant, 𝑅 𝑅𝑇 where Cads is adsorbed on LBSP
where KCCis
(mol/L), is the
sol the concentration in
thermodynamic equilibrium
equilibrium solutionwhere
constant, (mol/L).CadsThe ∆H and ∆S
is adsorbed oncan
LBSPbe
determined by plotting lnK c
(mol/L), Csol is the concentrationagainst 1/T from the slope and intercept, respectively.
in equilibrium solution (mol/L). The ΔH and ΔS can be All of
the thermodynamic parameters are summarized in Table 3. T is the absolute temperature
determined by plotting lnKc against 1/T from the slope and intercept, respectively. All of
(K)
the and R is the gas constant
thermodynamic (8.314
parameters areJ/(K ·mol)). in Table 3. T is the absolute temperature
summarized
(K) and R is the gas constant (8.314 J/(K·mol)).
Table 3. Thermodynamic parameters of polycarboxylate water reducer onto LBSP.
Table 3. Thermodynamic parameters of polycarboxylate water reducer onto LBSP.
Temperature/K Kc (×10–3 ) ∆G/(kJ/mol) ∆H/(J/mol) ∆S/(J/(K·mol))
Temperature/K
293 Kc0.351
(×10–3) ΔG/(kJ/mol)
13.77 ΔH/(J/mol) ΔS/(J/(K·mol))
303 0.458 13.57 19.47 19.52
293
313 0.351
0.585 13.77
13.38

303 0.458 13.57 19.47 19.52

313 0.585 13.38

When temperature increases from 293 K to 313 K, ΔG slightly decreases from 13.77
kJ/mol to 13.38 kJ/mol, demonstrating that the energy barrier decreases with the increase
Materials 2021, 14, 2736 8 of 12

Materials 2021, 14, x FOR PEER REVIEW 9 of 14

When temperature increases from 293 K to 313 K, ∆G slightly decreases from 13.77 kJ/mol
to 13.38 kJ/mol, demonstrating that the energy barrier decreases with the increase of
temperature and the adsorption reaction is more likely to occur. Chemical adsorption and
of temperature and the adsorption reaction is more likely to occur. Chemical adsorption
physical adsorption can be distinguished by enthalpy change ∆H value, which is in the
and physical adsorption can be distinguished by enthalpy change ΔH value, which is in
range of −20~400 kJ/mol for physical adsorption, and this enthalpy change is 19.47 kJ/mol
the range of −20~400 kJ/mol for physical adsorption, and this enthalpy change is 19.47 kJ
for physical adsorption. The adsorption enthalpy change ∆H is positive, which means
/mol for physical adsorption. The adsorption enthalpy change ∆H is positive, which
that the adsorption process is an endothermic process [27]. The entropy change ∆S is
means that the adsorption process is an endothermic process [27]. The entropy change ΔS
19.52 J/(K·mol), the values of enthalpy change and entropy change are greater than 0,
is 19.52 J/(K·mol), the values of enthalpy change and entropy change are greater than 0,
indicating that the adsorption reaction can be spontaneous at high temperature.
indicating that the adsorption reaction can be spontaneous at high temperature.
3.3. The Influence of pH and PCE Concentration on the Zeta Potential of LBSP
3.3. The Influence of pH and PCE Concentration on the Zeta Potential of LBSP
Zeta potential is a powerful tool for investigating the adsorption behavior in a biphasic
Zeta potential is a powerful tool for investigating the adsorption behavior in a bipha-
system. For example, Plank et al. studied the PCE adsorption coverage of cement particles
sic system. For example, Plank et al. studied the PCE adsorption coverage of cement par-
via zeta potential and concluded changes in zeta potential were an indication of high
ticles via zeta potential and concluded changes in zeta potential were an indication of high
PCE adsorption [28]. Moreover, Zingg et al. suggested that the switch from positive to
PCE adsorption [28]. Moreover, Zingg et al. suggested that the switch from positive to
negative charge in cement and gypsum measured with zeta potential was evidence of PCE
negative charge in cement and gypsum measured with zeta potential was evidence of PCE
adsorption [29].
adsorption [29].
To assess the effects of these two essential factors on the interactions between PCE
To assess the effects of these two essential factors on the interactions between PCE
and LBSP, the change in the LBSP surface charge was measured at different pH and PCE
and LBSP, the change in the LBSP surface charge was measured at different pH and PCE
concentrations. As shown in Figure 7a, the zeta potential increased from negative to
concentrations. As shown in Figure 7a, the zeta potential increased from negative to pos-
positive and then decreased to an even lower surface charge as the pH rose from 2 to 11.
itive and then decreased to an even lower surface charge as the pH rose from 2 to 11.
Evidently, either strong acidic (pH = 2) or strong basic conditions (pH > 10) improved the
Evidently, either strong acidic (pH = 2) or strong basic conditions (pH > 10) improved the
stability of the suspension, particularly in the case of high pH values (pH = 11).
stability of the suspension, particularly in the case of high pH values (pH = 11).
-12 -12
(a) (b)
-14
-14
-16
-16
-18
Zeta Potential (mV)
Zeta potentail (mV)

-18 -20

-20 -22

-24
-22
-26
-24
-28
-26
-30
-28 -32

2 4 6 8 10 12 0.0 0.5 1.0 1.5 2.0 2.5

pH value PCE Concentration (g/L)

Figure 7. Effect of pH and PCE concentration on the measured zeta potentials of LBSP. (a) pH values.
Figure 7. Effect of pH and PCE concentration on the measured zeta potentials of LBSP. (a) pH val-
(b) PCE
ues. (b) concentration.
PCE concentration.

In contrast to Figure 7b, the surface charge declined gradually with increasing PCE
In contrast to Figure 7b, the surface charge declined gradually with increasing PCE
concentration. The increment in the zeta potential looks similar to the changes in isothermal
concentration. The increment in the zeta potential looks similar to the changes in isother-
adsorption rate in Section 3.2. Moreover, the adsorption saturation point was reached at a
mal adsorption rate in Section 3.2. Moreover, the adsorption saturation point was reached
PCE concentration of 2.0–2.5 g/L where the change in zeta potential plateaued. It is known
at a PCE concentration of 2.0–2.5 g/L where the change in zeta potential plateaued. It is
that PCE binding onto cement is due to chelation between the anchoring groups in the
known that PCE binding onto cement is due to chelation between the anchoring groups
polymer and the free Ca2+ in solution in the cement pores [30]. As a result, only a finite
in the polymer and the free Ca2+ in solution in the cement pores [30]. As a result, only a
amount of PCE was absorbed onto the cement since there were a finite number of Ca2+
finite amount of PCE was absorbed onto the cement since there were a finite number of2+
cations in solution. Similarly, there are restricted binding sites since the limited free Ca
Ca2+ cations in solution. Similarly, there are restricted binding sites since the limited free
ions2+ in the pores of the stone powder solution and, as such, the zeta potential plateaus
Ca ions in the pores of the stone powder solution and, as such, the zeta potential plateaus
when all of the binding sites are occupied.
when all of the binding sites are occupied.
3.4. Characterization of the PCE/LBSP Compound
3.4. Characterization of the PCE/LBSP Compound
As shown in Figure 8, the FTIR spectrum of the PCE/LBSP compound was more
similarAsto
shown in Figure
the pure LBSP 8,asthe FTIR spectrum
compared to pureofPCE-1.
the PCE/LBSP compound
However, was more
the measured sim-
spectrum
ilar to the pure LBSP as compared to pure PCE-1. However,
− 1 the measured spectrum
for the compound had an additional peak at −2867 cm that belonged to the C–H bonds for
the compound had an additional peak at −2867 cm−1 that belonged to the C–H bonds in
Materials 2021, 14, x FOR PEER REVIEW 10 of 14
Materials 2021, 14, 2736 9 of 12

Materials 2021, 14, x FOR PEER REVIEW 10 of 14

the PCE-1
in the methylenes
PCE-1 andand
methylenes supported the assertion
supported that PCE
the assertion was adsorbed
that PCE on to the
was adsorbed on toLBSP
the
LBSP surface.
surface.
the PCE-1 methylenes and supported the assertion that PCE was adsorbed on to the LBSP
surface.
100 LBSP

100 LBSP

80
Compound
80
Transmittance (a.u)

Compound
60
Transmittance (a.u)

60
PCE-1
40 PCE-1
40

20
20

0
0

4000 3500 3000 2500 2000 1500 1000 500 0

4000 3500 3000 2500 2000 1500
-1
1000 500 0
Wavelength (cm )-1
Wavelength (cm )
Figure
Figure 8.
8. Fourier-transform
Fourier-transform infrared
infrared (FTIR)
(FTIR) spectra
spectra of
of PCE-1,
PCE-1, LBSP, and the
LBSP, and the PCE/LBSP
PCE/LBSP compound.
compound.
Figure 8. Fourier-transform infrared (FTIR) spectra of PCE-1, LBSP, and the PCE/LBSP compound.
If the
If the PCE
PCE polymers
polymers were were present
present on on the
the surface
surface or or in
in the
the pores
pores ofof the
the LBSP,
LBSP, then
analysis Ifofthe
the PCE
TGA polymers
curves were show
should present on the surface
additional weight or in in
loss the pores
the of the LBSP,
compounds duedue tothen
the
analysis the TGA curves should show additional weight loss in the compounds to
analysis of the TGA curves should show additional weight loss in the compounds due to
decomposition of the polymers. This method was also used in the
the decomposition of the polymers. This method was also used in the study of Ait-Akbour study of Ait-Akbour et al.
the decomposition of the polymers. This method was also used in the study of Ait-Akbour
and
et al.Tan
andetTan al.,et
toal.,
study intercalation
to study of PCE
intercalation ofonPCEmontmorillonite
on montmorillonite [31,32]. As expected
[31,32]. in the
As expected
et al. and Tan et al., to study intercalation of PCE on montmorillonite [31,32]. ◦ C withAs expected
present
in results,results,
the present there wasthereanwas
additional weightweight
an additional loss plateau at 553~580
loss plateau at 553~580 °Ca weight
with a
in the present results, there was an additional weight loss plateau at 553~580 °C with a
◦ C due
loss ratio
weight loss ofratio
0.132% of in addition
0.132% in to the first
addition to weight
the first loss plateau
weight loss at 175~258
plateau at 175~258 °Ctoduethe
weight loss ratio of 0.132% in addition to the first weight loss plateau at 175~258 ◦ C °C due
water
to the associated
water with
associated the
with LBSP
thetheand
LBSP a second
and weight
a second loss plateau at 260~290 due to
to the water associated with LBSP and a secondweight
weightloss lossplateau
plateauat at260~290
260~290 °C °C duedue
the decomposition
to the decomposition of the
of ofLBSP
thethe
LBSPcrystal lattice
crystal as seen in Figure 9a,b. The extra weight loss
to the decomposition LBSP crystallattice
latticeasasseen
seenininFigure
Figure9a,b.
9a,b. The
The extra
extra weight
weight
plateau
loss further supported the assertion that the PCE-1 had adsorbed into the LBSP pores
loss plateau further supported the assertion that the PCE-1 had adsorbed into the
plateau further supported the assertion that the PCE-1 had adsorbed into the LBSP
LBSP
as anyaspolymer
pores only bound to thetosurface should havehave been washed away during the
pores any polymer
as any polymer only
onlybound
bound to thethesurface
surfaceshould
should havebeen beenwashed
washed away away during
during
PCE/LBSP
the PCE/LBSP compound
compound preparation.
preparation.
the PCE/LBSP compound preparation.

0.0 0.0
100 100 0.0
0.0
100100

-0.2-0.2
99 99 TG TG
99 99 -0.2
DTGDTG TG
TG
DTG (%/min)
DTG (%/min)

-0.4-0.4 DTG
DTG
(%/min)

98
DTG (%/min)

98
TG (%)
TG (%)

98 98
TG (%)

-0.4
TG (%)

97 -0.6-0.6
DTG

97
97 97
-0.6
-0.6

96 96 -0.8-0.8
96 96
-0.8
a a bb
-0.8
95 -1.0 95
95 -1.0 95
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700 800 900
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700 800 900
Temperature (Celsius) Temperature (Celsius)
Temperature (Celsius) Temperature (Celsius)

Figure 9.Thermogravimetry/derivative
Thermogravimetry/derivative thermogravimetry
thermogravimetry(TG/DTG) curves
(TG/DTG) of the
curves LBSP and and
Figure
Figure 9.9.Thermogravimetry/derivative thermogravimetry (TG/DTG) curves of theofLBSP
the LBSP
and
compound
compound(a) (a) LBSP;
(a)LBSP;
LBSP;(b) (b) PCE/LBSP
(b)PCE/LBSP compound.
PCE/LBSPcompound.
compound.
compound

In order
In order
order to furthershow
tofurther
further showthat
that PCE-1
PCE-1 had
had absorbed
absorbed into thethe
LBSP porous structure, the
In to show that PCE-1 had absorbed intointo
the LBSPLBSP porous
porous structure,
structure, the
pore
the pore size distribution of the LBSP and PCE/ LBSP compound was analyzed. As seen in
pore sizesize distribution
distribution of the
of the LBSP
LBSP andand PCE/
PCE/ LBSPLBSP compound
compound waswas analyzed.
analyzed. As As
seenseen
in
in Table 4 and Figure 10, the surface area of the stone powder decreased from 21.7 nm to
Materials 2021, 14, x FOR PEER REVIEW 11 of 14
Materials 2021, 14, x FOR PEER REVIEW 11 of 14

Materials 2021, 14, 2736 10 of 12

Table
Table44and
andFigure
Figure10,
10,the
thesurface
surfacearea
areaofofthe
thestone
stonepowder
powderdecreased
decreasedfrom
from21.7
21.7nm
nmtoto6.6
6.6
nm
nm after it was mixed with the PCE-1 solution. This pore size reduction is direct proof of
after it was mixed with the PCE-1 solution. This pore size reduction is direct proof of
the
the PCE-1
PCE-1 adsorption.
adsorption.
6.6 nm after it was mixed with the PCE-1 solution. This pore size reduction is direct proof
of theinPCE-1
Table 4. Pore size distribution adsorption.
the LBSP and PCE/ LBSP compound via the Barrett–Joyner–Halenda (BJH) method.
Table 4. Pore size distribution in the LBSP and PCE/ LBSP compound via the Barrett–Joyner–Halenda (BJH) method.
BET
Table 4. Pore sizeSurface
BET Average
distribution
Surface Pore
in the LBSP
Average Diameter
Poreand BJH
PCE/ LBSP
Diameter Volume
compound
BJH of
Volumevia Pores
ofthe in Adsorption
in Adsorption Surface
Barrett–Joyner–Halenda
Pores Area
Areaof
(BJH) method.
Surface of Pores
Pores
Powder
Powder Type
Type Area/m²/g
Area/m²/g /nm
/nm 1.7–30
1.7–30 nm/1*10 −3 cm³/g in 1.7–30 nm/cm 2/g
Volume ofcm³/g
BJHnm/1*10 in 1.7–30 nm/cm
Surface /g
−3 2
BET Surface Average Pore Pores in Adsorption Area of
Powder Type
Stone Area/m2 /g Diameter /nm nm/1*10−3 cm3 /g
1.7–308.474 1.7–30 nm/cm2 /g
Pores in0.749
Stone powder
powder 4.58
4.58 21.7
21.7 8.474 0.749
Stone powder 4.58 21.7 8.474 0.749
Compound
Compound
Compound 1.55
1.551.55 6.6
6.6 6.6 0.792
0.792
0.792 0.262
0.262
0.262

0.0006
0.0006

0.0005
0.0005
3 3/g·nm)
/g·nm)

0.0004
0.0004
(cm

LBSP
Volume (cm

LBSP
0.0003
0.0003
PoreVolume

0.0002
0.0002
dV/dWPore

Compound
0.0001 Compound
0.0001
dV/dW

0.0000
0.0000

1 10 100
1 10 100
Pore width (nm)
Pore width (nm)
Figure
Figure10.
10.The
Thederivative
derivativeininpore
porevolume,
volume,dv/dw,
dv/dw,in the LBSP and PCE/LBSP
PCE/LBSPcompound.
compound.
Figure 10. The derivative in pore volume, dv/dw, in the LBSP and PCE/LBSP compound.

As
As shown
As shown in
shown in Figure
in Figure 11,
Figure 11, the
11,the hydraulic
thehydraulic diameter
hydraulicdiameter distribution
diameter distribution of
distribution of PCE-1
of PCE-1
PCE-1 inin an
inan aqueous
anaqueous
aqueous
solution
solution (DI
solution(DI water)
(DIwater) varied
water)varied from
variedfrom 4.1
from4.1 nm
4.1nm to
nmtoto 8.7
8.78.7 nm,
nm,
nm, with
with the
thethe
with maximum
maximum
maximum diameter
diameter
diameter of
of 5.6
of 5.6 nm.nm.
5.6 In
nm.
In contrast,
contrast,
In contrast, in SCPS,
in SCPS,
in SCPS, the
the the hydrodynamic
hydrodynamic
hydrodynamic diameter
diameter
diameter distribution
distribution ranged
ranged
distribution from
fromfrom
ranged 4.1
4.1 nm
4.1tonm
nm to
11.7to 11.7
nm,
11.7
nm,
nm,where
where where the
themaximum
the maximum
maximum diameter
diameter waswas
diameter 7.57.5
was nm.
7.5 nm.
nm. This
This result
result
This shows
shows
result that
showsthat the
thatthe PCE-1
thePCE-1 polymer
PCE-1polymer
polymer
could enter the voids in the LBSP particles since the polymer had a smaller
could enter the voids in the LBSP particles since the polymer had a smaller hydrodynamic hydrodynamic
diameter
diameter than
than the
the LBSP
LBSPpore size.
poresize.
size.AsAsaaaconsequence,
consequence,
consequence,the the BJH
theBJH pore
BJHpore volume
porevolume
volumeof of PCE/LBSP
ofPCE/LBSP
PCE/LBSP
compound was reduced.
compound was reduced.

40 PCE-1
40 PCE-1
PCE-1 SCPS
PCE-1 SCPS

30
30
(percent)
Number(percent)

20
20
Number

10
10

0
0

1 10 100
1 10 100
Size (nm)
Size (nm)
Figure
Figure11.
11.Hydrodynamic
11. Hydrodynamicdiameter
Hydrodynamic diameterof
diameter ofofPCE-1
PCE-1
PCE-1 in water
inin and
water
water in
and
and inthe
in simulated
thethe stone
simulated
simulated powder
stone
stone solution
powder
powder solu-
solution
(SCPS).
tion (SCPS).
(SCPS).
Materials 2021, 14, 2736 11 of 12

4. Conclusions
The interactions between large bibulous stone powder and ether-based PCE were
studied. Significant amounts of PCE were sorbed both onto the surface and into the pores
of the LBSP in the first 5 min, then the adsorption rate gradually decreased. Finally, when
PCE polymers fully covered the surface and pores, an adsorption equilibrium was reached
after 30 min. The adsorption process of PCE onto LBSP was an endothermic process,
thus the equilibrium adsorption capacity increased with the increase of temperature. The
hypothesized adsorption mechanism was first studied with zeta potential measurements
where the zeta charge became more negative after an addition of the PCE solution. Also, the
FTIR spectrum for the PCE/LBSP compound displayed the C–H functional groups from
the methylenes in the ether-based PCE polymer. Furthermore, the PCE/LBSP compound
showed a reduction of both the BET surface area and pore size due to the presence of PCE
in the LBSP pores, and the hydrodynamic diameter of PCE-1 was smaller than the pore size
of LBSP. Moreover, TGA experiments also showed evidence of an additional weight loss
plateau at 553~580 ◦ C in the compound due to the degradation of the absorbed polymers.
The results of this study provide an important theoretical basis for the interaction
between PCE and porous aggregate, based on which, different molecular structure PCE will
be designed to improve the application performance in concrete with porous aggregate.

Author Contributions: Conceptualization, W.W.; Data curation, Z.D.; project administration, G.L.,
B.Z. and L.F.; resources, L.F. and B.Z.; supervision, G.L.; investigation, W.W.; writing—original draft,
Z.D. All authors have read and agreed to the published version of the manuscript.
Funding: The funding support was from the Science and Technology Commission of Shanghai
Municipality (1804QB1403200, 19DZ1205100).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable to this article.
Acknowledgments: The financial support (1804QB1403200, 19DZ1205100) from the Science and
Technology Commission of Shanghai Municipality is gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

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