Cement and Concrete Composites 133 (2022) 104710

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Cement and Concrete Composites

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

Molecular design and experiment of ion transport inhibitors towards

concrete sustainability
Jiale Huang a, b, c, Ruixing Chen a, b, c, Yang Zhou a, b, c, Jin Ming a, b, c, Jiaping Liu a, b, c, *
a
School of Materials Science and Engineering, Southeast University, Nanjing, 211189, China
b
Jiangsu Key Laboratory for Construction Materials, Southeast University, Nanjing, 211189, China
c
State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Research Institute of Building Science Co.,Ltd, Nanjing, 211103, China

A R T I C L E I N F O A B S T R A C T

Keywords: Regulating the transmission of chloride medium in concrete is the primary research work to improve the
Concrete sustainability durability and sustainability of concrete, effectively saving offshore buildings’ maintenance costs. Inspired by the
Molecular design molecular design of drug delivery, this study designed an erosive solution-responsive ion transport inhibitors
Ion transport inhibitor
(ITI) to restrain the transport of erosive solution in calcium silicate hydrates (C–S–H) gel pores, which is expected
Gel pore
Evaluation system
to reduce the water absorption and chloride diffusion coefficient of concrete efficiently. In this investigation,
molecular dynamics was applied to reveal the mechanism of ITI with different main-chain structures on the
atomic scale, and an evaluation system of such polymers was proposed. When the main chain is the carboxylic
group, the ITI is similar to the hinge of the door. Once the corrosion solution invades the gel channel, the hy­
drophobic group will be perpendicular to the surface of calcium silicate hydrates to prevent the transmission of
the solution. However, when the main chain is alcohol amine, the ITI can gather at the front of the erosion
solution to form a water plugging medium and complex with the eroded ions to inhibit the diffusion of ions. On
this basis, the optimal ITI is evaluated through water adsorption and chloride ion diffusion tests and further
applied in offshore engineering. The results show that they can effectively alleviate chloride ion erosion without
sacrificing mechanical properties.

1. Introduction At present, approximately 40% of the resources in the construction

Concrete is always the most frequently employed artificial material.
Its preparation and application have a profound impact on the envi­
ronment. In 2020, the total output of global cement was 4281 mt, and
approximately 0.59 tons of carbon dioxide was produced per ton of
cement [1]. The carbon dioxide emitted by cement production accounts
for approximately 7% of the carbon dioxide produced by global human
activities, which has dramatically exacerbated the process of global
warming [2]. The extreme climate environment of global warming will
reduce the service life and durability of cement-based materials. For
example, the rise of sea level will lead to the erosion of offshore build­
ings by seawater [3], the severe weathering and erosion of buildings by
land desertification [4,5], and the corrosion of structures by acid rain
[6–8]. However, the cost of maintaining the durability of buildings is
enormous. In 2014, Chinese road and bridge structures and port corro­
sion costs reached 62.37 and 2.63 billion yuan, respectively. If corrosion
inhibition measures were taken, 15%–35% of the corrosion was lost [9].
building industry are applied to repair and maintain existing structures,
and 60% are used for new structures, which means that prolonging the
service life of building materials is very important for resource conser­
vation and sustainability [10]. If the durability of concrete structures is
250 years instead of 50 years, the resource productivity of the concrete
industry can jump five times [11]. Besides, with the rise of coastal
high-speed rail transit in recent years [12–16], traditional cement-based
materials can not meet the requirements of high durability in harsh
environment of marine engineering, which also makes it imminent to
improve the durability of concrete.
As a heterogeneous material, the surface structure of concrete pro­
duces many transmission channels, such as microcracks and holes, due
to the enrichment and evaporation of water [17,18]. The external
corrosion ions gradually enter the concrete gel channel to attain the
surface of the rebar, causing the corrosion of the rebar inside the con­
crete, resulting in the degradation of the concrete structure, which poses
a significant threat to the durability and sustainability of the concrete

* Corresponding author. School of Materials Science and Engineering, Southeast University, Nanjing, 211189, China.
E-mail address: liujiaping@cnjsjk.cn (J. Liu).

https://doi.org/10.1016/j.cemconcomp.2022.104710
Received 6 March 2022; Received in revised form 28 July 2022; Accepted 3 August 2022
Available online 13 August 2022
0958-9465/© 2022 Elsevier Ltd. All rights reserved.
J. Huang et al.
[19–21]. Therefore, inhibiting erosion ion penetration is the key mea­
sure to enhance the durability of concrete. In recent years, many
scholars have regulated the microstructure of cement-based materials by
adding organic substances into concrete, which can effectively upgrade
the durability of concrete. It is mainly divided into three aspects. First,
incorporating organic substances such as PVA and EVA can reduce the
risk of cracking and microcracks by improving the toughness of concrete
structures [22–25]. Second, nanomaterials are applied to fill the gel
channels of cement-based materials, slowing down or blocking the fluid
transmission channels and increasing the permeation resistance of
harmful ions [26–28]. Finally, the steel bar rust inhibitor forms a rust
prevention protective layer on the steel bar surface to prevent chloride
ion adsorption and pit corrosion [29,30]. Although the addition of
polymer in the above research has a good effect on the macro perfor­
mance of concrete, the effect of disparate organic substances on the
performance of concrete has both advantages and disadvantages. For
example, the addition of nanomaterials increases the water demand of
concrete [31], When there are many admixtures, it will cause false
setting of concrete and affect the working performance [32–34]. Actu­
ally, the development of these organics is mainly carried out through a
large number of experiments and exploration by testers, and the
development cost is prohibitive. Furthermore, due to the limitation of
the resolution of modern experimental methods, researchers are less
involved in the study of organic–inorganic interactions on the nanoscale
and the structure-activity relationship of polymers. In recent years,
molecular simulation has played an essential role in revealing the
interaction between organic and cement-based materials. Zhou explored
the interface interaction mechanism between different polymers and
calcium silicate hydrates to improve the toughness of calcium silicate
hydrates gels [35–39]. Yu revealed the improvement effect of dissimilar
silanes on the mechanical properties of rubber concrete [40,41]. This
illustrates that molecular simulation is an effective tool for exploring
organic compound structure-activity relationships.
Inspired by modern drug delivery methods, the new drug delivery
system can significantly promote the efficient utilization of drug com­
ponents, produce an effective response according to external factors
such as ion concentration, light, and temperature, and cause changes in
drug micelle morphology hydrophilicity and hydrophobicity [42–46].
By introducing this design idea into improving the durability of con­
crete, an environment-responsive polymer can be designed to inhibit the
transmission of erosion fluid in nanopores. However, the design and
development of suitable polymers involve the structure-activity rela­
tionship between the polymer molecular structure and action effect [47,
48]. In addition, establishing an evaluation system for this kind of
polymer is also a critical problem to be solved.
Therefore, in this research, three ion transport inhibitor molecules
with different main-chain structures were designed for the ion transport
process based on the research idea of the modern drug delivery system.
Molecular dynamics was employed to reveal the inhibition mechanism
and structure-activity relationship of three ion transport inhibitor mol­
ecules in calcium silicate hydrates channel transport. In addition, an
evaluation system of ion transport inhibitors on the molecular scale was
proposed. Furthermore, the ion transport inhibitor with the best theo­
retical calculation results was selected and organically synthesized.
Finally, it was added to the concrete system and offshore engineering for
durability verification. In summary, a bottom-to-up ion transport in­
hibitor design evaluation application system was established.
2. Materials and simulations
2.1. Molecular dynamics simulation
2.1.1. Calcium silicate hydrates model
In this study, a nanopore transmission model involved with calcium
silicate hydrates was constructed, and the transmission driving force
was provided by negative capillary pressure, which was consistent with
2
Cement and Concrete Composites 133 (2022) 104710
the physical significance of the water adsorption test. The calcium sili­
cate hydrates matrix model was established in accordance with the
realistic model devised by Pellenq [49]. First, all H2O molecules were
deleted from the 11 Å tobermorite structure proposed by Hamid [50],
and then several silica tetrahedrons were randomly deleted to meet the
silicon chain information measured by 29Si NMR(Q0 = 4.7%, Q1 =
73.9%, Q2 = 21.4%) [51,52]. The Ca/Si ratio of the constructed calcium
silicate hydrates model was 1.7 and the mean chain length(MCL) was
2.58, which matched the results of 29Si NMR [52].
Then, the model was saturated with water through large-scale Monte
Carlo simulation where the chemical potential was set to 0 ev and the
temperature was set to 300 K. After that, the Reax force field(ReaxFF)
was employed to optimize the model to simulate the hydrolysis reaction.
Specifically, the relaxation simulation was done in the Iso­
thermal–isobaric ensemble(NPT) for 1000 ps and then done in the Ca­
nonical ensemble(NVT) for 1000 ps. Hereinafter, the calcium silicate
hydrates model with a chemical structural formula of (CaO)1⋅69(SiO2)
(H2O)1.83 was established, which was similar to the structural formula
obtained by Small Angle Neutron Scattering(SANS) [53]. After satis­
fying the requirements of the calcium silicate hydrates model, this
model was cut in the parallel (001) direction according to the diameter
range of the gel hole from 50 Å to 100 Å (Mindess [54]) to build 60 Å
wide and 100 Å long nanochannels.
As displayed in Fig. 1, 0.5 mol/l sodium chloride solution is placed
on the lower side of the model, and three polymers with different main
chain structures (ITI_1, ITI_2, and ITI_3) are selected to be located in the
nanopores to calculate the influence of these polymers on the trans­
mission of nanopores. Among them, ITI_1 is a polymer prepared from a
fatty acid with a hydrophobic carbon chain of 12 and alcohol amine,
ITI_2 is the carboxylate of calcium, which is insoluble in water, and ITI_3
is a carboxylate polymer with a hydrophobic carbon chain of 12. The
three polymers were placed on the surface of matrix before the simu­
lation to meet the previous test results. The total number of atoms in the
model is more than 40000, which is statistically significant on the
atomic scale.
2.1.2. Force field
The hybrid force fields of clay force field (CLAYFF) and consistent
valence force field (CVFF) were applied to represent the mutual effect
between calcium silicate hydrates and polymer. For C–S–H and NaCl
solution, CLAYFF has been implemented administered in the research of
clay and hydrated mineral materials, especially in simulating the
interaction between layered clay and water [55]. In the CLAYFF force
field, the total interaction can be expressed by Coulomb interaction and
Van Der Waals interaction as shown in Equation (1). The O–H bonding
parameters Ebond and H–O–H bonding angle parameters Eangle in water
molecules are expressed by Harmonic potential function as shown in
Equation (2) and Equation (3).
{ [( ) ( )6 ]}
∑ qi qj σ ij 12 σij
E = Evdw + Ecoul = + 4εij + (1)
i,j
4πε0 r ij r ij rij
Where
rij represents the distance of the atom i and j;
qi represents the charge of atom i;
qj represents the charge of atom j;
ε0 is the vacuum dielectric constant and the value is 8.85E-12 (F/m);
σ ij is the energy parameters in Lennard-Jones potential function;
εij is the distance parameters in Lennard-Jones potential function.
Ebond = k1 (r − r0 )2 (2)
Eangle = k2 (θ − θ0 )2 (3)
Where
J. Huang et al.
k1 represents tensile stiffness;
r indicates the length of hydroxyl bond of water molecule;
r0 indicates the length of hydroxyl bond of water molecule in equi­
librium state;
k2 indicates torsional stiffness;
θ represents the bond angle of water molecules;
θ0 represents the bond angle of water molecules in equilibrium state.
For polymers, CVFF can accurately predict the vibration of various
bonds, angles and surfaces in polymers [56]. In this study, the force field
parameters of the mutual effect between the polymer and calcium sili­
cate hydrates are resolved by the mean law [39]. Specifically, the dis­
tance arguments are obtained by arithmetic averaging, and the capacity
parameters are obtained by geometric averaging as shown in Equation
(4) and Equation (5).
σ ii + σ jj
σ ij = (4)
2
√̅̅̅̅̅̅̅̅̅
εij = εii εjj (5)
In recent years, Zhou and Hou have successfully applied the hybrid
force field of CLAYFF and CVFF to related research on C–S–H systems
[36,39,57]. They explored the mutual effect between calcium silicate
hydrates and the erosion solution [58–60], the interaction between
calcium silicate hydrates and the polymers [35,61], the properties of
calcium silicate hydrates/C-A-S-H and the changes in the intrinsic
physical properties of calcium silicate hydrates/C-A-S-H with diverse
boundary conditions [62,63]. In addition, deep learning also had a good
application in force field fitting, which laid the foundation for
large-scale and high-precision ab initio molecular dynamics [64].
3
Cement and Concrete Composites 133 (2022) 104710
Fig. 1. Schematic illustration of the computational
model(the down part represent the erosion solution:
purple balls represent sodium ions, cyan balls repre­
sent chloride ions; the up part represent the nanopore
of calcium silicate hydrates matrix: green balls
represent calcium ions, red and yellow balls denote
silicate tetrahedra, white and gray balls represent
polymers; the molecular structure of ITI_1, ITI_2, ITI_3
polymers are given in the upper part of the model).
(For interpretation of the references to colour in this
figure legend, the reader is referred to the Web
version of this article.)
2.1.3. Simulation details
The establishment of the nanopore transport model and the calcu­
lation of the Monte Carlo adsorption model were carried out on Material
Studio 8.0 of the high-performance computing center of Nanjing Uni­
versity. Molecular dynamics calculations were implemented in LAMMPS
software [65]. These models adopted periodic boundary in all di­
rections. Firstly, the atoms in the system were appointed by the hybrid
force field of CLAYFF and CVFF. After that, rigid constraints on the
upper and lower boundaries of calcium silicate hydrates were admin­
istered to fix the calcium silicate hydrates gel channel. Then, the energy
relaxation of the system was carried out in the NVT ensemble at 298 K.
Before calculation, first, a rigid area of approximately 3 Å was set
between the calcium silicate hydrates nanopores and erosion solution to
prevent the thermodynamic balance destroying. After that, the solution
was given a temperature of 300 K, and the other structures were given an
NVE ensemble. The whole system was relaxed at 1000 ps to ensure that
the solution and nanopores reached thermodynamic equilibrium. Then,
the rigid area was removed, and the model was given a 300 K NVT
ensemble, which allows the erosion solution to complete the fluid
transportation driven by capillary negative pressure. The running time
was 2000 ps, and the step length was 0.1 ps. In the process of fluid
transmission, thermodynamic parameters such as the pressure, energy
and temperature of the model were inspected in real time, and the tra­
jectory, coordinates and velocity of each atom in the model were
recorded for the statistical analysis of molecular dynamics [11,28,66].
2.2. Material synthesis and experimental methods
2.2.1. Preparation of ITI
In this study, the ITI_1 polymer was prepared in the Jiangsu subote
J. Huang et al. Cement and Concrete Composites 133 (2022) 104710

New Material Co., Ltd. Aliphatic organic carboxylic acids with 12 carbon Table 2
atoms, alkyl alcohol amines, ethanol and appropriate catalysts were put Mix design of concrete (kg/m3).
into a three-neck beaker and stirred evenly. After heating to 140 ◦ C for Cement Slag Fly Water Sand Fine Coarse
12 h, water and other functional additives were added and stirred for 12 Ash Aggregate Aggregate
h [28,67]. 270 150 70 196 690 400 620
270 150 70 196 690 400 620
2.2.2. Preparation of concrete
The gel materials used in this study include the common Portland
Cement P.I. 42.5 produced by Jiangnan Onoda Cement Co., Ltd. and fly
ash and slag supplied by China United Cement Co., Ltd. The chemical
components are manifested in Table 1. Natural river sand and crushed
stone are applied as aggregates. The fineness modulus of sand is 2.3 and
the water absorption of stone is 1.4%. The water reducing agent is
Polycarboxylate superplasticizer(PCA) produced by Jiangsu subote New
Material Co., Ltd. The solid content is 18%, and the water reduction rate
is 25%.The mixing amount of PCA and ITI_1 is 0.8‰ and 1.80%
respectively. The concrete mix is described in Table 2.

3. Results and discussion

Based on the statistical analysis of molecular dynamics, Section 3.1

reports the effect of ITI with different main chain structures on the
transport of erosion fluid in nanopores and the conformational changes
in nanopores to reflect the aggregation trend of ITI, which may consti­
tute the physical barrier influence of ITI on the permeation of erosion
fluid in channel. Furthermore, Section 3.2 focuses on the mutual effect
between ITI and the calcium silicate hydrates matrix and reports the
static connection mechanism and the dynamic characteristics between
ITI and calcium silicate hydrates. On the other hand, Section 3.3 reports
the diffusion characteristics of ITI in nanopores and the interaction with
erosion fluid, which may reflect the hydrodynamic characteristics of ITI
in nanopores and the targeted adsorption of the erosion medium. Based
on the above mechanisms, Section 3.4 summarizes the structure-activity
relationship between the main chain structure of ITI and the action
mechanism of inhibiting erosion fluid transport in nanopores and pro­
poses an evaluation system for ion transport inhibitors. Section 3.5 re­
ports the verification of the inhibitory effect of ITI_1 in concrete and
bridge structures through modern experimental means and engineering
applications.

3.1. Inhibitory effect of ITI with different main chain structures on

nanopore transmission
Fig. 2. The process diagram of calcium silicate hydrates nanopore corrosion by
The corrosion depth of ITI with different main chain structures can erosion solution without or with ITI_1, ITI_2, ITI_3 polymers(purple balls
supply a preliminary insight of the inhibition effect of sodium chloride represent sodium ions, cyan balls represent chloride ions, green balls represent
solution at various stages of the transport process. Fig. 2 implies snap­ calcium ions, red and yellow balls denote silicate tetrahedra, white and gray
shots of the fluid transport of calcium silicate hydrates nanopores in the balls represent polymers). (For interpretation of the references to colour in this
existence of different polymers. Obviously, the transmission of erosion figure legend, the reader is referred to the Web version of this article.)
fluid in the nanopores was inhibited at any time with ITI. At 400 ps, the
fluid erosion depth with ITI was slightly less than that without ITI, which was not inhibited. In addition, the nanopore transmission process of the
indicated that the inhibition effect of ITI was not obvious at the initial other three groups obviously lagged behind that of the control group
stage of transmission because the erosion liquid did not contact ITI at the because the erosion fluid contacted and interacted with ITI, which
initial stage of transmission, so the inhibition effect was poor. At 800 ps, hindered the transmission process of erosion fluid. Furthermore, at 1400
the erosion fluid of the reference group continued to be transported in ps, the erosion fluid of the control group almost broke through the
the calcium silicate hydrates nanochannel, and the transmission process calcium silicate hydrates nanochannel, while the erosion depth of the
fluid with ITI was only 1/2–3/4 of that of the control group. ITI inhibited
Table 1 the transmission of erosion solution driven by capillary negative pres­
Chemical composition of the binding material (mass %). sure. At 2000 ps, the erosion solution in the reference group completely
penetrated the calcium silicate hydrates nanopore, while the other three
Oxide Cement Fly Ash Slag
experimental groups containing ITI did not complete the penetration of
CaO 62.05 12.5 40.7
the calcium silicate hydrates nanopore. Specifically, the penetration
SiO2 19.89 53.7 31.3
Al2O3 4.52 30.78 16.4
depths of the ITI_1 group, ITI_2 group and ITI_3 group were 2/3, 3/4 and
Fe2O3 2.87 5.5 0.83 4/5 of the nanopore depth, respectively. Interestingly, the conforma­
K2O 0.53 0.65 0.65 tions of the three polymers in the corrosive liquid implied different
MgO 1.83 0.08 6.53 states. ITI_1 broke away from the bondage of the calcium silicate

4
J. Huang et al.
hydrates at the moment of contact with the erosive liquid and accu­
mulated at the forepart of the erosive liquid. One end of ITI_ 2 was
adsorbed on the calcium silicate hydrates, and the other end was hy­
drophobic in solution. However, ITI_ 3 was partially adsorbed on the
calcium silicate hydrates and partially aggregated at the forepart of the
eroded liquid. The conformational changes of these polymers may have
different effects on the transport of corrosive liquid.
3.2. Interaction between ITI and calcium silicate hydrates
The deviations in the physical barrier effect and chemical binding
effect came from the interaction mechanism between ITI and calcium
silicate hydrates. On the one hand, this section implies the bonding
network between the ITI and calcium silicate hydrates interfaces from
the static connection part; on the other hand, it provides insight into the
temporal and spatial distribution law of the bonding network in the
process of erosion solution transmission.
The radial distribution function (RDF) can provide structural infor­
mation on the atomic spatial correlation in the system, as unveiled in
Equation (6).
/
gAB(r) = 〈NAB (r)〉 ρdV(r) (6)
where.
gAB(r) is the feasibility of the B atom emerging at r around the A atom;
〈NAB (r)〉 is the par of B atom from r to r + dr around A atom;
ρ is the density of B atom;
dV(r) is the volume of the spherical shell from r to r+ dr around the A
atom.
Fig. 3 shows the Ca–O bonding network at the interface field between
the polymer and calcium silicate hydrates. It can be observed from Fig. 3
that the bonding distance between CaITI_2 and OsiO2(C–S–H) is approxi­
mately 2.5–3 Å, and the peak value of ITI_2 is much larger than that of
other polymers. However, the bonding distance between the OITI_2 and
the CaC–S–H interface is approximately 5 Å. Therefore, the interaction be­
tween ITI_2 and calcium silicate hydrates is mainly contributed by the
Ca–O bonding network formed by the CaITI_2 and the OC-S-H interface. The
bonding distance between the OITI_1 and the CaC–S–H interface is approxi­
mately 4.5–5 Å, while that in ITI_3 is 3–4 Å. Previous studies [39] proved
that the attraction effect distance between Ca and O was approximately
2.8 Å. So the attraction order of the mutual effect between the three
Fig. 3. The radial distribution function of calcium atoms and oxygen atoms.
5
Cement and Concrete Composites 133 (2022) 104710
polymers and the calcium silicate hydrates interface is ITI_2>
ITI_3>ITI_1.
Fig. 4 illustrates the RDF between OC-S-H interface and Hpolymer. It can
be detected from Fig. 4 that the bonding distance between HITI_1 and OC-
S-H interface is approximately 1.8–2 Å, while the bonding distance between
ITI_3 and ITI_2 and OC-S-H interface is 2.5–3 Å. This bond cooperation has
previously been proven to be an important contribution to interface
interaction [68]. It can also be observed from the conformational
changes in Fig. 2 that the aggregation trend of the ITI_1 polymer on the
solution surface is stronger than those of ITI_3 and ITI_2, which implies
that the interaction mechanism between ITI_1 and the C–S–H interface
mainly comes from the H bond network. However, when the H bond
network encounters water, the hydroxyl groups and hydrogen ions in
the water will interact with the calcium silicate hydrates interface,
resulting in the destruction of the H bond network and the weakening of
the interaction between ITI_1 and the calcium silicate hydrates interface.
Thus, ITI_1 desorbs at the interface with calcium silicate hydrates and
diffuses in the solution.
Figs. 3 and 4 reveal the static bonding network of the interface
interaction between three organic substances and calcium silicate hy­
drates, and the transmission of erosion solution in nanopores will
destroy the atomic distribution and disrupt the bonding network,
resulting in instability of the interaction between the polymer and cal­
cium silicate hydrates. Therefore, it is necessary to gain insight into the
atomic kinetic trajectory, the chemical state of interface atoms and the
stability of the bonding network. The mean square displacement func­
tion (MSD) and time correlation function (TCF) can further estimate the
stability of atomic diffusion and the connection between polymer and
calcium silicate hydrates, as unveiled in Equation (7) and Equation (8),
respectively.
[ ]
|ri (t) − ri (0)|2
2Dt = (7)
n
where.
ri (t) is the coordinates of atom i at time t;
ri (0) is the initial coordinates of atom i;
n stands for dimension, and when calculating the spatial diffusion
coefficient, n = 3.
Fig. 4. The radial distribution function of hydrogen atoms and oxygen atoms
(green balls represent calcium atoms, blue balls represent amine atoms, gray
balls represent carbon atoms, white balls represent hydrogen atoms, and red
balls represent oxygen atoms). (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)
J. Huang et al.
〈δb(s) δb(0) 〉
TCF = (8)
〈δb(0) δb(0) 〉
where
δb(s) = b(s) − 〈b〉
b(s) is a binary operator. If a connection is established, b(s) equals 1,
and if the connection is destroyed, it becomes 0.
〈b〉 implies the mean of this operator for all of the pairs and simu­
lation times.
Fig. 5 implies the MSD of the CaC–S–H interface with the transport
process of the erosion solution. The MSD evolution curve of the control
group gradually increased with the transport time and began to fluctuate
sharply after 600 ps, indicating that the Ca was initially bound by the
valence bond on the calcium silicate hydrates. When the erosion solution
contacted the calcium silicate hydrates, the hydroxyl and hydrogen ions
in the solution destroyed the valence bond network on the calcium sil­
icate hydrates, weakened the binding of the Ca–O bond network on the
calcium silicate hydrates, and then caused the diffusion of Ca in the
solution. In the presence of ITI, the MSD evolution curve of Ca illustrated
lower volatility than that of the control group. On the one hand, ITI was
adsorbed on the surface of calcium silicate hydrates and interacted with
the calcium silicate hydrates, which hindered the diffusion of Ca; on the
other hand, ITI restricted the transport of the erosion solution, and the
hydroxyl and hydrogen ions in the erosion solution preferentially
reacted with the ITI. The hydrophobicity of ITI reduced the probability
of the valence bond network at the calcium silicate hydrates interface
destroying by the erosion solution. Interestingly, when ITI_1 existed, the
MSD of the Ca was slightly larger than those of ITI_2 and ITI_3, which
echoed the interaction mechanism of ITI_1 displayed in Fig. 4. Compared
with the Ca–O network, the H bond network is more vulnerable to
damage from the corrosive solution, which makes ITI_1 separate from
the calcium silicate hydrates. According to the mechanism proposed in
Refs. [26,27], ITI_1 no longer has the effect of inhibiting the trans­
mission of the erosion solution. In other words, one end of ITI_1 is not
fixed on the interface of calcium silicate hydrates, and the hydrophobic
group at the other end prevents the transmission of the erosion solution.
However, it can be detectable from the erosion depth of ITI_1 in Fig. 2
that ITI_1 has a certain inhibition on the transmission of erosion solu­
tion. It seems that polymer diffusion and interaction with the erosion
solution would influence the transport of the erosion solution, which
Fig. 5. The evolution of mean square displacements calcium atoms of calcium
silicate hydrates along the solution advancing direction during the
erosion process.
6
Cement and Concrete Composites 133 (2022) 104710
will be further discussed in Section 3.3.
Furthermore, the mechanism of the inhibition of Ca diffusion was
understood by analysing the coordination environment of CaC–S–H inter­
face and the stability of bonding network connections in ITI with different
structures. Fig. 6 extrapolates the coordination number of bridging ox­
ygen between CaC–S–H interface and OC-S-H interface and between CaC–S–H
interface and Obridge SiO4. Both coordination numbers were approximately
1.8 without polymers. When the polymer existed, the polymer inter­
acted with the OC-S-H interface, which reduced the coordination number to
approximately 1, resulting in change in the calcium oxygen binding
environment in calcium silicate hydrates. The coordination number of
CaC–S–H interface and Obridge SiO4 increased to 3. At this time, the
connection between calcium and the calcium silicate hydrates matrix
was closer, which weakened the spalling of Ca. The polymer may reduce
the coordination number by affecting the connection between OC-S-H
interface and CaC–S–H interface to make the connection between CaC–S–H
interface and Obridge SiO4 closer.
Fig. 7 provides insight into the bonding stability between OC-S-H
interface and CaC–S–H interface and further reveals the mechanism of poly­
mer regulation of the bonding network. Fig. 7 illustrates that the
connection stability between OC-S-H interface and CaC–S–H interface is high
without ITI. After 600 ps, the corrosive solution broke the valence bond
steady state between the Ca and OH, and the bond stability between the
OH and Ca gradually decrease. However, when the polymer existed, the
bonding stability between OH and Ca was disturbed, which was mainly
caused by the interaction between ITI and the calcium silicate hydrates
interface. As illustrated in Figs. 3 and 4, on the one hand, the ITI formed
a Ca–O bond with the CaC–S–H interface, which formed a competitive effect
with the Ca–O bond on the original calcium silicate hydrates surface, on
the other hand, the ITI formed H bond network with the OHC–S–H interface,
thereby reducing the electron exchange capacity between OH and Ca. It
is worth mentioning that ITI_1 seems to have a greater disturbance on
the stability of Ca–O bonds at the calcium silicate hydrates interface. It
has been explained that the interaction mechanism between ITI_1 and
the calcium silicate hydrates interface is mainly H bond network, which
implies that OH on the calcium silicate hydrates surface is more
vulnerable to the newly formed H bond network, thus weakening the
binding of Ca on the calcium silicate hydrates surface.
Fig. 6. The evolution of the coordination number of calcium on the surface of
calcium silicate hydrates (green balls represent calcium atoms, blue balls
represent amine atoms, gray balls represent carbon atoms, white balls represent
hydrogen atoms, and red balls represent oxygen atoms). (For interpretation of
the references to colour in this figure legend, the reader is referred to the Web
version of this article.)
J. Huang et al.
Fig. 7. Comparisons in time correlation function of the oxygen atoms and
calcium atoms from the surface of calcium silicate hydrates without and with
ITI_1, ITI_2, ITI_3.
3.3. Polymer diffusion and interaction with solution
The diffusion behavior of polymers in nanopores affected not only
the interface characteristics of calcium silicate hydrates but also the
transport dynamics of the eroded solution. Fig. 2 implies that the three
polymers exhibit different transport properties, conformations and
diffusion properties in calcium silicate hydrates nanopores. To quanti­
tatively describe the polymerization characteristics, diffusion charac­
teristics and interaction with the solution of three polymers in calcium
silicate hydrates nanochannels, the density distribution function (PDF)
of different polymers before and after the reaction, the MSD with the
geometric center of the polymer as the central atom, and the RDF of Cl−
in different polymers and corrosive solutions were calculated.
It can be observed from Fig. 8 that each polymer is evenly distributed
around the calcium silicate hydrates nanopores at 0 ps. After the
transmission of the erosion solution, the aggregation characteristics of
various polymers are different at 2000 ps. It can be detected from the
density distribution of ITI_2 that the density distribution peak of the
ITI_2 polymer gradually changes to the platform type with the progress
of the transport process of the erosion solution. This is because one end
of ITI_2 is constrained on the surface of calcium silicate hydrates, and the
flexible chain at the other end can rotate and bend in the solution so that
Fig. 8. Density distribution characteristics of initial position and final position
of polymers in calcium silicate hydrates nanopores.
7
Cement and Concrete Composites 133 (2022) 104710
the morphology of ITI_2 in calcium silicate hydrates nanochannels is
similar to that of door locks. The diffusion of ITI_3 in calcium silicate
hydrates nanochannels implies that a part of ITI_3 continues to be
adsorbed on the calcium silicate hydrates surface, and a part of ITI_3
breaks away from the binding of the calcium silicate hydrates surface,
diffuses inside the erosion solution and accumulates at the end of the
erosion solution. The interaction mechanism between ITI_3 and calcium
silicate hydrates is mainly composed of a calcium oxygen bonding
network and a hydrogen bonding network. Specifically, on the one hand,
Fig. 3 implies that the strength of the calcium oxygen network formed by
the ITI_3 and calcium silicate hydrates surfaces is weaker than that
formed by ITI_2. Therefore, the adsorption capacity of ITI_3 on calcium
silicate hydrates surface is less than that of ITI_2. On the other hand,
Fig. 4 illustrates that ITI_3 and calcium silicate hydrates surfaces can
also form H bond networks, and the vitality of H bond networks is far
worse than calcium oxygen networks, so that ITI_3 is partially adsorbed
on the calcium silicate hydrates surface and partially desorbed from the
calcium silicate hydrates surface. It is worth mentioning that the dis­
tribution of ITI_1 is completely different from that of ITI_2 and ITI_3. At
2000 ps, most of ITI_1 gathers at the forepart of the erosion solution
because the interaction between ITI_1 and calcium silicate hydrates is
mainly contributed by the H bond network. When the erosion solution
contacts the H bond network, the H bond network is damaged by hy­
droxyl groups and hydrogen ions in the solution, making ITI_1 free from
the bondage of the calcium silicate hydrates surface. Then, it diffuses in
the nanopores.
The polymer diffusion characteristics described in Fig. 9 imply that
ITI_1 begins to diffuse in calcium silicate hydrates nanopores after 800
ps, and its diffusion becomes stronger with the progress of trans­
portation. This is because the erosion solution contacts more ITI_1 H
bond networks, which destroys the affinity between ITI_1 and calcium
silicate hydrates more seriously, making more and more ITI_1 desorb
from the surface of calcium silicate hydrates. The average mean square
displacements of ITI_2 and ITI_3 fluctuates less. It is worth noting that
ITI_3 is slightly greater than ITI_2 because the adsorption force of the
interaction between ITI_3 and calcium silicate hydrates is less than that
of ITI_2 and greater than that of ITI_1. Therefore, ITI_3 began to partially
separate from the calcium silicate hydrates surface and diffuse in the
solution after 1200 ps. The MSD of ITI_3 at 2000 ps is 150% of that of
ITI_2. ITI_2 began to diffuse gradually in the solution at 1600 ps because
the hydroxyl and hydrogen ions in the eroded solution continued to
attack the calcium oxygen bonding network formed by ITI_2 and
weakened the stability of the calcium oxygen bonding network by
Fig. 9. The evolution of mean square displacements of polymers during the
erosion process.
J. Huang et al.
complexing the calcium ions of ITI_2 and the oxygen atoms on the sur­
face of calcium silicate hydrates.
Furthermore, the ITI diffused into the solution and interacted with
the ions in the solution. On the one hand, ITI gathers at the forepart of
the erosion solution and fills calcium silicate hydrates nanopores to form
water blocking clusters. On the other hand, the transmission of erosion
solution driven by capillary pore pressure meets the hydrophilic form (i.
e., the solution presents a concave liquid surface). Cl− may penetrate
into capillary pores and then reach the surface of rebar. At this time, the
complexation effect of the polymer on Cl− may be more important than
inhibiting solution transport, Chang also proved that the combination of
chloride ions can delay the permeation process, which gave us great
inspiration [69]. As unveiled in Fig. 10, it can be found that the inter­
action ability between ITI_1 and Cl− is obviously better than that of the
other two polymers by calculating the RDF of three ion transport in­
hibitors and Cl− . The reason is that once ITI_1 is desorbed from the
surface of calcium silicate hydrates, the activity of its surface hydrogen
site is restored. However, the active sites on the other two polymers are
occupied by the calcium silicate hydrates surface, and the electron ex­
change ability with Cl− is weaker than that of ITI_1. For ITI_3, part of
ITI_3 will be transported in calcium silicate hydrates nanochannels after
desorption from the calcium silicate hydrates surface and gradually
gather at the forepart of the solution. It can be detectable from Fig. 10
that ITI_3 interacts with Cl− , which is less than ITI_1 but greater than
ITI_2, which further verifies the ITI_3 inhibition mechanism described in
Section 3.2. ITI_2 maintains a forceful interaction with the calcium sil­
icate hydrates surface due to the strong calcium oxygen bonding
network.
In conclusion, the interaction between ITI_1 and the calcium silicate
hydrates surface is weakest. The transport of the erosion solution de­
stroys the affinity network between ITI_1 and the calcium silicate hy­
drates surface, causing ITI_1 to diffuse in the erosion solution. However,
due to the vacant active sites on the surface of ITI_1, ITI_1 accumulates at
the forepart of the erosion solution to form a water blocking medium, on
the other hand, ITI_1 interacts with Cl− to weaken the diffusion of Cl− in
the solution.
3.4. Structure-activity relationship and evaluation system of ITI
In the field of polycarboxylate superplasticizers, many scholars have
Fig. 10. The radial distribution function of hydrogen atoms from polymers and
chloridion atoms from erosion solution(green balls represent calcium atoms,
purple balls represent chloridion atoms from erosion solution, white balls
represent hydrogen atoms from polymers). (For interpretation of the references
to colour in this figure legend, the reader is referred to the Web version of
this article.)
8
Cement and Concrete Composites 133 (2022) 104710
studied the structure-activity relationship of PCE and found that the
dispersion of cement particles can be controlled by the chemical struc­
ture of PCE [70–72]. Similarly, the molecular structure of PCE can also
be designed reversely according to the rheological requirements. At
present, there is little analysis on the structure-activity relationship of
ITI. Zhou and Hou conducted a preliminary study on silalkyl waterproof
agents, and excellent waterproof agents can be obtained after screening
[27,40,41]. This section focuses on the regulation of erosion solution
transport. First, the molecular structure differences of the three ion
transport inhibition methods used in this study and the mechanism of
inhibiting erosion solution transport are introduced. Second, the trans­
port evaluation index system of the erosion solution in nanopores is
proposed. Finally, the effects of different ITI structures on erosion so­
lution transport are compared, and the excellent ITI in the evaluation
system proposed in this study are selected.
Fig. 11 shows the ion transport inhibitors with three structures. The
three polymers have hydrophilic groups at one end and hydrophobic
groups at the other end. ITI_2 is a calcium carboxylate made by heating
stearic acid and calcium oxide. The CaITI_2 in its main chain can form a
Ca–O bonding network with the OC-S-H interface so that ITI_2 can be stably
adsorbed on the surface of calcium silicate hydrates, and the branched
chain extends into the solution to provide steric hindrance and produce
a hydrophobic effect. ITI_3 is a carboxylic ester polymer. The carboxylic
Fig. 11. Configurations of three polymers with different main chain structure
(The part with orange background on the left represents the branched chain of
the polymers, and the part with cyan background on the right represents the
main chain structure of the polymers, green balls represent calcium atoms, blue
balls represent amine atoms, gray balls represent carbon atoms, white balls
represent hydrogen atoms, and red balls represent oxygen atoms). (For inter­
pretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)
J. Huang et al.
acid group of its main chain can bond with CaC–S–H interface to form an
interactive network, but its interaction strength is not as strong as that of
ITI_2 because the main chain part of ITI_2 can not only bind with
OHC–S–H interface but also bond with Obridge SiO4 with a certain probability.
In addition, the interaction network formed by ITI_3 may also attack the
hydroxyl and hydrogen ions in the solution, which weakens the
adsorption between ITI_3 and calcium silicate hydrates, resulting in the
desorption of part of ITI_3 from the surface of calcium silicate hydrates
and diffusion in the solution. ITI_1 is a fatty acid and alkanolamine salt
polymer, and its main chain is an alkanolamine group. Therefore, the
interaction between the ITI_1 main chain and calcium silicate hydrates is
mainly provided by the H bond network. The disadvantage is that when
the erosion solution contacts ITI_1, hydroxyl and hydrogen ions will
attack the H bond network with a short service life. This makes ITI_1
desorb and gather at the forepart of the erosion solution due to the
hydrophobic characteristics of the hydrophobic chain, thus forming
water blocking clusters. In addition, ITI_1 can interact with Cl− in the
erosion solution, reduce the diffusion path of Cl− in the solution, and
inhibit erosion ions from penetrating calcium silicate hydrates
nanopores.
In this study, the transport of eroded solution in nanopores mainly
focuses on three aspects: ① the erosion depth of the solution mainfested
Fig. 12. The density distribution of water molecules along the penetration through the nanopore of calcium silicate hydrates(a)without polymer, (b)with ITI_1, (c)
with ITI_2, (d)with ITI_3.
9
Cement and Concrete Composites 133 (2022) 104710
in Fig. 12, ② the erosion depth of Cl− demonstrated in Fig. 13, and ③ the
diffusion rate of Cl− manifested in Fig. 14. Aiming at these three indexes,
an evaluation index system of nanopore transmission was proposed. The
evaluation system is mainly composed of the above three indicators.The
relevant calculation results of the experimental group were compared
with the REF group and then multiplied by 10 to obtain the score of the
experimental group taking the calculation results of the REF group at
2000 ps as the reference. The total score is 30 points, and the REF group
is the full score. The lower the score obtained in the experimental group,
the better the effect of the ion transport inhibitor corresponding to the
experimental group. The evaluation results are demonstrated in Table 3.
It can be detected that ITI_1 has the best inhibition effect, approximately
half of the fraction of the control group, because the inhibition mecha­
nism of ITI_1 can not only slow down the transmission of erosion solu­
tion but also hold back the diffusion of Cl− . The scores of ITI_2 and ITI_3
are similar, and ITI_2 is better due to the advantage of inhibiting chlo­
ride ion erosion. Fig. 2 also shows that ITI_2 and ITI_3 have similar ef­
fects on inhibiting the transmission of erosion solution. However, the
effect of ITI_3 is relatively poor. This is because the ITI_3 inhibition
mechanism is the combination of the other two polymer inhibition
mechanisms, and the generation of the other two polymer inhibition
mechanisms requires a certain amount of polymer, such as a large
J. Huang et al. Cement and Concrete Composites 133 (2022) 104710

Fig. 13. The density distribution of chloride ions along the penetration through the nanopore of calcium silicate hydrates(a)without polymer, (b)with ITI_1, (c)with
ITI_2, (d)with ITI_3.

amount of adsorption on the calcium silicate hydrates surface or a large

amount of aggregation at the end of the erosion solution to form water
blocking clusters. According to the evaluation system proposed in this
study, the ITI_1 polymer has the best effect.

3.5. Experimental verification and engineering application

According to the above ion transport inhibitor mechanism and

Fig. 14. The evolution of mean square displacementys of chloride ions along
the erosion solution advancing direction during the erosion process.
evaluation system, ITI_1 can effectivelyinhibit the transport of the
erosion solution, which is better than the other two ITIs. On the one
hand, ITI_1 forms water blocking clusters to prevent the diffusion of
water. On the other hand, ITI_1 interacts with Cl− in the erosion solution
to inhibit the diffusion of Cl− in calcium silicate hydrates nanopores. In
this investigation, excellent ion transport inhibitors were selected ac­
cording to the results of molecular simulation, and organic polymers
were synthesized according to the chemical structure formula. Then, the
ion transport inhibitor was applied to concrete preparation, and the
effect of ITI_1 in preventing water diffusion and chloride ion diffusion
was tested by a macro test. Water adsorption is often employed in
evaluating the ability of concrete to resist erosive solution penetration.
In this section, the test results are applied to verify the water plugging
effect of ITI_1. The chloride diffusion test is an important durability
index [10].In this section, the test results will be administered to test the
chloride diffusion resistance of ITI_1. On this basis, ITI_1 is also applied

10
J. Huang et al.
Table 3
Evaluation system of ion transport inhibitors.
① ① ②Value/Å
Value/Å Score
REF 100 10 100
ITI_1 62 6.2 58
ITI_2 80 8 67
ITI_3 85 8.5 79
to the concrete structure of the bearing platform and pier column of a
bridge. The water absorption, charge passed and strength of test blocks
with and without ITI are compared to judge whether ITI_1 has engi­
neering application value.
The results of concrete mixing experiments illustrated that ITI_1
increased the workability of concrete. Specifically, ITI_1 improved the
air content of fresh concrete from 2.2% of the reference group to 3.3%.
Moreover, ITI_1 raised the slumps of fresh concrete from 190 mm in the
reference group to 245 mm. The water absorption of concrete were
measured based on the DB32/T 3696-2019. The size of concrete is
formed as 150 mm * 150 mm * 150 mm. After 72 ± 2 h of standard
curing, a concrete core sample with a diameter of 75 ± 3 mm was
drilled. The upper and lower surfaces of the concrete core sample were
cut off, and then a cylindrical sample with a height of 75 ± 3 mm was
prepared. After that, the test piece was exsiccated in an oven at 100 ±
5 ◦ C for 72 ± 2 h and then removed and placed in a sealed container for
cooling for 24 ± 0.5 h. The mass W1 of the sample was registered. After
that, the specimens were immersed in water at 25 ± 3 ◦ C. Then, the
samples were taken out according to the timetable and the water on the
surface was wiped off with a rag. The mass Wt of the samples were
recorded at time t. The water absorption was calculated according to
Equation (9).
Wt − W1
f= × 100 (9)
W1
where.
f is the water absorption of the concrete specimen (%);
W1 represents the mass of the specimen before soaking (g);
Wt represents the mass of the specimen after soaking for time t (g).
The chloride concentration in concrete was measured by titration
according to NT build 443 [73]. The sample size is ɸ100 mm × 50 mm.
First, epoxy resin was applied to the concrete surface except the expo­
sure. Then the concrete specimens were sealed and placed in tanks
containing water. When the mass change of concrete specimens was less
than 0.1% every 24 h, the concrete specimens would be immersed in
165 g/L NaCl solution. Finally, after 57 days, the samples were ground
layer by layer with a thickness of no more than 2 mm, starting from the
concrete surface. The chloride ion concentration in the concrete sample
was measured, and then the initial chloride ion concentration was
deducted to obtain the chloride ion concentration depth curve. The
chloride diffusion coefficient can be calculated by Equation (10), [74].
{ [ ]}
x
Cx = Ci + (Cs − Ci ) 1 − erf √̅̅̅̅̅̅̅̅̅̅̅ (10)
2 Dnss ⋅t
where.
Cx is the Cl− concentration at depth x (%);
Cs is the Cl− content of concrete surface (%);
Ci is the original Cl− content (%);
x is the depth below the external exposure to the midpoint of the
grounding layer (m);
Dnss is the nonsteady state Cl− diffusion coefficient in concrete (m2/
s);
t is the time concrete was soaked in NaCl solution (s).
11
Cement and Concrete Composites 133 (2022) 104710
② ③ ③ Total score
Score Value/Å2 Score
10 6640.32674 10 30
5.8 3074.29107 4.629728612 16.62972861
6.7 4159.12778 6.263438446 20.96343845
7.9 4047.63546 6.095536588 22.49553659
Fig. 15 implies the water absorption of concrete without and with
ITI_1. The results illustrate that the water absorption rate of concrete
increases gradually with soaking time, in which the water absorption
rate of concrete without ITI_1 is 6.3% and that of concrete with ITI_1 is
2.4%. The addition of ITI_1 reduces the water absorption rate of concrete
by 62%, which proves that the addition of ITI_1 can effectively inhibit
the transmission of water in concrete.
Combining the results of molecular dynamics simulation, it can be
considered that ITI_1 inhibits the transfer of water molecules in gel
channels through interaction with calcium silicate hydrate and hydro­
phobic groups. At first, ITI_1 was adsorbed on the calcium silicate hy­
drates surface, and its hydrophobic end group reduced the
hydrophilicity of the calcium silicate hydrates surface. Later the inter­
action between ITI_1 and calcium silicate hydrates was destroyed by the
erosion solution, so ITI_1 desorbed from the calcium silicate hydrates
surface and gathered in the front of the solution to form a water-
plugging medium to inhibit the transmission of water molecules in the
gel channels.
In concrete structures, the penetration of Cl− is the decisive factor for
the corrosion of reinforcement. Fig. 16 (a) shows the relationship be­
tween the content of Cl− in the concrete and the penetration depth. ITI_1
not only reduces the diffusion rate of Cl− but also reduces the content of
Cl− in concrete. This result is substituted into Equation (10) to obtain the
chloride ion diffusion coefficient manifested in Fig. 16 (b). When ITI_1
was not added, the chloride ion diffusion coefficient was 3.2 × 10− 12
m2/s. After adding ITI_1, the chloride ion diffusion coefficient was 2.1 ×
10− 12 m2/s. The diffusion coefficient of Cl− was significantly reduced by
34.4%. This is consistent with the conclusion of the molecular dynamics
calculation, such as the chloride ion erosion depth displayed in Fig. 13
and the chloride ion diffusion rate illustrated in Fig. 14. Obviously, the
results of the chloride ion diffusion test verify the correctness of the
conclusion of the molecular simulation calculation.
ITI_1 can inhibit the diffusion of erosion ions in theory and
Fig. 15. The water adsorption of concrete as a function of the square root of
immersing time.
J. Huang et al. Cement and Concrete Composites 133 (2022) 104710

Fig. 16. The durability of concrete: (a) chloride erosion depth and (b) chloride diffusion coefficient.

experiment. Furthermore, they were applied to practical offshore

Table 4
structures. Fig. 17 implies the application of ITI_1 in the concrete
Durability experiments results of the project.
structure of the bearing platform and pier column of the bridge. The
cushion cap is immersed in the seawater for a long time, and the Water Charge passed/C Compressive strength/MPa
absorption/%
continuous action of seawater pressure makes the eroded ions in the
seawater continuously penetrate into the concrete. The pier column is 7d 14d 28d 28d
located in the splash area of sea water. The concrete in the pier column Without ITI_1 2.0 1.75 1435 58.6
area has been affected by alternating dry and wet sea water for a long With ITI_1 0.7 0.5 680 54.5
time.The capillarity in this region with strong adsorption capacity cau­
ses fast ion enrichment.
transport inhibitors inspired by modern intelligent drug delivery sys­
According to BS 1881–122:1983 [69], the water absorption of the
tems and explored the composition, structure and mechanism of
pretreated concrete test block was measured after soaking it in water for
organic–inorganic interactions in the process of erosion solution trans­
30min. The results are shown in Table 4. It can be seen that the addition
port by molecular dynamics. Ion transport inhibitors with different
of ITI_1 reduces the water absorption of concrete by 65% in 7 d and 71%
molecular structures implied different mechanisms to inhibit the trans­
in 14 d. At 28 d, the electric flux and strength of concrete decreased by
port of corrosive solutions. To evaluate the effect of ion transport in­
52.6% and 7%, respectively. This implies that ITI_1 can effectively
hibitors on the atomic scale, an evaluation system of ion transport
improve the durability of concrete with slight strength loss. It is further
inhibitors on the molecular scale was proposed for the first time, and the
proven that ITI_1 realizes the effect of hydrophobicity, jamming the
preferred ion transport inhibitor ITI_1 was added into concrete to test
pores and its applicability in engineering applications.
the water adsorption and ion diffusion coefficient on the macro scale. In
addition, ITI_1 was also applied to the bearing platform and pier column
4. Conclusion
of a bridge. After field detection, it is found that the test conclusion is
consistent with the calculation results, indicating that ITI_1 can
This investigation designed environmentally responsive ion

Fig. 17. Engineering application of ITI_1.

12
J. Huang et al.
effectively unravel the problem of Cl− corrosion of concrete in the early
stage. All in all, the following conclusions are obtained:
(1) When the main chain of the ion transport inhibitor is the car­
boxylic acid group, it has a forceful interaction with the calcium
silicate hydrates, which mainly comes from the formation of a
calcium oxygen bonding network. Ion transport inhibitors are
similar to the hinges of a door; when the gel pores are dry, the ion
transport inhibitors lie on the surface of the calcium silicate hy­
drates substrate. When the corrosion solution invaded the gel
channel, the hydrophobic groups were perpendicular to the sur­
face of calcium silicate hydrates to prevent the transmission of
the solution.
(2) When the main chain of the ion transport inhibitor is alcohol
amine, it also interacts with the calcium silicate hydrates surface.
However, this mainly comes from the formation of a H bond
network. When the corrosion solution invaded the gel channel,
the H bond network was attacked by hydroxyl and hydrogen ions
in the solution, resulting in the failure of the H bond network. The
alcohol amine ion transport inhibitor dropped off from the cal­
cium silicate hydrates surface and gathered in the front of the
etching solution to form a water plugging medium. It could also
bind with erosive ions and inhibit the diffusion of Cl− .
(3) Here, we report the mechanism, structure-activity relationship,
evaluation system, experimental verification and engineering
application of ion transport inhibition. This research realizes
closed-loop research of polymers. From this point of view, the
improvement of concrete durability can rely on molecular dy­
namics to simulate the fluid transport of nanopores and then
design ion transport inhibitors with different structures to regu­
late the sustainability of cement-based materials from the mo­
lecular structure design of admixtures.
Credit authorship contribution statement
Jiale Huang: Data curation, Formal analysis Conceptualization,
Investigation, Methodology, Software, Writing - original draft review &
editing. Ruixing chen: Data curation, Formal analysis, Investigation,
Methodology, Experiment, Writing - original draft review & editing.
Yang Zhou: Investigation, Methodology, Software. Jin Ming: Investi­
gation, Experiment, Review. Jiaping Liu: Resources, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
We acknowledge support from the National Natural Science Foun­
dation of China (Grant Nos. U1706222, 52078240, 51908254,
U2040222, 52008097), Jiangsu Planned Projects for Postdoctoral
Research Funds (2020Z029), the China Postdoctoral Science Foundation
funded project (2020M671298, 2021T140114). We are also grateful to
the High Performance Center (HPCC) of Nanjing University for per­
forming the numerical calculations in this paper on its IBM Blade cluster
system.
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