buildings
Review
Damage Mechanism and Modeling of Concrete in Freeze–Thaw
Cycles: A Review
Jinjun Guo 1 , Wenqi Sun 1 , Yaoqun Xu 1, *, Weiqi Lin 1
Citation: Guo, J.; Sun, W.; Xu, Y.; Lin,
W.; Jing, W. Damage Mechanism and
Modeling of Concrete in Freeze–Thaw
Cycles: A Review. Buildings 2022, 12,
1317. https://doi.org/10.3390/
buildings12091317
Academic Editor: Elena Ferretti
Received: 29 June 2022
Accepted: 25 August 2022
Published: 28 August 2022
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Attribution (CC BY) license (https://
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4.0/).
Buildings 2022, 12, 1317. https://doi.org/10.3390/buildings12091317
and Weidong Jing 2
1 School of Water Conservancy Engineering, Zhengzhou University, Zhengzhou 450001, China
2 Communications Construction Company of CSCEC 7th Division Co., Ltd., Zhengzhou 450004, China
* Correspondence: yaoqunxu_zzu@163.com
Abstract: The deterioration of concrete microstructures in freeze–thaw (F–T) cycles is the primary
reason for the reduction in the service life of concrete. This paper reviews recent progress in the
theory of damage mechanisms and damage models of concrete in F–T cycles. It is a detailed review
of the salt-freeze coupling condition, microstructure testing, and models for the evolution of concrete
properties that are subjected to F–T damage. Summarized in this paper are the deterioration theory
of water phase transition; the mechanism of chloride-F–T and sulfate-F–T damage; the microstructure
testing of hydration products, pore structure, microcracks, and interfacial transition zones (ITZ).
Furthermore, F–T damage models for the macrostructure are presented. Finally, the issues that are
existing in the research and outlook of concrete F–T damage are highlighted and discussed. This
paper is helpful in understanding the evolution of F–T damage, and also provides a comprehensive
insight into possible future challenges for the sustainable design and specifications of concrete in
cold environments.
Keywords: damage mechanism; freeze–thaw cycles; concrete durability; modeling; microstructure
1. Introduction
The destructive effect of freeze–thaw (F–T) cycles on concrete is the primary cause of
concrete failure in cold areas [1,2]. The F–T damage of concrete is a complex physical and
chemical phenomenon [3,4] that begins with the internal microstructure of concrete. For
example, in the F–T cycle, the pore structure of concrete deteriorates; thus, the permeability
of concrete increases, and the F–T damage is accelerated by the entry of an external water
and erosion medium [3]. The surface shedding and scaling of concrete is caused by the F–T
cycle, and the risk of steel bar corrosion is increased [4]. The precondition for improving
the frost resistance and service life of concrete is to understand the damage mechanism and
performance evolution model in an F–T environment.
Therefore, many studies on the deterioration of concrete under F–T cycle erosion
have been reported. The damage mechanism of concrete in an F–T environment has been
expounded by many researchers. The hydraulic pressure theory [5] and osmotic pressure
theory [6,7] were subjects of early research that was related to F–T damage mechanisms. The
migration of solution in pores is the cause of F–T damage in concrete in these two theories;
however, the direction of migration is different in both. In addition, the saturation theory [8],
crystallization pressure theory [9], micro-ice lens theory [10,11], glue spall theory [12],
and pore mechanics [13] have also been used to explain the F–T concrete deterioration
mechanism. Based on previous F–T theoretical studies, the latest research [14–16] suggests
that F–T damage is caused by the combined action of crystallization pressure, ice expansion
pressure, and low-temperature suction, rather than a single factor. For the damage resulting
from the coupling of ion erosion and F–T cycles, researchers believe that the combined
effects of F–T damage, salt crystallization, salt chemical corrosion, and calcium loss lead to
the deterioration of the pore structure [17].
https://www.mdpi.com/journal/buildings
Buildings 2022, 12, 1317 2 of 36

There have been many achievements in the performance evolution and micromor-
phology of concrete during F–T cycles, which are categorized into macro, meso, and micro
damage from different research scales. Macroscopic research [18,19] has mainly discrim-
inated the damage of concrete based on experimental indexes such as material surface
state, mechanical property test, ultrasonic, acoustic emission, and resistivity. In mesoscopic
research [20–23], nuclear magnetic resonance (NMR) and computed tomography (CT) tech-
niques were primarily used to identify the crack propagation and pore parameter evolution
of concrete. The evolution of microcracks and pores in the specimen was discussed using a
parameterized damage model. At the micro level [24–26], most of the studies analyzed the
microscopic pore structure of cement-based materials using scanning electron microscopy
(SEM) and mercury intrusion porosimetry (MIP). The changes in the chemical components,
microcracks, and micropores in the damage process were revealed. In addition, thermal
analysis and X-ray diffraction (XRD) techniques were often used to quantitatively analyze
the hydration process and deteriorated products of cementitious materials that were under
F–T erosion [27–29].
The deterioration of concrete under a F–T cycle can be characterized by establishing a
specific model. The parameters of the F–T damage model have gradually changed from a
macro index to a micro index in recent studies. The F–T damage mechanism is discussed
by comparing the evolution process of the concrete microstructures with the macroscopic
damage. The performance data are needed to establish a concrete damage model include the
mass loss rate [30], RDEM [31], compressive strength [32], resistivity, and micro-reference
quantity [33,34]. For the evolution of the microstructure, the changes in the pore structure
distribution, microcrack density, and fractal dimension have also become an important part
of the F–T damage model. Classical functions such as the parabola [35], power function [36],
exponential function [37], logistics function [38], Boltzmann function [39], and Weibull
distribution function [40] are used in common damage equation forms.
The F–T damage mechanism of concrete is significant for improving the durability of
concrete in cold areas. The prediction and evaluation of concrete service life are guided
by models of the F–T damage of concrete. To review the latest progress in the research
on F–T damage of concrete, the theoretical analyses and microscopic tests of the concrete
damage mechanism in F–T cycles are introduced in detail in this paper. A review of the F–T
damage theory, damage mechanism of salt-freezing coupling, and the quantitative analysis
of the microstructure are also presented. The F–T damage evolution models of macro index
and micro index are discussed. The theory and issue of the concrete F–T damage model,
especially combined with the application of advanced detection methods, are reviewed.
In conclusion, the scope of this paper is to provide a systematic review of concrete F–T
damage and future challenges for the sustainable design and specifications of concrete in
cold environments.

2. Damage Mechanism
2.1. Deterioration Theory
2.1.1. Hydraulic Pressure Theory and Osmotic Pressure Theory
According to the pore size, concrete pores are divided into gel pores, capillary pores,
and voids. Various pores are not isolated, and the types of water in the corresponding
pores are also different: bulk water, capillary water, gel pore structure water, and gel
pore adsorption water [41]. Bulk water and capillary water can freeze in the natural
environment [42], while saturated gel pore water can freeze at −30 ◦ C to −80 ◦ C. These
two theories suggest that the difference in the freezing point between pores is the initial
factor of concrete frost damage.
These two theories were first proposed by Powers and were based on Darcy’s law.
According to the hydraulic pressure theory, when concrete is affected by an external low
temperature, its effect occurs from the outside to the inside. First, the pore water on the
surface of the concrete is frozen, and the volume difference between ice and water leads
to the migration of liquid water through the capillaries. If the temperature continues to
 temperature, its effect occurs from the outside to the inside. First, the pore water on the
surface of the concrete is frozen, and the volume difference between ice and water leads
Buildings 2022, 12, 1317 to the migration of liquid water through the capillaries. If the temperature continues to3 of 36
decrease, the volume of ice increases to compress the liquid water continuously, resulting
in compressive stress in the pores and tensile stress in the concrete (Figure 1a). The capil-
lary decrease,
water flow theisvolume
proportional to the stress
of ice increases that is produced
to compress the liquidinwater
the concrete.
continuously,Withresulting
a con- in
tinuous increase in
compressive tensile
stress stress,
in the poresmicrocracks
and tensileoccur stressinside
in thethe concrete
concrete when1a).
(Figure it reaches its
The capillary
ultimate
watertensile
flow isstrength [43]. The
proportional hydrostatic
to the stress thatpressure
is produced is related
in theto pore length,
concrete. With viscosity
a continuous
coefficient,
increasepermeability coefficient,
in tensile stress, microcracks icingoccur
amount, insideandthe cooling
concreterate.
whenThe itgreater
reaches theitsicing
ultimate
rate tensile
is, thenstrength
the smaller[43].the
Thepermeability is, and the
hydrostatic pressure longer the
is related porelength,
to pore size is,viscosity
then thecoefficient,
more
vulnerable the concrete
permeability is to F-T
coefficient, icingdamage
amount, [44].and Reducing
cooling rate. the pore
The spacing
greater thein aicing
materialrate can
is, then
reduce
thethe hydrostatic
smaller pressure, which
the permeability is, andprovides
the longer theoretical
the poresupport for the
size is, then theair-entraining
more vulnerable
agentthe[45]. Because
concrete is toofF–T high w/c[44].
itsdamage ratio and porosity,
Reducing the pore ordinary
spacingconcrete will can
in a material gradually
reduce the
expand at low temperature
hydrostatic pressure, which due to the pressure
provides that issupport
theoretical causedfor by the
the air-entraining
continuous freezing agent [45].
of water;
Because for of
air-entraining
its high w/cconcrete,
ratio andice is formed
porosity, in theconcrete
ordinary micropores willthat is formed
gradually expandby the at low
air-entraining agent, and the cement paste gradually shrinks. Hydrostatic pressure theory for
temperature due to the pressure that is caused by the continuous freezing of water;
cannot explain theconcrete,
air-entraining expansion iceofisordinary
formed inconcrete and the that
the micropores freezing of non-expansive
is formed liq-
by the air-entraining
uids [36,46].
agent, and the cement paste gradually shrinks. Hydrostatic pressure theory cannot explain
In an
the experimental
expansion and practical
of ordinary concreteenvironment,
and the freezing the damage to concreteliquids
of non-expansive that is[36,46].
caused
by the F-T of the salt solution is more severe than that of pure water. Powers et al.ispro-
In an experimental and practical environment, the damage to concrete that caused
by the F–T of the salt solution is more severe than that of pure
posed the osmotic pressure theory in 1953 [6]. The theory holds that there are certain salt water. Powers et al. proposed
ionsthe osmotic pressure
in concrete. The freezingtheory in 1953
of the [6]. The and
macropores theory holds that
capillaries firstthere
leadsareto certain
an increase salt ions
in concrete. The freezing of the macropores and capillaries
in the solution concentration in the unfrozen pores, which causes the supercooled water first leads to an increase in the
in the gel pores to begin to migrate. Owing to the complexity of the pore structure, the the
solution concentration in the unfrozen pores, which causes the supercooled water in
gel pores
migration to begin torate
permeability migrate. Owingresulting
is different, to the complexity
in an osmotic of the pore structure,
pressure that damagesthe migration
the
permeability rate is different, resulting in an osmotic pressure that damages the interior
interior of the material. In addition, the saturated vapor pressure of water is higher than
of the material. In addition, the saturated vapor pressure of water is higher than that
that of ice, resulting in osmotic pressure when unfrozen water moves to the ice (Figure
of ice, resulting in osmotic pressure when unfrozen water moves to the ice (Figure 1b).
1b). The osmotic pressure is directly proportional to the solution concentration, but the
The osmotic pressure is directly proportional to the solution concentration, but the icing
icing amount is inversely proportional to the solution concentration. It can be seen that at
amount is inversely proportional to the solution concentration. It can be seen that at
a certain concentration, the coupling of the two pressures will produce the maximum
a certain concentration, the coupling of the two pressures will produce the maximum
value [47].
value [47].

(a) (b)
Figure 1. Hydrostatic
Figure pressure
1. Hydrostatic and osmotic
pressure pressure
and osmotic model.
pressure (a) Hydrostatic
model. pressure
(a) Hydrostatic principle
pressure [36]; [36];
principle
(b) Osmotic pressure
(b) Osmotic model
pressure [48]. [48].
model

2.1.2.2.1.2.
Critical Saturation
Critical Theory
Saturation Theory
F-T damage
F–T damagemay mayoccuroccur
only only
whenwhenthe moisture content
the moisture reaches
content a certain
reaches condition,
a certain condition,
and andthe the
external
external temperature alternates between positive and negative. Based on thethe
temperature alternates between positive and negative. Based on above
above conditions, Fagerlund
conditions, Fagerlund [8,49]
[8,49] proposed
proposed thethe critical
critical saturation
saturation theory,
theory, which
which holdsholds
that the
that critical
the critical saturation
saturation of concrete
of concrete is anisimportant
an important condition
condition for determining
for determining its dete-
its deterioration.
rioration. The gas content in the pores only affects the concrete at the time
The gas content in the pores only affects the concrete at the time of which the material of which the
water
material water
reaches thereaches the critical
critical value, value,
and the and the
damage damage
to the to the
concrete concrete
is slow whenisthe
slow when
water the
saturation
is below the critical saturation. However, concrete deteriorates rapidly when it exceeds the
critical saturation, and it is generally believed that the critical saturation is in the range of
78–91% (Figure 2). Subsequently, Fagerlund [50] determined that the diffusion of gas in
concrete is limited by multiple factors. A theory of gas dissolution and diffusion in concrete
Buildings 2022, 12, x FOR PEER REVIEW 4 of 37

water saturation is below the critical saturation. However, concrete deteriorates rapidly
Buildings 2022, 12, 1317 when it exceeds the critical saturation, and it is generally believed that the critical satura- 4 of 36
tion is in the range of 78–91% (Figure 2). Subsequently, Fagerlund [50] determined that
the diffusion of gas in concrete is limited by multiple factors. A theory of gas dissolution
and diffusion inwhich
is established, concrete
can is
beestablished, whichthe
used to evaluate can be used
effects to evaluate
of the the effects
void structure of the
parameters,
void structure parameters, material diffusivity, and time on the spacing factor.
material diffusivity, and time on the spacing factor. After entering the new century, owing After en-
tering
to the the new century,
development owing to the technology,
of experimental development of experimental
multi-medium technology,
water multi-me-
filling dynamics that
dium wateronfilling
are based dynamics
critical thattheory
saturation are based on critical
[51] have saturation Water
been proposed. theoryfilling
[51] have been
dynamics
proposed.
divide theWater
waterfilling dynamics
absorption divide the
of concrete intowater absorption
two stages. The of concrete
first stage isinto two stages.
affected by the
The first stage
properties is affected
of gel pores andbycapillaries;
the properties
theseofpores
gel pores
haveand capillaries;
a strong these porescapacity
water absorption have a
strong
owingwater
to theabsorption
influence ofcapacity
negativeowing to the
pressure. Theinfluence
second of negative
stage pressure.
is caused by theThe second
air in pores
stage is caused
that are dissolvedby the airsolution
in the in poresand
thatdiffused
are dissolved in the
to larger solution
pores and diffused
or surfaces. Throughtothe larger
pore
pores or surfaces.
elastic–plastic Through
model the pore
that was elastic–plastic
established model
[52], it was that was
verified thatestablished [52], itwhen
concrete shrinks was
verified
the water that concreteisshrinks
saturation whenthe
lower than thecritical
watervalue
saturation
and itisexpands
lower than
when the critical
it is higher value
than
and
the it expands
critical when it is higher than the critical value.
value.

Figure
Figure2.2.Schematic
Schematicdiagram
diagramofofsaturation
saturationtheory
theory[49].
[49].(a)
(a)The
Thewater
waterabsorption
absorptionrate
rateofofconcrete
concreteby
by
stages; (b) Matrix saturation state; (c) Pore saturation state.
stages; (b) Matrix saturation state; (c) Pore saturation state.

2.1.3.
2.1.3.Crystallization
CrystallizationPressure
PressureTheory
Theory
Scherer
Scherer[9] [9]proposed
proposedthat thatcrystallization
crystallizationpressure
pressureisisoneoneofofthe
themain
maincauses
causesof offrost
frost
damage
damagein inconcrete.
concrete.The Themagnitude
magnitudeand anddirection
directionof ofthe
thecrystallization
crystallizationpressure
pressuredepend
depend
on
onvarious
variousfactors,
factors,such
suchas as
thethe
pore shape,
pore the environmental
shape, the environmental temperature, the initial
temperature, con-
the initial
ditions, and the icing degree. The ice crystals that are inside the concrete tend totogrow
conditions, and the icing degree. The ice crystals that are inside the concrete tend grow
from
fromthe
the high-pressure
high-pressure areaarea totothe
thelow-pressure
low-pressuredirection,
direction,which
which ensures
ensures thethe stability
stability of
of the
ice crystal pressure [53]. Owing to the difference in curvature between
the ice crystal pressure [53]. Owing to the difference in curvature between the crystal sur-the crystal surface
and and
face the end, the cylindrical
the end, crystal
the cylindrical that isthat
crystal in the void
is in theattempts to increase
void attempts in the direction
to increase in the di-of
reducing the pressure difference (pore wall), and the pore wall produces
rection of reducing the pressure difference (pore wall), and the pore wall produces radial radial compressive
stress to resist
compressive the to
stress pressure difference.
resist the pressure When the corresponding
difference. circumferential
When the corresponding tensile
circumfer-
load in the pores exceeds the material threshold value, the pores inside
ential tensile load in the pores exceeds the material threshold value, the pores inside the the material are
destroyed (Figure 3a). For irregular ink-bottle pores, ice crystals are formed
material are destroyed (Figure 3a). For irregular ink-bottle pores, ice crystals are formed in the large
cavity in the capillary pore. When the ice crystal grows, the net circumferential stress in
the capillary cavity is compressed regardless of whether the ice is full of pores (Figure 3b).
This explains the instant shrinkage of concrete at the end of the freezing process. The
researchers found that the maximum crystallization pressure can be up to 10.9 MPa, which
 Buildings 2022, 12, x FOR PEER REVIEW 5 of 37

in the large cavity in the capillary pore. When the ice crystal grows, the net circumferential
Buildings 2022, 12, 1317 stress in the capillary cavity is compressed regardless of whether the ice is full of 5pores of 36
(Figure 3b). This explains the instant shrinkage of concrete at the end of the freezing pro-
cess. The researchers found that the maximum crystallization pressure can be up to 10.9
MPa, which
greatly exceedsgreatly exceeds
the failure the failure
stress stress
of 0.374 MPaof[54].
0.374 MPa the
When [54].temperature
When the temperature
is below theis
critical point, the concrete will crack and destroy; when the temperature rises, the icerises,
below the critical point, the concrete will crack and destroy; when the temperature will
the ice
melt, andwill
themelt, and crack
concrete the concrete crack
will close [55].will
Theclose [55].
fatigue The fatigue
damage leads todamage leads of
the damage tothe
the
damage of the concrete, and the repeated cracking that is caused by periodic crystalliza-
concrete, and the repeated cracking that is caused by periodic crystallization pressure leads
tion
to thepressure
gradual leads to theand
expansion gradual expansion
connection and connection
of concrete microcracks of concrete microcracks
and the nonlinear and
failure
the
of nonlinear failure of concrete.
concrete.

(a) (b)
Figure3.3.Schematic
Figure Schematicdiagram
diagramof ofcrystallization
crystallizationpressure
pressuretheory
theory[53].
[53].(a)
(a)Schematic
Schematicofdiagram of co-
a cylindrical
lumnar crystals in pores; (b) Crystallization pressure distribution in capillaries.
crystal in a pore of radius γ p . Both the hemispherical end (E) and the cylindrical body (B) adopt the
radius, γ p − δw . (b) Schematic of ice forming in a capillary cavity and in an air void. N is connection
2.1.4. Micro-Ice Lens Theory
pore between equivalent liquid and crystal interface. F point represent the curvature of the crystal is
Setzer
negative. A is[10–11,56] established
curvedliquid/vapor the theory of micro-ice lenses that was based on non-
meniscus.
equilibrium thermodynamics and the three-phase equilibrium theory of porous media.
This Micro-Ice
2.1.4. theory holds Lensthat concrete cannot reach complete saturation, and water, ice, and
Theory
steam coexist
Setzer in the pores.
[10,11,56] Duringthe
established thetheory
coolingofprocess,
micro-ice thelenses
chemicalthatpotential
was based of ice
on in the
non-
macropores thermodynamics
equilibrium is smaller than that andof water in the gel pores.
the three-phase The compression
equilibrium of the concrete
theory of porous media.
matrix
This causes
theory holdssupercooled
that concrete watercannot
to flow to the
reach macropores
complete and become
saturation, trapped
and water, ice,inand
the
micro-ice
steam lens,
coexist insothethe gel pore
pores. saturation
During decreases
the cooling and the
process, the chemical
concrete shrinks.
potentialInofthe iceheating
in the
process, theiswater
macropores smaller in than
the large
that of pores
water cannot
in theflow back to
gel pores. Thethe gel pores freely
compression of theunder
concretethe
action of the ice front that is produced by different pore interfaces and because the micro-
matrix causes supercooled water to flow to the macropores and become trapped in the
ice lens islens,
micro-ice still so
in the
the gel
frozen
porestate. If theredecreases
saturation is water situated outside, shrinks.
and the concrete the gel pore
In theabsorbs
heating it,
which leads
process, to aninincrease
the water the large inpores
the total
cannotsaturation
flow back and toexpansion
the gel pores of concrete.
freely under ThetheF-Taction
cycle
ofis the
likeice
a low-temperature
front that is produced pump, bywhich is powered
different by the change
pore interfaces and becauseof temperature
the micro-ice andlens
mi-
isgration
still in of
thesupercooled
frozen state.water. If thereTheis micro-ice
water situatedlens prevents
outside, the return
the gel poreofabsorbs
the water during
it, which
the heating
leads processinand
to an increase the absorbs the water
total saturation andcontinuously
expansion of duringconcrete. cooling,
The F–T resulting in the
cycle is like a
expansion of concrete during heating and the shrinkage of it during cooling. The satura-
low-temperature pump, which is powered by the change of temperature and migration of
tion of concrete
supercooled water. increases with anlens
The micro-ice increase in the
prevents thenumber
return of of cycles,
the water andduring
when the the ultimate
heating
saturation
process andisabsorbs
reached, thethe concrete
water fails (Figure
continuously during4). Incooling,
addition, the migration
resulting of water also
in the expansion of
providesduring
concrete conditionsheating forand
the the
growth of ice. of
shrinkage Initthe earlycooling.
during stage ofThe freezing and thawing,
saturation of concretethe
water ratewith
increases of thean concrete
increase isinfaster,
the numberthe macroscopic
of cycles, and micro-ice
whenlens the grows,
ultimate and the state is
saturation of
the concrete is similar to that of saturated soil; in the later stage, the ice stress provides
reached, the concrete fails (Figure 4). In addition, the migration of water also is greater
than the critical
conditions for thevalue,
growth andoftheice.micro-crack
In the earlypropagates. F-T damage
stage of freezing occurs in
and thawing, theconcrete
water
rate of the concrete is faster, the macroscopic micro-ice
under the combined action of the formation of the capillary ice lens and the movementlens grows, and the state of theof
concrete is similar to that of saturated soil; in the later stage,
water in gel pores, so reducing the capillary pores and increasing the gel pores can effec-the ice stress is greater than
the critical
tively value,
prevent F-Tand the micro-crack
damage, which can be propagates.
obtained by F–T damagethe
reducing occurs in concrete
water-cement under
ratio and
the combined action of
using an air entraining agent [57].the formation of the capillary ice lens and the movement of water
in gel pores, so reducing the capillary pores and increasing the gel pores can effectively
prevent F–T damage, which can be obtained by reducing the water–cement ratio and using
an air entraining agent [57].
Buildings 2022, 12, x FOR PEER REVIEW 6 of 37
Buildings 2022, 12,
Buildings 2022, 12, x1317
FOR PEER REVIEW 6 6ofof37
36

Figure 4. Micro-ice lens model [10].

Figure
Figure4.
4. Micro-ice
Micro-icelens
lensmodel
model[10].
[10].
2.1.5. Glue Spall Theory
2.1.5.
2.1.5. Glue
GlueSpall
SpallTheory
Theory
Aiming at understanding the spalling phenomenon of concrete surfaces under the
Aiming
Aiming at at understanding
understanding the the spalling
spalling phenomenon
phenomenon of of concrete
concrete surfaces
surfaces under
under the the
condition of F-T cycles, Valenza et al. [12,58,59] established the theory of adhesive spall-
condition
condition ofof F-T
F–T cycles,
cycles, Valenza
Valenza et et al.
al.[12,58,59]
[12,58,59]established
establishedthethetheory
theoryofofadhesive
adhesive spall-
spalling.
ing. The theory holds that when concrete is damaged by the F-T process, a composite
ing.
The The
theorytheory
holdsholds that when
that when concrete
concrete is damaged
is damaged by theby theprocess,
F–T F-T process, a composite
a composite mech-
mechanism is formed between the ice shell that is formed by the freezing of water and the
mechanism
anism is formedis formed between
between the the
ice ice shell
shell thatthatis is formedbybythe
formed thefreezing
freezingof of water
water andand thethe
concrete surface, owing to the existence of the salt solution. The shrinkage of the ice body
concrete
concrete surface,
surface, owing owing toto the
the existence
existence of of the
the salt
salt solution.
solution. The
Theshrinkage
shrinkageof ofthe
theice
icebody
body
produces tensile stress on the surface of the concrete when it is shrinking in the external
produces
produces tensile
tensile stressstress on
on the
the surface
surface of of the
the concrete
concrete when
when itit is
is shrinking
shrinking in in the
the external
external
environment [60] because the linear expansion coefficients of the two are different (at −10
environment
environment [60]
[60] because
because the
the linear
linear expansion
expansion coefficients
coefficients of
of the
the two
two are
are different
different (at −
(at −10
10
°C,
◦ C,10 × 10−6−6K−−16−1 on−the
1 onsurface of the concrete and 50 × 10−6−6K−1−1 in−ice). 6 K−When the tempera-
°C, 10 × 10 K on the surface of the concrete and 50 × 10 K in ice). When the tempera-
10 × 10 K the surface of the concrete and 50 × 10 1 in ice). When the
ture reaches −20 °C, it will ◦produce 2.6 MPa of stress on the concrete, which exceeds the
ture reaches −20
temperature reaches°C, it−will
20 produce
C, it will2.6 MPa of
produce 2.6stress
MPaon of the concrete,
stress which exceeds
on the concrete, whichthe ex-
critical value of concrete strength and causes concrete failure (Figure 5). Valenza et al. also
critical value
ceeds the of concrete
critical value ofstrength
concreteand causesand
strength concrete
causesfailure (Figure
concrete failure5).(Figure
Valenza5).etValenza
al. also
proposed
et al. alsothat fracture mechanics can be usedcan to judge whether icewhether
cracks will penetrate
proposed that
proposed fracture mechanics
that can be used to be
fracture mechanics judge
usedwhether
to judge ice cracks will penetrate
ice cracks will
the crack surface andsurface
they considered that the damage to damage
the concrete surface is relatively
the crack surface
penetrate the crack and they considered that the damage
and they considered to the concrete
that the to thesurface
concreteis relatively
surface is
constant forconstant
each cycle.
constant
relatively for each cycle. for each cycle.

Schematic
Figure5.5.Schematic
Figure diagram
diagram of of glue
glue spall
spall theory
theory [53].[53]. (a) Rough glass surface, (b) Epoxy/glass
Figure 5. Schematic
composite diagram of glue
at initial temperature spall
T0 . (c) theoryof[53].
Interface composite, illustrating the islands of epoxy and the
2.1.6. Theoryofofglass
thin scallops Unsaturated
removed whenPorous
T Elasticity
T0 . (d,e) Schematic representation of an epoxy/glass/epoxy
2.1.6. Theory
sandwich sealofand
Unsaturated Porous
the stress that Elasticity
arises in the composite. (d) Sandwich seal, dimensions and
The theory of unsaturated porous elasticity was developed by Coussy [13] and it was
The theory
orientation. of unsaturated
(e) Schematic of stressporous elasticity
that arises was surface
in the glass developed bythe
under Coussy
epoxy,[13] and
σg , in theitepoxy,
was
based on continuum thermodynamics and water-phase transition kinetics. It was origi-
based
σe , andon
thecontinuum thermodynamics
glue spall stress and water-phase
around the boundary of the epoxy, σtransition
gs . kinetics. It was origi-
nally used to study the deformation that is caused by freezing water. The stress of porous
nally used to study the deformation that is caused by freezing water. The stress of porous
materials can be divided into matrix stress, thermal stress, and internal stress according
materials can be divided into matrix stress, thermal stress, and internal stress according
to the source of the force, in which thermal stress can be ignored. There are two different
to the source of the force, in which thermal stress can be ignored. There are two different
phases in the pores: solid crystal and liquid solution. When the concrete is saturated, the
phases in the pores: solid crystal and liquid solution. When the concrete is saturated, the
Buildings 2022, 12, 1317 7 of 36

2.1.6. Theory of Unsaturated Porous Elasticity

The theory of unsaturated porous elasticity was developed by Coussy [13] and it was
based on continuum thermodynamics and water-phase transition kinetics. It was originally
used to study the deformation that is caused by freezing water. The stress of porous
materials can be divided into matrix stress, thermal stress, and internal stress according
to the source of the force, in which thermal stress can be ignored. There are two different
phases in the pores: solid crystal and liquid solution. When the concrete is saturated,
the main reason for concrete expansion is the hydraulic pressure that is caused by water
condensation. In contrast to the hydrostatic pressure theory, the stress that is produced in
the freezing process of saturated non-air-entrained slurries is limited, owing to the action of
the matrix stress. The ice crystal pressure in the concrete becomes the only expansion source
when a bubble is introduced because the existence of the bubble suppresses the hydrostatic
pressure. Moreover, the concrete shrinks when the thermal shrinkage is dominant to it [61].
The theory of unsaturated porous elasticity, considering thermodynamic equilibrium,
mechanical equilibrium, and the conservation of pore water mass, provides sufficient
theoretical support for the analysis of the F–T mechanism of concrete, and the experimental
results of the model are highly correlated with the actual situation. Relevant scholars have
found that there is a significant correlation between pore pressure and freezing rate, and re-
gardless of the degree of supercooling, the volume of ice in the melting stage is significantly
larger than that in the cooling stage, so it can be considered that the ice is not discharged in
the melting process [52,58]. Using this theory, the freeze–thaw durability of concrete can be
predicted and the effects of air content, curing time, saturation, and water–cement ratio
on the F–T damage of concrete can be studied [62,63]. For different damage models, the
theoretical basis varies, such as in Darcy’s law, porous media mechanics, phase transition
theory, and thermodynamics (Table 1). For example, for the deformation performance of
concrete, the hydraulic pressure theory explains the expansion phenomenon of concrete
after cycles, but it cannot explain the concrete deterioration caused by the volume non-
expansion of some solutions after freezing. The theory of micro-ice lenses qualitatively
describes the phenomenon of the alternating shrinkage and expansion of concrete caused
by water migration and phase transformation. The glue spall theory explains the spalling
phenomenon of concrete surfaces by using an analogy. The relationship between the macro-
scopic damage degree and microcosmic performance evolution of concrete is established
using the unsaturated porous elasticity theory. Each theory has its scope of application,
and the study of F–T damage should not be limited to a specific theory. Recently, based
on previous F–T theory, researchers [14,15,64] believed that F–T damage is not caused by
a single factor, but by the combined action of crystallization pressure, the water pressure
caused by ice expansion, and low-temperature suction caused by the surface tension of
water. However, this is currently difficult to express quantitatively.
In recent years, damage mechanics has become a prominent topic in the theoretical
study of F–T damage; the original defects in concrete can be regarded as initial damage
variables, and concrete microcracks gradually expand and lead to concrete deterioration
failure with the deepening of the F–T degree, which is consistent with the law of the damage
accumulation process. The study of F–T damage mainly involves studying the interaction
mechanism between water and concrete, and not just the influence of stress that is caused
by water phase transformation on concrete. Most classical theories focus on the influence
of the water phase transition and pay less attention to changes in the local water–concrete
pore structure. It is suggested that the multi-scale evolution equation of damage to concrete
can be formulated by combining pore mechanics with concrete damage mechanics in the
future, and the coupling relationship between pore structure characteristics, liquid phase
transition, matrix deformation, and damage variable characterization can be completed.
The establishment and development of the F–T damage constitutive equation for porous
materials are analyzed based on the temperature–humidity–force field of concrete.
Buildings 2022, 12, 1317 8 of 36

Table 1. A brief introduction to the main F–T theories.

Model Pore Pressure Expression Symbolic Meaning Application/Limitation

p: Hydraulic pressure
The function of air entraining agent
k: Permeability coefficient
Hydrostatic and the phenomenon of freezing
 
K3E r2E K3E r2 n: Viscous resistance
3n ∆i
k
Pressure [5] p= rE + 2 + r − 2 expansion of materials/Unable to
rE : Pose radius
explain the critical water content.
KE : Pose influence range
P0 : Osmotic pressure difference
Solute precipitation in salt solution
P0 = RT 1.1489t V: Molar volume of solution
Osmotic Pressure [6] V ln10( 273.1+t + R: Gas constant
accelerates F–T damage/The
1.33 × 10 t − 9.084−8 t3 )
− 5 2
T: Temperature
formation and release of pressure
cannot be quantified.
t: Icing temperature
Effect of water saturation on
Critical saturation concrete deterioration/Macro
No definite formula
theory [49] description, unable to explain the
micro mechanism.
σs : Crystal tail pressure
σc : Pressure in the middle of the crystal Shrinkage of air-entraining
Crystallization 
1 1

γ γ: Surface energy of crystal and liquid concrete at low
pressure theory [9] σs = 2γ rp − r , σc = r p −δ r p : Small pore diameter temperature/Extension of
r: Radius of the crystal hydrostatic pressure theory.
δ: Thickness of unfrozen water layer
Explains the transport of water and
the obvious increase of water
Micro-ice lens absorption rate during F–T/There
No definite formula
theory [10] is no theoretical expression, which
is essentially an extension of
osmotic pressure theory.

"  # σx : Stress on the ice Intuitively explains the spalling

R Tx bσxn exp −TQ T: Temperature phenomenon of concrete surface
Glue spall theory [59] σx = B( T ) ac − as − q dT
T b, n: Theoretical parameter after F–T/difficult to explain the
q= dT ac , as : Coefficient of thermal expansion internal damage.
dt

Constructing the relationship

ρl , ρc : Density of water and ice between macroscopic damage and
Theory of unsaturated (ρl −ρc )nc nl , nc : Relative volume fraction of microscopic characterization of
p= nl ρl n ρ
porous elasticity [61] kl
+ kc c
c
water and ice concrete during F–T/The
k l , k c : Bulk modulus of water and ice theoretical basis is too complex to
carry out numerical calculation.

2.2. Salt-Freeze Coupling

2.2.1. Mechanism of Chloride-F–T Damage
In the actual service environment of concrete, it is eroded by various salt ions. Chloride
is widely used in cold areas as a de-icing salt to remove snow from concrete pavements and
other outdoor platforms, and there is also a large amount of chloride in seawater [27,65].
The existence of chloride salts reduces the various properties of concrete F–T cycles. Some
scholars in the United States have found that the concrete at pavement joints in cold areas
deteriorates prematurely. The study found that this is due to the accumulation of de-icing
salt solution, owing to the failure of waterproof material at the joint, which leads to the
continuous entry of the solution into concrete to increase local water saturation. According
to the critical saturation theory, this leads to the rapid deterioration of concrete [66,67].
The chemical corrosion effects of different chlorides on concrete are significantly dif-
ferent [68]. When chloride salt penetrates the concrete, it produces Friedel’s salt [18,69,70],
such as that in the main chemical reactions between NaCl and cementitious materials, as
shown in Equations (1) and (2), respectively. The damage caused by NaCl to concrete
and the volume expansion of concrete when in a NaCl salt solution is caused by the crys-
tallization of Friedel’s salt. This type of crystallization pressure causes little damage to
Buildings 2022, 12, 1317 9 of 36

concrete, and NaCl has a limited effect on the durability and safety of plain concrete during
long-term action.

3CaO· Al2 O3 + Ca(OH )2 + 2NaCl + 10H2 O → Ca4 Al2 (OH )12 Cl2 ·4H2 O + 2NaOH (1)

Ca4 Al2 (OH )12 SO4 ·6H2 O + 2NaCl → Ca4 Al2 (OH )12 Cl2 ·4H2 O + Na2 SO4 + 2H2 O (2)
CaCl2 produces Friedel’s salt when it is with cementitious materials and reacts with CH
to form calcium oxychloride [71], as shown in Equation (3). Calcium oxychloride can cause
serious damage to concrete in the absence of air-entraining agents or auxiliary cementitious
materials [32]. The volume of calcium oxychloride is 203% larger than that of unreacted
Ca(OH)2 (CH), which may cause concrete to be damaged by excessive tensile stress [72].

CaCl2 + 3Ca(OH )2 + 12H2 O → 3Ca(OH )2 ·CaCl2 ·12H2 O (3)

The reaction of MgCl2 is similar to that of NaCl. It also reacts with Ca(OH)2 and calcium
silicate hydrate gel (C-S-H) to produce magnesium silicate hydrate (M-S-H) and Mg(OH)2
without a cementing ability, which leads to the rapid failure of concrete. Simultaneously,
MgCl2 and Mg(OH)2 also produce magnesium oxychloride under certain conditions [73,74],
as shown in Equations (4)–(6). A study has found that when concrete is exposed to different
chloride solutions in an F–T environment, the corrosion of concrete in CaCl2 is more serious.
The authors believe that this is caused by expansive calcium oxychloride, which causes
cracks in the concrete [75].

Ca(OH )2 + MgCl2 → Mg(OH )2 + CaCl2 (4)

C − S − H + MgCl2 → M − S − H + CaCl2 (5)

(3 or 5) Mg(OH )2 + MgCl2 + 8H2 O → (3 or 5) Mg(OH )2 · MgCl2 ·8H2 O (6)
Due to the different expansion properties of solutions and concrete during freezing,
concrete surface spalling and concrete cracks [76,77] are caused, which is called surface
scaling. This makes it easier for the solution to invade into the concrete (Figure 6a). When
the concentration of NaCl is 3%, the damage of the concrete reaches its maximum. This is
the result of the comprehensive action of osmotic pressure and hydrostatic pressure. When
the concentration of ions increases due to the freezing or evaporation of the solution when
it is entering the pores of the concrete, the ions may crystallize. For the crystallization
that appears on the surface of concrete, we call it ‘efflorescence’. As for the crystallization
phenomenon that occurs inside the pores, we call it ‘subflorescence’, which is an important
cause of concrete microcracks (Figure 6b). When the volume of ice increases, ions gather
due to osmotic pressure, and NaCl or sulfate crystals precipitate. In contrast, crystallization
has not been found in most studies because the concentration of salt ions that are used in
the experiment is not supersaturated. However, Xiao [37] et al. and Li [78] et al. found the
phenomenon of ion crystallization in their experiments.
The existence of chloride salt in F–T conditions will also cause the following haz-
ards [17,58,59,65]: the water retention and moisture absorption function of salt itself speeds
up the water absorption rate of concrete and shortens the time for it to reach the critical
water retention degree; the concentration difference occurs when the salt permeates from
the outside to the inside, and the difference in the icing rate of salt solution at different
concentrations simultaneously leads to a stress difference and a greater osmotic pressure;
the main function of de-icing salt is to eliminate snow, which causes snow to absorb a
lot of heat, which rapidly decreases the surface temperature of the concrete, accelerates
the freezing rate of supercooled water that is in the capillaries, increases the hydrostatic
pressure, and makes surface spalling more serious; in the process of constant circulation,
the expansion pressure that is caused by the repeated crystallization of salt in concrete due
to supersaturation leads to frost heave damage.
Buildings 2022, 12, x FOR PEER REVIEW 10 of 37

Buildings 2022, 12, 1317
crystallization has not been found in most studies because the concentration of salt ions
that are used in the experiment is not supersaturated. However, Xiao [37] et al. and Li
10 [78]
of 36
et al. found the phenomenon of ion crystallization in their experiments.

(a) (b)
Figure
Figure 6.
6. Physical
Physical erosion
erosion mechanism of salt
mechanism of salt ions.
ions. (a)
(a) Surface
Surfacescaling
scalingmechanism;
mechanism;(b)
(b)Salt
Saltcrystalliza-
crystalli-
zation mechanism.
tion mechanism.

The existence the

Accordingly, of chloride salt in F-Talso
F–T environment conditions will alsoeffect
has a negative causeonthe thefollowing
resistance hazards
of con-
[17,58,59,65]: the water retention and moisture absorption function of salt itself speeds up
crete to chloride-ion penetration. Some studies [29,79,80] have found that the permeability
the water absorption
of concrete rate of
increases after F–Tconcrete
cycles, and shortens
the level of thedamage
time forisitproportional
to reach the to critical water
the number
retention
of F–T cycles,degree;
which theisconcentration difference occurs
caused by the degradation of the when
concrete thesurface
salt permeates from The
pore structure. the
outside to theenters
salt solution inside,theand the difference
concrete through the in the icing rate
capillaries, andof the
saltlarge
solution
osmoticat different
pressurecon-and
centrations
crystallization simultaneously
pressure inside leadsthetoconcrete
a stress lead
difference
to newand a greater osmotic
microcracks. Moreover, pressure; the
water and
main function of de-icing salt is to eliminate snow, which causes snow to absorb a lot of
chloride ions accelerate the erosion that occurs [81]. The coupling effect of chloride and F–T
heat,
cycleswhich
also has rapidly decreases the
some advantages: thesurface
existence temperature
of chloride of saltthe concrete,
increases the accelerates
compressibilitythe
freezing rate of supercooled water that is in the capillaries, increases the hydrostatic
of ice and the freezing point of the water drops, which reduces the damage degree pres-
incurred
sure,
by theand makes[82].
concrete surface spalling more serious; in the process of constant circulation, the
Currently,
expansion pressure the damage mechanism
that is caused by theofrepeated
the chloride-F–T process
crystallization ofissalt
stillininconcrete
the qualitative
due to
research stage [79]. Some scholars
supersaturation leads to frost heave damage. [83–85] do not agree with the above research results, for
example, some scholars have found that the spalling of concrete
Accordingly, the F-T environment also has a negative effect on the resistance of con- surfaces has little to do
with the existence of salt. F–T damage does not always occur at
crete to chloride-ion penetration. Some studies [29,79,80] have found that the permeability3% concentration, and even
theconcrete
of presence of salt can
increases afterdelay the failure
F-T cycles, andtime of concrete.
the level of damage Theisdeformation
proportionaloftoconcrete
the num- at
low concentrations is mainly due to the action of water, and the
ber of F-T cycles, which is caused by the degradation of the concrete surface pore struc- effect of salt is gradually
strengthened only when the concentration is more than 15%. These disputes show that
ture. The salt solution enters the concrete through the capillaries, and the large osmotic
salt freezing is not only the result of a single factor, but also the result of the joint action of
pressure and crystallization pressure inside the concrete lead to new microcracks. More-
the salt solution, types of concrete, and environmental conditions, which cannot be fully
over, water and chloride ions accelerate the erosion that occurs [81]. The coupling effect
revealed by an exact model.
of chloride and F-T cycles also has some advantages: the existence of chloride salt in-
creases the compressibility
2.2.2. Mechanism of ice Damage
of Sulfate-F–T and the freezing point of the water drops, which reduces
the damage degree incurred by the concrete [82].
Concrete also suffers from sulfate erosion when it is affected by F–T cycles in winter
Currently, the damage mechanism of the chloride-F-T process is still in the qualita-
and early spring [86–88]. Sulfate erosion is divided into physical and chemical types [68,89,
tive research stage [79]. Some scholars [83–85] do not agree with the above research re-
90]. In terms of physical erosion, the external sulfate enters the concrete through the micro-
sults, for example, some scholars have found that the spalling of concrete surfaces has
cracks of the concrete, and the diffusion rate is accelerated if the external concentration is
little to do with the existence of salt. F-T damage does not always occur at 3% concentra-
greater than the internal concentration. Crystallization occurs when the solution concen-
tion, and even the presence of salt can delay the failure time of concrete. The deformation
tration in the pores reaches a supersaturated state. The crystallization expansion rates of
of
Naconcrete at low concentrations is mainly due to the action of water, and the effect of salt
2 SO4 and MgSO4 in a supersaturated solution are 311% and 11%, respectively [91–93].
is gradually strengthened
Salt crystallization will make onlythewhen the concentration
concrete fill the void andis more
make than
the15%. Thesedense,
concrete disputes
but
show
the concrete will be destroyed when the expansion pressure caused by continuousofcrys-
that salt freezing is not only the result of a single factor, but also the result the
joint actionexceeds
tallization of the salt
the solution, types
critical value ofoftheconcrete,
concreteand [94].environmental
The chemical erosion conditions, which
of concrete
cannot
by sulfatebe fully
can revealed
be divided by into
an exact
two model.
aspects. Sulfate reacts with the internal hydration
products of concrete. On the one hand, it produces expansive insoluble substances such
2.2.2. Mechanism
as ettringite of Sulfate-F-T
and gypsum, Damage
as shown in Equations (7) and (8), respectively, which fills the
Concrete
interior also suffers
of the concrete from
in the sulfate
early stageerosion when
but leads it is affected
to concrete by F-T cycles
deterioration when in winter
it exceeds
and earlyamount.
a certain spring [86–88]. Sulfate
On the other erosion
hand, is divided intoofphysical
the decomposition andCH
C-S-H and chemical types
under sulfate
erosion leads to a gradual loss of the cement shape, as shown in Equation (9). At low
temperatures [95–97], gypsum may form tobermorite (CaCO3 ·CaSO4 ·CaSiO2 ·15H2 O) with
compounds such as CH, silica, and calcium carbonate. The volume of the reaction product
expands, and cracks appear in the concrete to reduce its strength. In addition, when the
Buildings 2022, 12, 1317 11 of 36

temperature is less than 15 ◦ C, it may be attributed to the reaction of sulfate with C-S-H
and carbonate under the condition of exposure to sufficient water, which may lead to the
formation of white carbothiosilicate (CaSiO3 ·CaCO3 ·CaSO4 ·15H2 O, TSA) without a cemen-
tation ability. TSA itself does not cause the expansion. However, the TSA crystal nucleus
continues to form and consume C-S-H. This causes the concrete to lose its cementation
ability, and the structure gradually deteriorates and fails.

Na2 SO4 ·10H2 O + Ca(OH )2 = CaSO4 ·2H2 O + 2Na(OH ) + 8H2 O (7)

3CaSO4 ·2H2 O + 4CaO· Al2 O3 ·13H2 O + 14H2 O = 3CaO· Al2 O3 ·3CaSO4 ·32H2 O + Ca(OH )2 (8)

Na2 SO4 + Ca(OH )2 + 2H2 O = CaSO4 ·2H2 O + 2Na(OH ) (9)

The interaction mechanism between sulfate and F–T cycles is complicated [28,37,98];
the sulfate diffusion rate decreases at low temperatures, whereas the large pores created by
F–T cycles lead to increased sulfate permeability. Sulfate increases the compressibility of ice,
and the freezing point of water inside the concrete decreases; however, the crystallization
pressure that is produced by the supersaturated solution promotes the F–T damage of the
concrete. Sulfate crystal expansion, chemical corrosion, and a water frost heaving force
lead to sulfate-F–T coupling damage [24,35,99]. When the coupling erosion begins, the F–T
cycles cause microcracks on the concrete surface, and SO4 2− is quickly transferred to the
interior. The surface voids that are filled by ettringite and gypsum which are produced by
the reaction of SO4 2− with concrete decrease the porosity of concrete, and concrete becomes
dense, which restricts the effect of the cycles. With the deepening of the F–T erosion, the
growing micro-cracks accelerate sulfate erosion, while C-S-H and CH continue to decrease.
Finally, the crystallization pressure that is produced by sulfate, frost heave pressure, and
the expansion pressure of ettringite and gypsum acts on the pores of the concrete. Wang
et al. [38] proposed a united damage model and found that the corrosion products that
were produced by sulfate in the early stage protected the concrete, and that the cycles
caused damage. In the later stage, the physical and chemical actions of salt ions are the
first causes of concrete deterioration, while the F–T damage effect is weakened owing to
the loose internal structure of the concrete. For a low-concentration (3%) sodium sulfate
solution, owing to the slow production rate of corrosion products, its reinforcement effect
on concrete lasts longer [35]. Li et al. [24] analyzed the effect of sulfate types on F–T concrete
and found that magnesium sulfate produces corrosion products and converts CH into
gypsum, which reduces the alkalinity of concrete and further promotes the decomposition
of C-S-H. Therefore, the magnesium sulfate solution had a stronger corrosion effect than
the sodium sulfate solution did.
Generally speaking, salt freezing damage mainly leads to the surface spalling and
the internal deterioration of concrete, which is the result of salt crystallization, phase
transformation, and chemical corrosion [17,100]. Figure 7 reveals this process. Firstly, CH
is unstable during concrete freezing, resulting in a frost heave pressure and an osmotic
pressure. The increase in the ion concentration of unfrozen water in macropores causes CH
to migrate to macropores when it is under osmotic pressure. Salt ions react with CH to
form expansion products. At the same time, ice crystals gradually increase and squeeze
the pore wall. Subsequently, due to the increase in the crystallization pressure and osmotic
pressure in the large pore, the unfrozen water flows to the small hole, and micro-cracks also
appear in the small hole under the action of hydrostatic pressure. In the process of melting,
some of the erosion products decompose instantly (such as Friedel’s salt), ice crystals melt,
and CH from decomposition begins to precipitate, which may block the channel between
macropores and small pores. With each cycle, the more the internal crack space expands,
then the more serious the concrete deterioration is.
 of the concrete compact and delay the corrosion of chloride salt. However, when chloride
ion has penetrated into the concrete, sulfate has little effect on the corrosion rate of chlo-
ride ions [101]. On the other hand, the existence of chloride ion also delays sulfate corro-
sion. The reason is that chloride ions permeate into the concrete to fill the void with
Friedel’s salt, and chloride leads to the increase of the solubility of sulfate corrosion prod-
Buildings 2022, 12, 1317 12 of 36
ucts and the decrease of pore pressure [102,103]. Up to now, the research on the coupling
effect of chloride-sulfate-F-T cycle is still very limited [104].

Figure7.7. Principle
Figure Principleof
ofsalt
saltfreezing
freezingfailure
failuremechanism.
mechanism.

In the case of Testing

2.3. Microstructure the coupling erosion of chloride salt and sulfate, they have a certain
inhibitory effect [23,68]. The diffusion rate of sulfate is slower than that of chloride salt, but
2.3.1. SEM Observation
it can produce expansion products such as ettringite and gypsum to make the surface of
SEM observes
the concrete compactthe changes
and delay thein concrete morphology
corrosion of chloride and
salt. the processwhen
However, of microstructure
chloride ion
has penetrated into the concrete, sulfate has little effect on the corrosiondegradation
deterioration at the micro level to explain the mechanism of performance [24–
rate of chloride
26,79].
ions As On
[101]. shown in Figure
the other hand, 8, the
SEM images of
existence of chloride
concrete ion
in the
alsoinitial
delaysconditions without
sulfate corrosion.
visible
The microcracks
reason show that
is that chloride ionsthe concreteinto
permeate is dense. After F-T
the concrete to cycles,
fill the the expansion
void of the
with Friedel’s
salt, and chloride leads to the increase of the solubility of sulfate corrosion products and
the decrease of pore pressure [102,103]. Up to now, the research on the coupling effect of
chloride-sulfate-F–T cycle is still very limited [104].

2.3. Microstructure Testing

2.3.1. SEM Observation
SEM observes the changes in concrete morphology and the process of microstruc-
ture deterioration at the micro level to explain the mechanism of performance degrada-
tion [24–26,79]. As shown in Figure 8, SEM images of concrete in the initial conditions
without visible microcracks show that the concrete is dense. After F–T cycles, the expansion
of the corrosion products and ice in the pores causes the nanostructure of the concrete
to deteriorate [105]; pores and microcracks grow and expand, and the structure becomes
loose [36,80,106]. Wen et al. [107] reported a large amount of fibrous and coral-like C-S-H
gels at the beginning of the F–T erosion. With the extension of the F–T experiment, ettringite
began to appear. The expansion, caused by excessive ettringite, caused concrete cracking,
and visible pores and so, cracks appeared in concrete.
When concrete is subject to the coupling action of chloride-F–T cycles, SEM shows
that the void expands, microcracks develop into cracks, the concrete becomes loose and
porous, and the degree of the internal microdamage of the concrete when it is subject to
the coupling action is much more serious than a single erosion factor is [29,108]. For the
concrete that is under the condition of the F–T cycles in 4% NaCl solution (see Figure 9),
it was found that at the initial stage, there were a few micropores and microcracks; after
20 F–T cycles, the internal pores expanded and C-S-H was consumed; after 40 F–T cycles,
the C-S-H was flocculent, and the microcracks expanded; after 60 F–T cycles, the cracks
were connected with each other, the pore expanded, the C-S-H decreased, and the concrete
lost its bond property [109].
 corrosion products and ice in the pores causes the nanostructure of the concrete to deteri-
orate [105]; pores and microcracks grow and expand, and the structure becomes loose
[36,80,106]. Wen et al. [107] reported a large amount of fibrous and coral-like C-S-H gels
at the beginning of the F-T erosion. With the extension of the F-T experiment, ettringite
Buildings 2022, 12, 1317
began to appear. The expansion, caused by excessive ettringite, caused concrete cracking,
13 of 36

and visible pores and so, cracks appeared in concrete.

(a) (b)
Figure 8. Microstructure of concrete under different F-T cycles in water [79]. (a) 0 times 1000×; (b)
300 times 1000×.

When concrete is subject to the coupling action of chloride-F-T cycles, SEM shows
that the void expands, microcracks develop into cracks, the concrete becomes loose and
porous, and the degree of the internal microdamage of the concrete when it is subject to
the coupling action is much more serious than a single erosion factor is [29,108]. For the
concrete that is under the condition of the F-T cycles in 4% NaCl solution (see Figure 9), it
was found that at the initial stage, there were a few micropores and microcracks; after 20
F-T cycles, the internal pores expanded and C-S-H was consumed; after 40 F-T cycles, the
(a) (b)
C-S-H was flocculent, and the microcracks expanded; after 60 F-T cycles, the cracks were
connected
Figure 8. with
Figure 8. each other,
Microstructure
Microstructure of the poreunder
of concrete
concrete expanded,
under the
different
different C-S-H
F-T
F–T decreased,
cycles
cycles inin water
water and (a)the
[79].
[79]. (a) 0concrete
times
0 times lost
1000×;
1000 × ; (b)
its (b)
bond
300 300 property
times 1000×. [109].
times 1000× .

When concrete is subject to the coupling action of chloride-F-T cycles, SEM shows
that the void expands, microcracks develop into cracks, the concrete becomes loose and
porous, and the degree of the internal microdamage of the concrete when it is subject to
the coupling action is much more serious than a single erosion factor is [29,108]. For the
concrete that is under the condition of the F-T cycles in 4% NaCl solution (see Figure 9), it
was found that at the initial stage, there were a few micropores and microcracks; after 20
F-T cycles, the internal pores expanded and C-S-H was consumed; after 40 F-T cycles, the
C-S-H was flocculent, and the microcracks expanded; after 60 F-T cycles, the cracks were
connected with each other, the pore expanded, the C-S-H decreased, and the concrete lost
its bond property [109].
(a) (b)

(c) (d)
Figure 9. Microstructure
Figure
(a)
ofofconcrete
9. Microstructure 4% NaCl
concreteinin4% NaCl solution different(b)
underdifferent
solution under cycles[109].
cycles [109].(a)(a) 0 times
0 times
2000×;
2000(b) 20 times
×; (b) 2000×;
20 times 2000(c) 40 40
×; (c) times 2000×;
times (d)
2000× 6060
; (d) times 2000×.
times 2000×.

The SEM images of concrete that was frozen and thawed with different sulfate ions
have great differences in micro-morphology [88]. After F–T cycles in water (Figure 10),
the pore structure is loose and there is a small amount of acicular ettringite crystals in
the pores. Hydrated calcium silicate covers the surface of the spherical particles that are
not completely hydrated; the F–Ted concrete in 10% Na2 SO4 solution produces massive
amounts of acicular ettringite and parts of the C-S-H gel, which form a complex network
structure. It surrounds the cement-based surface, and the unhydrated particles basically
disappear, indicating that sodium sulfate causes deep erosion on cement-based materials;
the concrete in the 10%(c)
MgSO4 solution is similar to that in the sodium(d)sulfate solution, but
Figure 9. Microstructure
the ettringite of concrete in
content is significantly 4% NaCland
reduced, solution under
there are different
massive cycles
C-S-H gels.[109]. (a) 0 times
2000×; (b) 20 times 2000×; (c) 40 times 2000×; (d) 60 times 2000×.
 pores. Hydrated calcium silicate covers the surface of the spherical particles that are not
completely hydrated; the F-Ted concrete in 10% Na2SO4 solution produces massive
amounts of acicular ettringite and parts of the C-S-H gel, which form a complex network
structure. It surrounds the cement-based surface, and the unhydrated particles basically
disappear, indicating that sodium sulfate causes deep erosion on cement-based materials;
Buildings 2022, 12, 1317
the concrete in the 10% MgSO4 solution is similar to that in the sodium sulfate solution,
14 of 36

but the ettringite content is significantly reduced, and there are massive C-S-H gels.

(a) (b)

(c)
Figure 10.10.
Figure Effect of of
Effect different sulfate
different ions
sulfate onon
ions micro-morphology of of
micro-morphology concrete after
concrete F-TF–T
after [88]. (a) (a)
[88]. Water
Water
5000×;
5000(b) 10%10%
×; (b) SO24SO
Na2Na 5000×; (c) 10% MgSO4 5000×.
4 5000×; (c) 10% MgSO4 5000×.

From
From thetheresults
resultsof of
thetheSEMSEMtesting,
testing,under
under thethe
action ofof
action F-TF–Tcycles, thethe
cycles, pores
poresof of
thethe
concrete
concrete increased
increased and
and thethemicrocracks
microcracks expanded,
expanded, leading
leadingto to
loosening
loosening of of
thethe
concrete
concrete
microstructure
microstructure [110]. Pores
[110]. Pores and microcracks
and microcracks appeared
appeared in in
thethe
concrete
concreteafter chloride
after chloride ionion
infiltration.
infiltration. After saltsalt
After freezing cycles,
freezing a large
cycles, number
a large numberof large pore holes
of large and cracks
pore holes ap-
and cracks
peared. For the
appeared. For sulfate-F-T cycle, the
the sulfate-F–T researchers
cycle, found that
the researchers foundin the
thatearly stage
in the earlyof stage
the cycle,
of the
a large number of columnar or acicular ettringite crystals were formed at the edge of the
cycle, a large number of columnar or acicular ettringite crystals were formed at the edge
macropore, and ettringite played a filling role. After 200 cycles, ettringite filled the channelthe
of the macropore, and ettringite played a filling role. After 200 cycles, ettringite filled
and the concrete
channel and the began to produce
concrete began new microcracks.
to produce At the same At
new microcracks. time,
theitsame
was found
time, that
it was
in found
the low concentration
that (2%) Na2SO4(2%)
in the low concentration solution,
Na2 SO the morphology
4 solution, of the concrete
the morphology changed
of the concrete
little after the
changed cycle,
little afterwhile the high
the cycle, whileconcentration of Na2SOof
the high concentration 4 (5%)
Na2 SOhad an important
4 (5%) effect
had an important
on the morphology of the concrete. Hence, under the action of an F-T cycle and ion cou-
effect on the morphology of the concrete. Hence, under the action of an F–T cycle and
pling, due to the increase in the pore size and the cracks, the deterioration of the concretethe
ion coupling, due to the increase in the pore size and the cracks, the deterioration of
concretewhen
structure structure
it waswhen
underit was
theunder
couplingthe coupling
action was action
morewas more than
serious serious
thatthan that was
which which
was under the single action
under the single action [111,112]. [111,112].

2.3.2. Composition
2.3.2. Composition
TG-DSC, XRD, and EDS are commonly used testing methods for the quantitative
TG-DSC, XRD, and EDS are commonly used testing methods for the quantitative
analysis of corrosion products in concrete [28,113]. Low-density C-S-H, high-density C-S-
analysis of corrosion products in concrete [28,113]. Low-density C-S-H, high-density C-S-
H, and CH are the main hydration products, and their contents are closely related to the
H, and CH are the main hydration products, and their contents are closely related to the
concrete performance. Xie et al. [114] tested the content of three types of hydration products
of UHPC in F–T cycles using the statistical nanoindentation method and deconvolution
technique. It was found that after 1500 F–T cycles, the low-density C-S-H, high-density
C-S-H, and CH decreased by 10.58%, 14.56%, and 3.3%, respectively. Liu et al. [115]
analyzed the volume fraction of the components under different cycles using micro-CT and
nanoindentation technology and found that the initial C-S-H and pore volume fractions
were 71.8% and 5.6%, respectively. After 600 F–T cycles, the initial C-S-H and pore volume
fractions were 63.0% and 18%, respectively. The increase in the pore structure was the main
factor for the decline in the RDEM of the specimen.
Through the analysis of the composition of concrete under different sulfate-F–T condi-
tions [25], it is found that regardless of the type of sulfate solution, the contents of ettringite
 Buildings 2022, 12, 1317 15 of 36

and gypsum increased, whereas the concentration of silicate decreased. The amount of
corrosion products in a MgSO4 solution was higher than that in a Na2 SO4 solution. Brucite,
which caused by the reaction between MgSO4 and silicate, was also observed. These results
Buildings 2022, 12, x FOR PEER REVIEWindicate that the erosion of MgSO4 is more severe under F–T conditions. The diffraction 16 of 37
peak of ettringite is positively correlated with Na2 SO4 in the sulfate-F–T cycle test, and the
occurrence time of the diffraction peak of gypsum is negatively correlated with the sulfate
concentration. This proves that the sulfate concentration is beneficial for the corrosion of
0.00
concrete [110]. TheC-S-H
acicular crystals were mainly composed of ettringite after the 200th
F–T cycle, while columnar gypsum crystals began to appear after 300 F–T cycles. XRD
-0.01
analysis revealed that after 300 cycles, the diffraction peak of CH disappeared and CH
disappeared completely, while the diffraction peaks of ettringite and gypsum reached
-0.02highest points [35,37]. Wang et al. [17] used XRD and thermal analysis to determine
their FS
that the amount of CH was inversely proportional Cc to the number of F–T cycles in NaCl.
-0.03
DTG (%/℃)

Qiao et al. [65] carried out the thermal separation of F–T damaged and undamaged mortars
using a de-icing salt (Figure 11). At 400–500 ◦
CH C, the CH content of the damaged mortar was
-0.04
1/12 that of the undamaged mortar. Combined thermal analysis, EDS, and XRD and found
that although the microcracks that were produced in the chloride-F–T environment could
-0.05 sufficient water, the amount of CH and C-S-H that were produced by volcanic ash
provide
FS+MH
was not high, and the gel was loose owing to a low temperature, ion erosion, crystallization
-0.06
pressure, and other factors [116]. The analysis of the phase composition in the F–T cycles
shows that C-S-H is constantly decomposed and new pores appear. The existence of salt
erosion
-0.07 leads to the further consumption of C-S-H, significantly reducing the content of
Ettr Undamaged Mortar
cement hydration products and accelerating the deterioration of the microstructure of
concrete.
Damaged Mortar
The existence of chloride and sulfate leads to the accelerated decomposition of
-0.08
0
C-S-H and 200
CH in concrete, 400 ettringite,
forming 600 gypsum, 800
and unstable1000
Friedel’s salt. For each
cycle, more corrosion products Temperature
are formed,(℃)
and to a certain extent, the expansion pressure
that causes cracks in the concrete is increased, and this accelerates the entry of the solution,
and as a result, the concrete fails [117,118].

Figure 11. DTG data of mortar before and after F–T cycles [65].
Figure 11. DTG data of mortar before and after F-T cycles [65].
2.3.3. Pore Structure
The Structure
2.3.3. Pore pore structure is the main factor affecting the durability and safety of concrete.
The pores of concrete are generally distributed in the range of 3–100,000 nm, and the
Thethat
pores porearestructure is the
smaller than 50main factor
nm are affecting
considered to the
havedurability
little effectand
on safety
the F–Tofproper-
concrete.
The pores of concrete are generally distributed in the range of 3–100,000 nm, and the
ties [119,120]. The experimental methods also differed according to the pore size. Methods pores
that are smaller than 50 nm are considered to have little effect on the F-T properties
[119,120]. The experimental methods also differed according to the pore size. Methods for
testing the pore structure include optical microscopy, MIP, CT, NMR, and nitrogen ad-
sorption [121–123].
Zhang et al. [124] explored the change in porosity of concrete with different water–
Buildings 2022, 12, 1317 16 of 36

for testing the pore structure include optical microscopy, MIP, CT, NMR, and nitrogen
adsorption [121–123].
Zhang et al. [124] explored the change in porosity of concrete with different water–
cement ratios (w/c) before and after F–T cycles using the MIP technique. The porosity with
a w/c of 0.4 was increased by 2.7% after 50 cycles, whereas that of concrete with 0.6 w/c
increased by 7% after 25 cycles. It can be observed that the lower the w/c, then the smaller
the change in the concrete pore structure after cycling is (Figure 12). There was a linear
correlation between porosity and the number of cycles, and the correlation between the
two linear fitting curves was excellent. The peak diameters of the pore size distributions of
concrete that was mixed with nano-silica, nano-TiO2, and polypropylene fiber are 30 nm,
40 nm, and 50 nm, respectively, whereas ordinary concrete has two peak diameters of 80 nm
and 3000 nm [99]. Other scholars [33] used MIP to test the pore structure of concrete with
different auxiliary cementitious materials; the shape of the pore structure curves of the
concrete did not change after the F–T cycles, i.e., the macropores (>1000 nm) increased, the
transitional pores (10–100 nm) decreased, and other pores changed slightly. These results
indicate that some transition pores deteriorated seriously under F–T cycles and were torn
into macropores, and thus, the pore structure became loose. However, other scholars have
expressed different opinions. Sun et al. [125] used the NAM method to test the MIP of
concrete with a different diatomite content after F–T. The F–T damage was most apparent
in the pore structure of small concrete pores (≤100 nm).
CT [20–22,122] technology is often used to detect changes in concrete porosity. The
X-ray absorption coefficients of the different concrete component densities were different.
The internal damage incurred by the concrete can be analyzed according to its CT grey value,
and the pores are extracted according to the three-dimensional reconstruction technique to
calculate the pore characteristic parameters.
Liu et al. [115] analyzed the internal pores of shotcrete using micro-CT technology and
performed a 3D reconstruction (Figure 13). The cracks are shown in red, and the micropores
are shown in blue. The micropores in the concrete mainly appeared near the initial defects
in concrete that did not undergo F–T cycles. With the deepening of the F–T deterioration,
the micropores began to appear far away from the cracks, some pores began to connect,
and the cracks began to expand. Finally, the size of the micropores increased, and most of
the micropores penetrated each other. The expansion of microcracks and micropores were
the key factors for the F–T deterioration of concrete.
Zheng et al. [126] used CT technology and 3D reconstruction to integrate pores into
small pores (V < 0.1 mm3 ), mesopores (0.1 ≤ V ≤ 1 mm3 ), and macropores (V > 1 mm3 ),
according to their pore volume. The proportions of small, medium, and large pores were
47.3%, 39.8%, and 12.9%, respectively, before the F–T cycles, and 35.8%, 45.7%, and 18.5%,
respectively, after 50 cycles. The proportion of small pores was decreased, whereas that of
large and middle pores was increased. Li et al. [20] found a linear relationship between the
increment in porosity and the number of F–T cycles using the CT scanning of mortar in 4%
NaCl. In addition, it is found that the shape factor of pores is less than 1 (between 0.2 and
0.4), which shows that these pores are not spherical. The application of F–T cycles cause
concrete pores to be torn, making them more irregular [21]. Through the reconstruction
of the concrete pore structure that was scanned using CT, it was found that the concrete
porosity (>0.1 mm) increased slowly at first, then increased rapidly, and finally slowed
down gradually [127]. After 25 cycles, the porosity only increased by 0.18% after 50, 75, and
100 cycles. Small pores (0–0.5 mm2 ) had increased at first, then they decreased slightly, and
finally they increased rapidly. This may be because larger pores were cut by cracks to form
smaller pores, while mesopores (0.5–5 mm2 ) were increasing. In addition, it was found
that 3DP technology can simulate the actual axial compression behavior of a concrete well.
Chen et al. [128] supported this result.
NMR has the advantages of being nondestructive, fast, and accurate; therefore, it is
often used to obtain the pore structure parameters of concrete [24,129,130]. Liu et al. [131]
investigated the effect of F–T damage on the pore size distribution of cement mortar for
Buildings 2022, 12, 1317 17 of 36

the first time, using NMR. The first spectral peak (approximately 1 ms) was a small pore,
whereas the second spectral peak (approximately 40–60 ms) was a large pore. The F–
T cycles caused the spectral curve to expand outward as a pore, and the spectral peak
increased by approximately 25% after 100 cycles, whereas the macropore peak increased
by 100%. The F–T cycles caused the micropores in the mortar to change to large pores
and the emergence of many new micropores. Wang et al. [129] carried out more detailed
NMR tests of mortar pore structures and divided the pores into micropores (<5 nm), small
pores (5 nm < r < 20 nm), mesopores (20 nm < r < 100 nm), and macropores (>100 nm), and
they considered that the degree of harm had increased. Figure 14a shows the pore size
distribution trend of mortar with 0.45 w/c, that underwent F–T cycles. The macropore
porosity increased rapidly. However, the other pores did not change significantly, indicating
that F–T cycles mainly lead to the upgrading of mesopore pore cracking to macropores,
but it had little effect on small pores. In a study [132], it was also found by using low-
frequency NMR, that after 200 cycles, the porosity of concrete increased by 53.49%, and the
number of harmless pores (<20 nm), medium pores (20–200 nm), and macropores (>200
nm) had increased (Figure 14b). The proportion of harmless pores decreased from 84.9% to
approximately 50%, whereas the proportion of medium and large pores increased rapidly
from 15.1% to 50%. The deterioration that was caused by the F–T cycles mainly caused
the micropores to gradually become medium-sized pores and large pores. Shen et al. [133]
investigated the effect of F–T cycles on concrete porosity by using NMR and found that
there was an abrupt change in the changing trend of concrete porosity in 10 cycles; the
porosity of concrete increased by 12% in the first 10 cycles and 22% after 10–20 cycles. The
pores were divided into micropores (<10 nm), mesopores (10–100 nm), and macropores
(>100 nm). After 20 F–T cycles, the micropores and mesopores were increased by 62%
and 155%, respectively, while the macropore increase had exceeded 100%. The F–T cycles
mainly affected the mesopores and macropores of the concrete.

7
1-w/c=0.45-(Zhang,2021)
2-w/c=0.55-(Zhang,2021)
6 3-w/c=0.50-(Li,2018)
R2=0.99 4-w/c=0.55-(Tian,2018)
Linear fitting for 1
5 Linear fitting for 2
Linear fitting for 3
Linear fitting for 4
R2=0.95
Porosity(%)

3
R2=0.99

2
R2=0.96
1

0
0 50 100 150 200 250
Number of F-T cycles
Figure 12.Variation
Figure 12. Variation of porosity
of porosity after
after F–T F-T under
cycles cyclesdifferent
under different water–cement
water–cement ratios.
ratios [20,127,131].
 and performed a 3D reconstruction (Figure 13). The cracks are shown in red, and the mi-
cropores are shown in blue. The micropores in the concrete mainly appeared near the
initial defects in concrete that did not undergo F-T cycles. With the deepening of the F-T
deterioration, the micropores began to appear far away from the cracks, some pores began
to connect, and the cracks began to expand. Finally, the size of the micropores increased,
Buildings 2022, 12, 1317 18 of 36
and most of the micropores penetrated each other. The expansion of microcracks and mi-
cropores were the key factors for the F-T deterioration of concrete.

Buildings 2022, 12, x FOR PEER REVIEW Figure 13. 3D reconstruction model of cracks and pores in shotcrete that underwent different
19 of 37F-T
Figure 13. 3D reconstruction model of cracks and pores in shotcrete that underwent different F–T
cycles [115].
cycles [115].

Zheng et al. [126] used CT technology and 3D reconstruction to integrate pores into
1.0 300
small
0.9
pores
5 cycles(V < 0.1 mm³), mesopores (0.1 ≤ V ≤ 1 mm³), and macropores 0(V
cycles> 1 mm³),
10 cycles 50 cycles
0.8 15 cycles 250
100 cycles
20 cycles 150 cycles
Fractional porosity(%)

0.7 30 cycles
200 200 cycles
0.6 40 cycles 225 cycles

Amplitude
0.5 150

0.4
100
0.3

0.2
50
0.1

0.0 0
0.01 0.1 1 10 100 1000 10000 0.01 0.1 1 10 100 1000 10000
Pore radius(nm) Time(ms)

(a) (b)
Figure 14. Change
Figure of pore
14. Change structure
of pore after
structure F-TF–T
after cycles. (a) NMR
cycles. test test
(a) NMR results of mortar
results [129];
of mortar (b) NMR
[129]; (b) NMR
test test
results of concrete
results [133].
of concrete [133].

TheThedegree
degree of F-T damage
of F–T damage mainly depends
mainly depends on the pore
on the structure,
pore structure, andand the the
pore sizesize
pore
of concrete
of concrete varies from
varies 0.5 0.5
from nmnm to centimeter
to centimeter [134]. TheThe
[134]. sizesize
of the
of theporesporeshashas a decisive
a decisive
effect on on
effect thetherolerole
of water freezing.
of water freezing. First of all,
First thethe
of all, surface
surfaceadsorption
adsorption forceforcebetween
between thethe
water and the pore wall increases with the decrease of the pore size, so the pore diameter
water and the pore wall increases with the decrease of the pore size, so the pore diameter
is inversely
is inversely proportional
proportional to the freezing
to the freezingpoint. Secondly,
point. Secondly, thethe
smaller
smaller the theporeporesizesize
is, then
is, then
the the
lower
lowerthe the
humidity
humidity requirement
requirement of the pore
of the is, and
pore the the
is, and easier it isitfor
easier is itfor
toitabsorb water.
to absorb water.
It isItfound
is foundthatthat
when whenthe the
porepore is 0.01 mm,mm,
is 0.01 the freezing
the freezing temperature
temperature of water is less
of water is than -
less than
◦ C when the relative humidity is 90% to 99%. When the pore is greater than 0.1 mm
20 °C−20when the relative humidity is 90% to 99%. When the pore is greater than 0.1 mm
◦ C [135]. On the other
andand thethe
relative humidity
relative humidity is more
is morethan 99%,
than 99%,it can be be
it can frozen
frozenat at
−4~0
−4~0 °C [135]. On the other
hand, thethe
hand, value of the
value w/cw/c
of the has ahas great influence
a great influenceon theon pores because
the pores becausethe the
hydration
hydration reaction
reaction
consumes the water of the pores and fills the pores, resulting in an increase in the number
consumes the water of the pores and fills the pores, resulting in an increase in the number
of gel pores.
of gel TheThe
pores. pores almost
pores almost disappear
disappear when when thethew/cw/c
is less thanthan
is less 0.360.36
[136]. [136].
MIP,MIP,CTCT scanning,
scanning, NMR,NMR, andand other techniques
other techniques werewereused to analyze
used to analyze thethechanges
changes in in
the concrete pore structure [137]. During cycling, concrete porosity is proportional to thethe
the concrete pore structure [137]. During cycling, concrete porosity is proportional to
number
number of cycles.
of cycles. Many Many researchers
researchers have have explored
explored the the changing
changing trend trend of characteristic
of characteristic
parameters, such as pore size distribution and pore shape,
parameters, such as pore size distribution and pore shape, with F-T cycles. First, the with F–T cycles. First,
pro-the
proportion of mesopores and macropores increased,
portion of mesopores and macropores increased, micropores continued to expand, mi- micropores continued to expand,
micropores
cropores developeddeveloped into microcracks,
into microcracks, and microcracks
and microcracks expandedexpanded
into macroscopicinto macroscopic
cracks
and pores. Second, the pore structure deteriorated slowly during the early the
cracks and pores. Second, the pore structure deteriorated slowly during early
cycles. cycles.
With
With the expansion of the pores, water entered completely, and the porosity of the concrete
the expansion of the pores, water entered completely, and the porosity of the concrete
increased rapidly. After 200 F–T cycles, the pore structure deteriorated significantly [132],
increased rapidly. After 200 F-T cycles, the pore structure deteriorated significantly
and the growth slowed after the basic failure of the concrete. The pores in the concrete were
[132], and the growth slowed after the basic failure of the concrete. The pores in the con-
round when they were not frozen or thawed. The pores of the concrete were torn under the
crete were round when they were not frozen or thawed. The pores of the concrete were
torn under the action of F-T, and the pore shape evolved in an irregular direction. Hence,
it is necessary to optimize the w/c and material ratio in order to obtain the best pore struc-
ture.

2.3.4. Microcracks
 Buildings 2022, 12, 1317 19 of 36

action of F–T, and the pore shape evolved in an irregular direction. Hence, it is necessary to
optimize the w/c and material ratio in order to obtain the best pore structure.

2.3.4. Microcracks
The F–T cycles no longer solely deteriorated the pore shape of concrete; however,
they also expanded the preliminary microcracks of concrete and had produced new mi-
crocracks [138]. There were some micropores and a small number of microcracks in the
concrete itself, and the width of the microcracks was approximately 5–10 µm. With an 20 of 3
Buildings 2022, 12, x FOR PEER REVIEW
increase in the number of cycles, microcracks had started to develop. When a massive
range of microcracks increased, the mechanical properties of concrete was decreased, and
the transmission performance was increased [139].
respectively.
The propagationF-T damage led to awas
of microcracks rapid increase inanalyzed
quantitatively microcracks
usingin the concrete,
a scanning elec- and th
width was also increased. Liu et al. [141] used convolution neural network technology t
tron microscope and image processing technology [140]. After 300 cycles, the maximum
segment
crack length CT(MCL)
scan images
and maximum and performed
crack width a three-dimensional
(MCW) increased byreconstruction.
114.8% and 72.3%, It was dis
covered that after 0, 300, and 600 cycles, the length of the micro-cracks in the concrete wa
respectively. F–T damage led to a rapid increase in microcracks in the concrete, and the
width was also increased. Liu et al. [141] used convolution neural network technology
172.5 μm, 323.9 μm, 532.0 μm, respectively, and the number of micro-cracks per unit are
to segment CT scan images and performed a three-dimensional reconstruction. It was
was 84,112,214. Every 300 cycles, the number of microcracks was increased by 34% and
discovered that after 0, 300, and 600 cycles, the length of the micro-cracks in the concrete
91%.
was Theµm,
172.5 F-T323.9
cyclesµm,lead
532.0toµm, therespectively,
enlargement andand initiation
the number of concrete microcracks.
of micro-cracks per unit A
shown
area wasin Figure 15,
84,112,214. Li et300
Every al. cycles,
[34] extracted
the number the ofdistribution
microcrackscharacteristics
was increased by of concrete
34% mi
crocracks in the cycles using a fluorescence microscope; when
and 91%. The F–T cycles lead to the enlargement and initiation of concrete microcracks. As the RDEM was from 1 t
0.4, the
shown length15,density
in Figure andextracted
Li et al. [34] volumethe density of microcracks
distribution characteristicswere increased
of concrete micro-by 0.17
mm/mm
cracks 2 and
in the 0.295%,
cycles using arespectively. Both are linearly
fluorescence microscope; when the related
RDEMtowas thefrom
RDEM, indicating
1 to 0.4, the tha
2 and
the formation and development of microcracks are closely related to the degree of the F
length density and volume density of microcracks were increased by 0.175 mm/mm
0.295%, respectively. Both are linearly related to the RDEM, indicating that the formation
T damage of the concrete. The microcracks of abnormal saturated specimens after cyclin
and development of microcracks are closely related to the degree of the F–T damage of the
were analyzed by means of three-dimensional X-ray and an acoustic emission technique
concrete. The microcracks of abnormal saturated specimens after cycling were analyzed by
It wasoffound
means that the volume
three-dimensional X-rayofand microcracks
an acousticexpanded with the increase
emission technique. It was foundin the
thatF-T cycle
andvolume
the the formation of microcracks
of microcracks expanded with wastheclosely related
increase in thetoF–T
saturation.
cycle, andConcrete microcrack
the formation
with 95% saturation were distributed in all components, whereas
of microcracks was closely related to saturation. Concrete microcracks with 95% saturation the 75% saturation o
concrete
were only found
distributed microcracks whereas
in all components, in the ITZ.the The
75% critical saturation
saturation of concretevalue
onlyoffound
concrete wa
85% [142].
microcracks in the ITZ. The critical saturation value of concrete was 85% [142].

Figure15.
Figure 15.Concrete
Concrete micro-crack
micro-crack [34].[34].

Liu[143]
Liu [143]
andand Dong
Dong [144,145]
[144,145] used used CT technology
CT technology to find
to find that that theinincrease
the increase micro- in mi
crocracks after F-T cycles changes the bending degree and macroscopic crackoflength
cracks after F–T cycles changes the bending degree and macroscopic crack length the of th
concrete, which causes the fracture path to change from a straight line to a bending path,
concrete, which causes the fracture path to change from a straight line to a bending path
and therefore, the crack resistance of concrete decreases. Luo et al. [146], through nano-CT
and therefore, the crack resistance of concrete decreases. Luo et al. [146], through nano
scanning, found that under the initial conditions, the surface of the concrete was intact,
CT scanning,
and the overallfound
defectsthat under
were few. the initial
After conditions,
500 cycles, many the surface of
microcracks the concrete
appeared aroundwas intact
the aggregate and extended into the cement paste. After 700 F–T cycles, microcracks were around
and the overall defects were few. After 500 cycles, many microcracks appeared
the aggregate and extended into the cement paste. After 700 F-T cycles, microcracks wer
found in all components, indicating that the F-T cycles destroy the matrix and the aggre
gate. In a study [147], it was found that there were also microcracks in the surface and
interior of the macropores in concrete, which may also be due to concrete pore tearin
Buildings 2022, 12, 1317 20 of 36

found in all components, indicating that the F–T cycles destroy the matrix and the aggregate.
In a study [147], it was found that there were also microcracks in the surface and interior
of the macropores in concrete, which may also be due to concrete pore tearing which was
precipitated by applying a hydrostatic stress and a freezing pressure.
F–T cycles accelerate the growth and propagation of microcracks in concrete, which
inevitably influences the macroscopic properties of concrete. In the existing research, the
microcrack information of concrete during F–T cycles is extracted by microscopy and
CT reconstruction technology; the evolution process of concrete microcracks is analyzed
qualitatively or quantitatively, and the relationship is established between the processes
Buildings 2022, 12, x FOR PEER REVIEW
of change undergone by the concrete’s macroscopic properties, and the deterioration 21 of 37
mechanism of the concrete during these cycles is revealed. In addition, the w/c also has an
effect on the microcracks of concrete. With the increase of w/c, there are more initial defects
in concrete and the crack width increases. The microcracks expand under the action of F–T,
Therefore, low water-cement ratio concrete can have better freeze-thaw resistance
and different pores (10~50 µm) are connected, which leads to the deterioration of pores.
[119,133].
Therefore, low water–cement ratio concrete can have better freeze–thaw resistance [119,133].
2.3.5.
2.3.5. Interfacial
Interfacial Transition
Transition Zone
Zone
Concrete
Concrete is a composite phase
is a composite phase composed
composed of of different
different engineering
engineeringmaterials,
materials,namely,
namely,
aggregate, paste, and ITZ. Owing to the micro-zone bleeding effect
aggregate, paste, and ITZ. Owing to the micro-zone bleeding effect in the formation in the formation pro-
process
cess of concrete,
of concrete, the porosity
the porosity of thisofarea
thisisarea
high,iswhich
high, iswhich is thelink
the weak weak linkconcrete
in the in the concrete
strength
strength chain [148,149], and is usually the site of the beginning of pores
chain [148,149], and is usually the site of the beginning of pores and microcracks in concrete and microcracks
in concrete
after after F-T
F–T damage damage
[150]. [150]. The microcracks
The microcracks in the ITZ can in the ITZ can
account foraccount
more thanfor more
70% ofthan
the
70%
total matrix microcracks [34], and can be used as a channel to make it easier foreasier
of the total matrix microcracks [34], and can be used as a channel to make it for
external
external solutions to invade the interior and accelerate the deterioration
solutions to invade the interior and accelerate the deterioration of concrete under the of concrete under
the action
action of F-T
of F–T [151,152].
[151,152]. In the
In the initial
initial statestate (Figure
(Figure 16a),16a), the ITZ
the ITZ produced
produced many many
porespores
and
and microcracks
microcracks because
because of initial
of its its initial defects.
defects. In In the
the processofofF–T
process F-Tcycles,
cycles,the
the ITZ
ITZ produces
produces
many
many newnewmicrocracks
microcracks(Figure
(Figure 16b),16b), microstructure
microstructure deterioration,
deterioration, ITZ thickness
ITZ thickness in-
increases,
creases, and strength decreases [153]. Qiao et al. [27] quantified the
and strength decreases [153]. Qiao et al. [27] quantified the microcracks in concrete undermicrocracks in con-
crete under
different different of
conditions conditions of deicing
deicing salts-F–T salts-F-T
erosion erosion
using using microscope
an optical an optical microscope
(OM) and
(OM)
foundandthatfound
the ITZthat the main
is the ITZ iszone
the main zone of microcracks.
of microcracks.

Figure
Figure 16.
16. Deterioration
Deteriorationmechanism
mechanismofofITZ ITZbefore
beforeand
andafter F-T
after cycles
F–T [113].
cycles (a) ITZ
[113]. initial
(a) ITZ state;
initial (b)
state;
Deterioration of ITZ
(b) Deterioration afterafter
of ITZ F-TF–T
cycles.
cycles.

Microhardness
Microhardness testing
testing and
and nanoindentation
nanoindentation technology
technology are are the
the main
main methods
methods that that
are
are used
used to
to characterize
characterize the
the thickness
thickness ofof the
the ITZ.
ITZ. Yang
Yang et
et al.
al. [140]
[140] found
found that
that after
after 00 cycles,
cycles,
225
225 cycles,
cycles, and
and 300
300 cycles,
cycles, the
the ITZ
ITZ thickness
thickness ofof concrete
concrete was
was 2020 μm,
µm, 40
40 μm,
µm, andand 50 50 μm,
µm,
respectively, and the
respectively, and the hardness
hardness waswas decreased
decreased significantly.
significantly. After
After cycling,
cycling, microcracks
microcracks had had
first appeared around the aggregate [146]. Xie et al. [107] [107] used
used nanoindentation
nanoindentation to analyze
analyze
the performance
performance evolution
evolution of the ITZ after the F–T F-T cycles. After 0 and 1500
After 0 and 1500 cycles, the
concrete ITZ thicknesses were 22 μm and 60 μm, respectively. Lyu et al. [116] explored
concrete ITZ thicknesses were 22 µm and 60 µm, respectively. Lyu et al. [116] explored
the
the performance
performance evolution
evolution of
of aa concrete ITZ under
concrete ITZ under chloride-F–T
chloride-F–T conditions.
conditions. After
After 140
140 F–T
F-T
cycles,
cycles, the
the aggregate
aggregate andand mortar
mortar gradually
gradually separated,
separated, and
and the
the ITZ
ITZ width
width increased
increased fromfrom
42 to 76 μm. In a study [113], after 200 F-T cycles, the ITZ thickness of cement models 32.5,
42.5 and 52.5 increased by 25%, 20%, and 18%, respectively, which may be related to dif-
ferences in the cement hydration process. As shown in Figure 17, the ITZ indentation
modulus of shotcrete was 30% lower than that of cement slurry when using nanoindenta-
 Buildings 2022, 12, 1317 21 of 36

42 to 76 µm. In a study [113], after 200 F–T cycles, the ITZ thickness of cement models
32.5, 42.5 and 52.5 increased by 25%, 20%, and 18%, respectively, which may be related to
differences in the cement hydration process. As shown in Figure 17, the ITZ indentation
modulus of shotcrete was 30% lower than that of cement slurry when using nanoindentation
and CT technology. At 0–300 cycles and 300–600 cycles, the ITZ width increased by 20%
Buildings 2022, 12, x FOR PEER REVIEW
and 27.7%, respectively. After 600 cycles, a portion of the aggregate was detached 22 of 37
from
the paste. The permeability of the ITZ was positively correlated with the number of F–T
cycles [115,133,141].

(a)

(b) (c)
Figure
Figure17.
17.Changes
Changes of ITZwidth
of ITZ widthand
and elastic
elastic modulus
modulus under
under different
different F-T (a)
F–T [115]. [115]. (a) 0(b)cycle;
0 cycle; (b) 300
300 cycles;
cycles; (c) 600
(c) 600 cycles.cycles.

Hao
Haoetetal.
al.[154]
[154]studied
studied the
the performance
performance of of the
thenew
newvs.
vs.old
oldITZ
ITZofofrecycled
recycledconcrete
concrete
under
underthe
theconditions
conditions ofof chloride-F-T erosionand
chloride-F–T erosion andfound
foundthat
that
thethe
oldold
ITZITZ
hashas higher
higher poros-
porosity
ity and more cracks after erosion, and the new transition zone mortar has a higher strength
and more cracks after erosion, and the new transition zone mortar has a higher strength
and
anda astronger
strongercorrosion
corrosion resistance.
resistance. Zou
Zou et al. [147]
[147] analyzed
analyzedthe theITZITZporosity
porosityofofsilane-
silane-
modified
modifiedrecycled
recycledconcrete
concrete after
after F-T
F–T cycles using backscattering
cycles using backscatteringelectron
electronmicroscopy
microscopy and
and
found that the surface-modified concrete had the lowest ITZ porosity. The ITZ of concrete
found that the surface-modified concrete had the lowest ITZ porosity. The ITZ of concrete
changedafter
changed afteradding
addingsteel
steelfiber
fiber during
during the
the cycles,
cycles, and
andthe
thedifference
differenceininthermal
thermalexpansion
expansion
between the steel fiber and matrix caused the surrounding
between the steel fiber and matrix caused the surrounding ITZ to crack and ITZ to crack and produce
produce mi-
micropores [155]. Pang et al. [156] explored the effects of different types of aggregates on
cropores [155]. Pang et al. [156] explored the effects of different types of aggregates on the
the F–T resistance of a concrete ITZ. Using EDS and nanoindentation, it was found that the
F-T resistance of a concrete ITZ. Using EDS and nanoindentation, it was found that the
width of ITZ in NA, SSA, and CSA concrete was 42.6 µm, 37.6 µm, and 45 µm, respectively,
width of ITZ in NA, SSA, and CSA concrete was 42.6 μm, 37.6 μm, and 45 μm, respec-
and the Vickers hardness was 27.59, 31.65, and 43 respectively. After 60 cycles, the RDEM
tively,
of NA,and theand
SSA, Vickers
CSAhardness was 27.59,
concrete were 31.65,and
80%, 52%, and19%,
43 respectively.
respectively.After
Sicat60
et cycles, the
al. [157]
RDEM
examined the deformation behavior of the ITZ during F–T cycles by preparing artificialal.
of NA, SSA, and CSA concrete were 80%, 52%, and 19%, respectively. Sicat et
[157]
ITZ examined
specimens,the deformation
as shown behavior
in Figure 18. Theofresults
the ITZ during
show that F-T cycles by
the mortars preparing
and aggregates arti-
ficial ITZ specimens, as shown in Figure 18. The results show that the mortars and aggre-
gates are undeformed, while the deformation of the ITZ increases significantly during the
cycles. The microscopic observation results reveal that the deformation behavior of the
ITZ is closely related to the occurrence and development of microcracks. With the increase
in the number of cycles, the proportion of pores in the ITZ increases gradually. The coa-
Buildings 2022, 12, 1317 22 of 36

are undeformed, while the deformation of the ITZ increases significantly during the cycles.
The microscopic observation results reveal that the deformation behavior of the ITZ is
closely related to the occurrence and development of microcracks. With the increase in the
number of cycles, the proportion of pores in the ITZ increases gradually. The coalescence
and expansion of pores increase the thickness of the ITZ. The F–T cycles will widen the
overall thickness of the weak band ITZ, resulting in a decrease in the interfacial bonding
Buildings 2022, 12, x FOR PEER REVIEW 23 of 37
performance between the aggregate and the cement paste. Therefore, the macroscopic
mechanical properties of the concrete deteriorate [116].

ITZ
5000 Mortar
Aggregate

0
Strain(μ)

-5000

-10000

-15000
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Time(minutes)

Figure18.
Figure 18.Measurement
Measurementof
ofITZ
ITZdeformation
deformationduring
duringF–T
F-Tcycles
cycles[157].
[157].

3.3.Modeling
ModelingforforConcrete
ConcreteininF–T
F-T Environments
Environments
Differentcharacterization
Different characterization indices
indices can
can bebeobtained
obtainedby bytesting
testingthe deterioration
the deteriorationperfor-
per-
mance of of
formance F-T concrete.
F–T A damage
concrete. A damage evolution
evolutionmodel
model of of
concrete under
concrete F-TF–T
under cycles was
cycles es-
was
tablished by quantifying these data. It plays a key role in evaluating the frost resistance
established by quantifying these data. It plays a key role in evaluating the frost resistance
andpredicting
and predictingthe
thedeterioration
deteriorationprocess
processofofconcrete
concrete[158].
[158].
3.1. Damage Model for RDEM
3.1. Damage Model for RDEM
Mass loss, relative strength, and RDEM are common damage indices used when eval-
Mass loss, relative strength, and RDEM are common damage indices used when eval-
uating the degree of F–T damage of concrete. RDEM is the most common nondestructive
uating the degree of F-T damage of concrete. RDEM is the most common nondestructive
real-time testing technique for analyzing the degree of internal damage of the coagula-
real-time testing technique for analyzing the degree of internal damage of the coagulation
tion [159]. Combined with the change in the RDEM and material damage theory, many
[159]. Combined with the change in the RDEM and material damage theory, many schol-
scholars have established the damage evolution equation of concrete under F–T cycles
ars have established the damage evolution equation of concrete under F-T cycles (Table
(Table 2).
2).
Theoretical equations that are related to the F–T damage model of concrete involve
many types of material damage theories, such as the material mechanical fatigue equation,
Table 2. F-T cyclic damage model of concrete based on RDEM.
macroscopic phenomenological damage mechanics, and meso-statistical damage mechanics.
Formula The specific establishment Theoretical
process isBasis
not repeated inApplicable
this study, Scope Provenance
but the above model in-
0.6 𝑙𝑙𝑙𝑙𝑙𝑙 𝑁𝑁
evitably has a certain scope of application in the process of establishment. Wang et al. [4,38]
𝐷𝐷𝑛𝑛 = 1 −
𝑙𝑙𝑙𝑙𝑙𝑙 𝑁𝑁 − 0.4 𝑙𝑙𝑙𝑙𝑙𝑙(𝑁𝑁
regarded − 𝑛𝑛)concrete that was subjected to salt erosion and F–T cycles to be in different
Mechanical fatigue equation
N: Standard F-T fatigue life, generallydamage set atand established a nonlinear superposition
states F-T in model
pure water Yu etdamage
of the double al. [36]
of material
300; state; however, the model ignores the effect of salt solution concentration and needs to be
n: Number of cycles. tested separately in practical applications. The RDEM index is difficult to characterize for
𝐷𝐷1 = 𝑎𝑎 + 𝑏𝑏𝑏𝑏 + 𝑐𝑐𝑥𝑥 the2 spalling phenomenon of the surface after many cycles. Wang et al. [129] proposed a
𝑘𝑘 coupling model that considered the mass loss rate and RDEM. Nili et al. [160] believed
𝐷𝐷2 = 𝛼𝛼 − 𝛽𝛽 𝑙𝑙𝑙𝑙 � that − 𝛾𝛾�the deterioration of concrete under F–T conditions can be divided into two parts, and
𝑛𝑛
𝐷𝐷𝑛𝑛 = 𝐷𝐷1 + 𝐷𝐷2 − 𝐷𝐷 1 𝐷𝐷2 is no apparent direction in the concrete deterioration in the initial stage. When the
there
D1: Salt erosion factor; RDEM of concrete was 0.8, the concrete entered the development stage, and the internal
Macroscopic phenomenologi- Wang et al.
D2: F-T cycles factors; damage of the concrete accumulated and it deteriorated Salt-freeze
rapidly;coupling
however, the model was
cal damage mechanics [38]
Dn: Coupling situation, n: Number of F-T for
only suitable cy-ordinary concrete with a w/c of 0.4–0.5. The applicability of these models
cles; is limited, and the correlation between different models is poor. At the same time, it is
difficult to explain the performance of other types of concrete. In the future research, it is
x: Sulfate erosion days;
α, β, γ, k, a, b c: Fitting parameters.
𝑛𝑛 0.819
𝐷𝐷𝑛𝑛 = 1 − 𝑒𝑒𝑒𝑒𝑒𝑒 �− � � � Meso-statistical damage me- 5% sodium sulfate F-T cy-
3878.347 Xiao et al. [37]
n: Number of F-T cycles. chanics cles
Buildings 2022, 12, 1317 23 of 36

far from enough to take RDEM as the research object. We need to study the freeze–thaw
damage model of concrete more comprehensively [158,159].

Table 2. F–T cyclic damage model of concrete based on RDEM.

Formula Theoretical Basis Applicable Scope Provenance

0.6logN
Dn = 1 − logN −0.4log( N −n)
N: Standard F–T fatigue life, Mechanical fatigue equation
F–T in pure water Yu et al. [36]
generally set at 300; of material
n: Number of cycles.
D1 = a + bx+ cx2 
D2 = α − βln nk − γ
Dn = D1 + D2 − D1 D2
D1 : Salt erosion factor; Macroscopic
D2 : F–T cycles factors; phenomenological Salt-freeze coupling Wang et al. [38]
Dn : Coupling situation, damage mechanics
n: Number of F–T cycles;
x: Sulfate erosion days;
α, β, γ, k, a, b c: Fitting parameters.
h
0.819 i
n
Dn = 1 − exp − 3878.347 Meso-statistical
5% sodium sulfate F–T cycles Xiao et al. [37]
n: Number of F–T cycles. damage mechanics

Dn = 1 − e−bn , n ≤ nc
r h i
ln(k)
Dn = 1 − k12 − c n − b , nc ≤ n ≤ 300 Low cycle fatigue theory &
F–T cycles of 0.4~0.5
meso-statistical Nili et al. [160]
b: Fitting parameters; water–cement ratio concrete
damage theory
k: The general value is 1.25;
nc : The number of cycles when RDEM is 0.8.
Dn = an2 + bn + c
a, b, c: Fitting parameters; Empirical formula Steel slag concrete Wen et al. [107]
n: Number of cycles.
1 1
Dn = En + 
Wn
 −2
E0 10 W0−0.9
Dn = e an − 1
En /E0 , W n /W 0 : RDEM and relative mass loss Air entraining concrete.
Empirical formula Wang et al. [129]
after F–T cycles; (considering quality loss)
a: Fitting parameters;
n: Number of F–T cycles.
Note: Dn in the above formula is the RDEM of concrete.

3.2. Damage Layer Thickness Model

Although the damage model that was based on the RDEM and mass loss has a good
correlation with the experimental results, for practical engineering, the application of
the above experimental methods is very limited. Based on the ultrasonic method that is
commonly used in concrete engineering testing, Guan [161] proposed an F–T damage eval-
uation model and method for concrete with damage layer thickness, which is convenient
for engineering applications and can accurately reflect the development of the concrete
damage that is caused by F–T damage from the surface to the interior.
The damage-layer thickness model adopts the damage variable, Dh , which is based
on the damage-layer thickness. The damage variable of the concrete damage layer is
modified through the evolution of the damage layer area and the compressive strength
during concrete F–T cycles, as illustrated in Figure 19 and Equations (10) and (11).
 
f cn Acn Aco
β = 1− − (10)
f co Arn Arn
Buildings 2022, 12, 1317 24 of 36

(b − 2hdn β)(h − 2hdn β)

 
Dn = 1 − (11)
bh
where β is the correction coefficient, f cn , and Acn are the compressive strength and cross-
sectional area of concrete after cycles, respectively; f c0 and Ac0 are the compressive strength
and cross-sectional area of concrete in the initial state, respectively; Arn is the area of
Buildings 2022, 12, x FOR PEER REVIEW 25 of 37
concrete damage layer after F–T cycles; hdn is the thickness of the damage layer after F–T
cycles; b and h are the width and height of the specimen interface, respectively.

Figure19.
Figure 19. Thickness
Thickness model
model of
of F–T
F-T damage
damage layer
layer of
of concrete.
concrete.

When combined with the ultrasonic 𝑓𝑓test𝐴𝐴of the𝐴𝐴concrete damage layer under F–T cycles,
𝑐𝑐𝑐𝑐 𝑐𝑐𝑐𝑐 𝑐𝑐𝑐𝑐
Guan [161,162] found that the 𝛽𝛽 = 1 − � of the damage
thickness − � (10)
𝑓𝑓𝑐𝑐𝑐𝑐 𝐴𝐴𝑟𝑟𝑟𝑟 𝐴𝐴𝑟𝑟𝑟𝑟 layer increases gradually with the
increase in the influence of cycles on concrete. The T-evaluation result of the damage layer
model was accurate. (𝑏𝑏 − 2ℎ𝑑𝑑𝑑𝑑 𝛽𝛽)(ℎ − 2ℎ𝑑𝑑𝑑𝑑 𝛽𝛽)
𝐷𝐷𝑛𝑛 = 1 − � � (11)
𝑏𝑏ℎ
3.3. Damage Model for Bulk Resistivity
where β is the correction coefficient, fcn, and Acn are the compressive strength and cross-
sectional
In thearea of concrete
coupling after cycles,
environment respectively;
of the salt solution fc0 and
andAF–T
c0 are the compressive strength
cycles, the damage to the
concrete that in caused by F–T is more rapid. Hosseinzadeh
and cross-sectional area of concrete in the initial state, respectively; et al. [32]
Arn isinvestigated the
the area of con-
effect of different types of cementitious materials on the chloride-F–T resistance
crete damage layer after F-T cycles; hdn is the thickness of the damage layer after F-T cycles; of concrete
and found
b and h arethat
the the saturation
width and height andofelectrical
the specimenconductivity
interface, of concrete were changed by the
respectively.
entryWhen
of solution,
combined the bulk
withresistivity, and test
the ultrasonic the number of cycles
of the concrete of concrete
damage layer and
underthese
F-Tare
cy-
attenuated in a power law. According to this changing trend, a fitting
cles, Guan [161,162] found that the thickness of the damage layer increases gradually with formula for the
electrical resistivity
the increase of concrete
in the influence of was established
cycles on concrete. to characterize
The T-evaluation the damage
result ofdegree of the
the damage
F–T cycles, as shown in Figure 20 and Equation (12).
layer model was accurate.
D = an−(0.54∼1.04) (12)
3.3. Damage Model for Bulk Resistivity r
whereInDther is coupling
the damageenvironment
rate that isofcharacterized
the salt solution andresistivity
by the F-T cycles, ofthe damage
concrete, to the
n is the
concreteofthat
number in caused
cycles, and a isby F-T is more
a power-law rapid.
fitting Hosseinzadeh
parameter et al. [32]
that is related investigated
to the the
type of gel ma-
effect According
terial. of differentto types of cementitious
the power law fittingmaterials on the
of the above chloride-F-T
bulk resistance
resistivity and number ofof
concrete
cycles,
andfailure
the foundtimethat of
theconcrete
saturation
in aand electrical conductivity
salt-freezing environment of concrete
can were changed
be effectively by the
evaluated.
entryInofaddition
solution,tothethebulk
aboveresistivity,
commonly andused
the number of cycles
indicators, of concrete and
other macroscopic these are
indexes are
attenuated in a power law. According to this changing trend, a fitting
often used to characterize the damage evolution of concrete during F–T deterioration, such formula for the
electrical
as acousticresistivity
emissionof(AE),
concrete wasstrength
various established to characterize
indexes, density, andthe so
damage degree
on. These of the
models
F-Tbasically
are cycles, asempirical
shown in orFigure 20 and Equation
semi-empirical models(12).
that are obtained directly on the basis
of experiments (Table 3). Each model has its limitations, for example, the prediction of
ultra-high-performance concrete (UHPC) by the mass loss model is inconsistent with the
actual situation of concrete, and the strength index needs to carry out destructive tests on
concrete. Although the above macroscopic index model is accurate for a certain types of
concrete, it is not satisfactory for the damage prediction of other types of concrete when
they are under the action of multiple factors [163,164]. In the future research, the damage
model should pay more attention to the micro-damage of concrete and establish the exact
damage model in turn.
Buildings 2022, 12,
Buildings 2022, 12, 1317
x FOR PEER REVIEW 25 of
26 of 36
37

120
1
2
100 Fitted Y of 1
Fitted Y of 2
1： y=1583.49x-1.25； R2=0.95
80
2： y=1228.53x-0.93； R2=0.98

60
Bulk resistivity

40 Ohm.m）
（

20

0
0 50 100 150 200 250 300
Cycles
Figure 20.
Figure 20. Bulk
Bulk resistivity
resistivity of
of concrete
concrete under
under different
different F–T
F-T cycles.
cycles.

Table 3. F–T cyclic damage model of concrete that is based on other macroscopic indexes.
−(0.54~1.04)
𝐷𝐷𝑟𝑟 = 𝑎𝑎𝑛𝑛 (12)
Damage Model where Dr isFormula
the damage rate that is characterized Symbolicby the resistivity of concrete,
Meaning Provenance n is the
number of cycles, and a is a power-law fitting parameter
a: Fly that is related to the type of gel
ash content;
Compressive D material.
= 0.824w−According
0.133 (−2.528a to2 the power law fitting b:ofAir
+ 1.013a thecontents;
above bulk resistivity and number of
w: Water/binder ratio; Xiao et al. [165]
strength model +cycles,
0.956)(the failure
0.556lnb time)of
+ 2.779 e concrete in a salt-freezing environment can be effectively evalu-
− 0.001n
n: Number of F–T cycles;
ated. f0: Initial strength.
In addition to the above commonly used indicators, other macroscopic indexes are
a, b, c: Fitting parameters;
often( used to characterize the damage evolution of concrete during F-T deterioration, such
at, (0 ≤ t ≤ t0 ) t0 : Damage speed change point
Mass decay model Das=acoustic emission (AE), various strength indexes, t0 = density,
a−c and so on. These models
Yu et al. [166] are
b ;
2
2 + ct + (c− a) , ( t ≥ t )
basically empirical2bor semi-empirical
0.5bt 0 models
t: Mass that are obtained
denudation time.directly on the basis of ex-
periments (Table  3). Each model
 has its limitations, for example,
n: Number of F–T cycles;
the prediction of ultra-
100.01n−d
Mass decay model high-performance
D = alg(bn + 1) 1 + concrete
c 1+ 100.01n−d(UHPC) by the mass loss model is
a, b, c, d: Fitting parameters. inconsistentMuwith
et al.the actual
[167]
situation of concrete, and the strength index needs to carry out destructive tests on con-
ft0 : Initial tensile strength;
crete. Although
f the above macroscopic index strength
model isafter
accurate for a certain
Zhangtypes
et al. of con-
Tensile strength model D = 1 − ftnto = 1 − (1 − 0.00296n)0.234 ftn : Tensile F–T cycles; [168]
crete, it is not satisfactory for the damagen:prediction of other
Number of F–T cycles. types of concrete when they
are under the action of multiple factors [163,164]. In the future research, the damage model
D(·): Limit state function;
Dshould
(·) = 300pay more attention to−the micro-damage of concrete
ratio; and establish the exact dam-
− (5632.71 + 4957.77a
2 + 163.27b2 − a: w/b
Residual strain model 2300b + 6.64n −
age model in turn.
4411.99a Cho et al. [169]
−3 2 b: gas drainage;
8.88 × 10 n )
n: Number of F–T cycles.

 0, ε ≤ 0.4ε p a, b, c, d, e, f : Fitting parameters;
Acoustic emission D= aebx − be0.4b , 0.4ε p ≤ ε ≤ ε p ε p : Peak strain;
Qiu et al. [3]
stress-strain model 
c + dx + ex2 + f x3 , ε ≥ ε p x: Normalized strain;
ε: Compressive strain.

3.4. Damage Model for Microstructure

The microstructure of the concrete material determines its macroscopic performance,
and the deterioration and evolution of the microstructure, such as the pore structure
Buildings 2022, 12, 1317 26 of 36

and microcracks of concrete during F–T cycle damage, is the main mechanism of F–T
damage. Several researchers have established damage evolution equations by studying the
development of pore structures and concrete cracks.
Wang et al. [129] believed that the continuous deterioration of concrete pores at the
micro level is an essential factor of F–T damage and they proposed a comprehensive growth
coefficient of pore structure for the first time. The deterioration of concrete is characterized
by the increment of different pore porosities and total porosities, and the evolution equation
of the pore structure is established as shown in Equation (13). It was found to have a natural
logarithmic relationship with the number of cycles. Finally, a microscopic F–T damage
model (Equation (14)) was established by comprehensively considering the initial porosity
and the w/c of the concrete. The model can connect macroscopic indexes, such as the mass
damage rate and RDEM, with the deterioration of the internal pore structure, which makes
the F–T damage more detailed.
 4
Pan Pbn Pcn Pdn Pn
Cgp = (13)
Pa0 Pb0 Pc0 Pd0 P0
a +bA2c −cAc +d ( e + f Ac + g)ehAc
D = Cgp 1+ AC e 1+ A c (14)
where Cgp is the pore growth coefficient, Pan /Pa0 , Pbn /Pb0 , Pcn /Pc0 , Pcn /Pc0 , Pdn /Pd0 ,
and Pn /P0 are micropores (<5 nm), small pores (5 nm < r < 20 nm), medium pores
(20 nm < r < 100 nm), large pores (>100 nm), and the ratio of total porosity to initial value
after n F–T cycles, respectively; Ac is the initial porosity; a, b, c, d, e, f, g, and h are fitting
parameters.
Jin et al. [33] explored the distribution of pore size parameters of eight types of concrete
and found that the changes in the total pore surface area, porosity, and average pore size
were irregular; only the fractal dimension of the pore surface decreased after the F–T cycles.
Therefore, the pore evolution law of concrete is analyzed using microdamage mechanics
and the thermodynamic fractal theory, and therefore the fractal dimension of the pore
surface can be obtained. A micro-scale F–T damage model was established, which can
quantitatively compare the F–T damage of concrete under different mixed conditions and
verify that there is an apparent inverse relationship between the model parameters and the
durability coefficient, as shown in Equation (15).

Ds,n − Ds,min
w = 1− (15)
Ds0 − Ds,min

w: according to the relative damage degree of concrete based on fractal dimension, there
is no damage when it is walled at 0, and the maximum damage occurs when it is wicked
at 1. Ds,n is the fractal dimension of pore surface after n F–T cycles, Dso is initial pore
surface fractal dimension, and Ds,min is the fractal dimension and is the minimum, which is
usually 2.
Sun et al. [125] measured the pore size distribution of diatomite concrete using MIP
and NAM. The results showed that the pore structure, which was mainly smaller than
200 nm, deteriorated after the F–T cycles. The cumulative pore volume distribution
that was between 2 nm and 350 µm was analyzed using a multifractal theory, and the
multifractal F–T damage model of the diatomite concrete was established, as shown in
Equations (16) and (17).
log[k(q, ε)]
Dq = lim , q 6= 1 (16)
ε→0 log( ε )

N (ε)
∑i=1 pi (ε)log[ pi (ε)]
D1 = lim ,q = 1 (17)
ε →0 log(ε)
where Dq is other fractal dimensions except information dimension, D1 is the information
dimension, ε is the equal interval length, k(q,ε) is the distribution function of multifractal
 Buildings 2022, 12, 1317 27 of 36

theory, pi (ε) is the relative pore volume of each interval, and q is the moment order of
cumulative pore size distribution (−10–10). The information dimension characterizes the
uniformity of the pore size distribution; the larger the D1 is, then the more uniform the
pore size is. It was found that when the concrete goes through the cycles, D1 generally
increases by approximately 5%, which indicates that the F–T pressure causes the critical
pores around the larger pores to be destroyed first. The inhomogeneity and connectivity of
the concrete decreased, and the concrete began to deteriorate.
Zhang et al. [132] studied the change in the porosity of concrete with different w/c
and that underwent under F–T, and the change in porosity that was measured by NMR can
well characterize the deterioration of concrete, as shown in Equation (18). In this equation,
D is the relative porosity change, pn is the porosity after n F–T cycles, and p0 is the initial
porosity. The model calculation showed that the damage degree with w/c of 0.45a and
0.55 after 200 cycles was 0.9 and 1.2, respectively, which was similar to the trend of mass
loss and RDEM. It was also found that the correlation between porosity damage, bending
strength, and splitting tensile strength was higher than 0.95, as shown in Figure 21.
Buildings 2022, 12, x FOR PEER REVIEW 29 of 37
p n − p0
D= (18)
1 − p0

5.0
w/c=0.45 4.5 w/c=0.45
4.5 w/c=0.55 w/c=0.55
w/c=0.45 fitting curve 4.0 w/c=0.45 fitting curves
Spliting tensile strength / MPa

4.0
w/c=0.55 fitting curve w/c=0.55 fitting curves
Flexural strength / MPa

3.5
3.5 y=4.481-4.654*D +1.701*D2 y=4.15*exp(-0.69*D)
3.0
R2=0.982 3.0 R2=0.957

2.5 2.5

2.0 2.0
y=3.87*exp(-0.79*D)
1.5 2
y=3.912-3.348*D +0.822*D 1.5 R2=0.957
1.0 R2=0.964
1.0
0.5
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Figure
Figure21.
21.Correlation
Correlation between strengthand
between strength andrelative
relativeporosity
porosityofof concrete
concrete [132].
[132].

LiLietetal.
al.[170]
[170] iteratively calculateddifferent
iteratively calculated differentvoid
voiddistributions
distributions and
and they
they proposed
proposed a a
meso-damage model of pore distribution under F–T, which assumes that
meso-damage model of pore distribution under F-T, which assumes that the pores are the pores are
continuous and cylindrical. The characteristic pore diameter of the concrete after n cycles
continuous and cylindrical. The characteristic pore diameter of the concrete after n cycles
can be analyzed by DSC and MIP, and iterative calculations are performed.
can be analyzed by DSC and MIP, and iterative calculations are performed.
In the first step, the initial damage was zero, as shown in Equation (19):
In the first step, the initial damage was zero, as shown in Equation (19):
D0cum = ∗D0∗ = 0 (19)
𝐷𝐷0𝑐𝑐𝑐𝑐𝑐𝑐 = 𝐷𝐷0 = 0 (19)

InInthe
thesecond
second step,
step, the
the cumulative
cumulative damage
damagewas wasconsidered
consideredtoto
consist of of
consist thethe
initial
initial
damage in the first step and the damage after an F–T cycle, as shown in Equation (20):
damage in the first step and the damage after an F-T cycle, as shown in Equation (20):
𝜋𝜋(𝐷𝐷 ∗ +
∗ 𝐷𝐷 ∗ ) ∗


cum= π 0D0 +1D1
𝑐𝑐𝑐𝑐𝑐𝑐
𝐷𝐷1D (20)
= (20)
1 2(1
2(+ 1+𝜇𝜇)µ)
By analogy, the damage after n cycles was accumulated by the damage caused by the
By analogy, the damage after n cycles was accumulated by the damage caused by the
previous
previousnnF-T
F–Tcycles,
cycles, such
such as
as Equation (21):
Equation (21):
𝜋𝜋 ∑𝑛𝑛𝑖𝑖=0 𝐷𝐷𝑖𝑖∗
𝑐𝑐𝑐𝑐𝑐𝑐
𝐷𝐷𝐹𝐹−𝑇𝑇 = 𝐷𝐷𝑛𝑛 = π ∑n D ∗ (21)
DF−T = Dncum =2(1 +i=𝜇𝜇) 0 i
(21)
2(1 + µ )
In Equations (19)–(21), n is the number of F-T cycles; D0cum, D1cum, and Dncum are the
cumulative damages
In Equations after 0,
(19)–(21), n is1,the
and n cycles,
number respectively;
of F–T D,0*D
cycles; D0 cum , 1Dcum and D
1*, ,and areare
Dnn*cum damage
the
parameters
cumulativeafter
damages aftern0,cycles,
0, 1, and 1, andrespectively, and are related
n cycles, respectively; D0 , Dto
*
1
* , the
and change
D n
* arein pore
damage size
and characteristic pore diameter; DF-T are the mesoscopic frost damage parameters; μ: is
Poisson’s ratio. The characteristic pore diameter of concrete increases continuously under
F-T cycles. The necessary and sufficient condition for undamaged concrete is that the char-
acteristic pore diameter of the concrete is less than the critical aperture, and when the
characteristic pore diameter is larger than the critical pore diameter, then the concrete is
Buildings 2022, 12, 1317 28 of 36

parameters after 0, 1, and n cycles, respectively, and are related to the change in pore size
and characteristic pore diameter; DF–T are the mesoscopic frost damage parameters; µ: is
Poisson’s ratio. The characteristic pore diameter of concrete increases continuously under
F–T cycles. The necessary and sufficient condition for undamaged concrete is that the
characteristic pore diameter of the concrete is less than the critical aperture, and when
the characteristic pore diameter is larger than the critical pore diameter, then the concrete
is damaged.
Li et al. [20] believed that the damage of concrete under F–T cycles is caused by a
combination of external spalling and internal pore deterioration, and the effect of cycles on
internal pores can be obtained according to the change in porosity, as shown in Equation (22).
The mass-loss rate can characterize the effect of external spalling, as shown in Equation (23):

∆pn = 0.017n (22)

4.06 × 10−4 n2.33

Dm ( n ) = (23)
100
According to the synthesis of meso-mechanics, the macroscopic and microscopic cross-
scale damage model under the condition of chloride-F–T of cement mortar was established,
as shown in Equation (24). The maximum error between the model and the actual situation
was 3.6%, indicating that the fitting result was excellent.

[1 − Dm(n)](1 − ∆pn )
D (n) = (24)
1 + 0.017αn
where D(n) is a parameter of a macro- and micro-F–T damage model, ∆pn is the porosity
increment, n is the number of cycles, Dm (n) is the macroscopic damage that is characterized
by mass loss rate, and α is the fitting parameter related to Poisson’s ratio µ of concrete
(Equation (25)).
(13 − 15µ)(1 − µ)
α= (25)
14 − 10µ
Li et al. [34] obtained quantitative data on concrete microcrack evolution during F–T
cycles based on digital image processing (DIP) and a vacuum epoxy resin impregnation
technique. It was found that the area density and length density of matrix microcracks are
directly proportional to the number of cycles, and there is a good correlation between the
microcrack parameters and the macroscopic properties of concrete. The empirical formula
between the evolution of microcracks and the deterioration of the compressive strength of
concrete during F–T cycles is obtained, as shown in Equation (26).

αDc = −625.93x2 − 100.48x + 1.02 (26)

where Dc is the relative compressive strength of concrete, and x is the microcrack area
density (%).
The deterioration process of concrete under F–T conditions is a cumulative damage
process that is in accordance with irreversible thermodynamics, and the change in its
macroscopic performance is the result of the continuous deterioration of the microstructure.
The pore structure of concrete changes when it incurs the processes of damage. Micropores
gradually expanded and developed into macroscopic cracks. Few studies have been
conducted on the microstructure damage model, mainly focusing on the change in porosity
and microcrack parameters. In recent years, the fractal theory has revealed that the meso-
damage of concrete does not lie in the change in its porosity, but the change in its pore size
distribution is key to the deterioration of concrete performance [171,172].
From the above process of establishing the F–T damage model, based on various
indexes, it can be seen that the overall trend of the establishment of the damage model
shows a trend from experience to theory, from macro to micro index, and from single index
to comprehensive index. The early F–T damage model was mainly based on macroscopic
Buildings 2022, 12, 1317 29 of 36

indices such as the RDEM and compressive strength. In recent years, damage mechanics
and fractal theory have become prominent subjects in concrete F–T research [153,173]. Many
scholars have established concrete damage models based on the damage mechanics theory
and fractal theory, and the test index has gradually turned to micro-indicators. Different
testing methods have different applicable conditions; therefore, a variety of testing methods
can be combined to overcome the limitations of each testing method and accurately predict
the F–T deterioration process of concrete.

4. Summary
The damage mechanism and modeling of concrete under the F–T cycle are key issues
in durability research. This paper reviews the recent progress in the study of F–T damage
in concrete, focusing on the damage mechanism and modeling, and summarizes the
theoretical model of F–T damage for testing microstructure evolution. Based on this review,
the main conclusions are as follows:
(1) From the concrete F–T deterioration theory, it can be revealed that the water phase
transition during the F–T cycles is the main cause of concrete F–T damage;
(2) Under the condition of a salt-freezing coupling environment, the F–T damage of
concrete is accelerated by salt crystallization expansion and salt solution erosion. The
effects of various salt solutions on concrete F–T cycle damage are different because of
the inconsistent effects of salt solutions on the pores and hydration products;
(3) During the F–T cycles, the deterioration of the concrete microstructure is a synthetic
result. The microstructure test results show that the porosity increases, the microcracks
expand, and the ITZ widens during the F–T cycles. The loss of hydration products
and salt crystal expansion during salt freezing was determined by a phase analysis;
(4) The damage model for the concrete microstructure in the F–T cycle essentially reveals
the damage mechanism, and the deterioration model for the pore structure and the
microcrack growth model were established to reflect the F–T damage process.

5. Recommendations for Future Research

(1) The evolution of pore damage has always been the focus of the analysis of the concrete
F–T cycle mechanism. However, the applicable conditions for different mechanisms
are diverse, and the theoretical model of unified coordination among pore structure
damage, water-phase transformation, matrix deformation, and damage variables need
to be further explored.
(2) Pore structure degradation and microcrack growth have been used to model F–T
damage; however, the influence of erosion effects on hydration product components
and the deterioration of the ITZ are not involved in the F–T damage model, and the
response of the composition index and ITZ parameters in the damage model is novel
and creative. Further research should be conducted in this area.
(3) There are many detection techniques used to establish F–T damage models, but
some are superficial for characterizing the F–T damage of concrete. In the wake
of developments in science and technology, the emergence of advanced detection
methods, such as acoustic emission and optical fiber monitoring, has provided a new
field of vision for the study of concrete F–T damage. It is necessary to carry out related
research to further understand freeze–thaw fatigue damage.

Author Contributions: Conceptualization, J.G., Y.X. and W.J.; methodology, W.S., Y.X., W.L. and
W.J.; validation, J.G., Y.X., W.S., W.L. and W.J.; formal analysis, W.S., Y.X. and W.L.; investigation,
W.S. and Y.X.; resources, J.G., Y.X. and W.J.; data curation, W.S., W.L. and Y.X.; writing—original
draft preparation, W.S., Y.X. and W.L.; writing—review and editing, J.G., W.S. and Y.X.; visualization,
W.S., Y.X. and W.L.; supervision, J.G. and W.J.; project administration, J.G., W.S. and Y.X.; funding
acquisition, J.G. All authors have read and agreed to the published version of the manuscript.
Buildings 2022, 12, 1317 30 of 36

Funding: This research was funded by National Natural Science Foundation of China (U2040224,
52130901).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Mehta, P.K. Concrete durability-fifty years progress. In Proceedings of the 2nd International Conference on Concrete Durability,
Montreal, QC, Canada, 1 September 1991; p. 132.
2. Wenchen, M. Simulate Initiation and Formation of Cracks and Potholes. Master’s Thesis, Northeastern University, Boston, MA,
USA, 2016.
3. Qiu, J.S.; Zhou, Y.X.; Vatin, N.I.; Guan, X.; Sultanov, S.; Khemarak, K. Damage constitutive model of coal gangue concrete under
freeze–thaw cycles. Constr. Build. Mater. 2020, 264, 120720. [CrossRef]
4. Wang, B.; Wang, F.; Wang, Q. Damage constitutive models of concrete under the coupling action of freeze–thaw cycles and load
based on Lemaitre assumption. Constr. Build. Mater. 2018, 173, 332–341. [CrossRef]
5. Powers, T.C. A working hypothesis for further studies of frost resistance of concrete. J. Proc. 1945, 41, 245–272.
6. Powers, T.C.; Helmuth, R.A. Theory of Volume Changes in Hardened Portland-Cement Paste During Freezing. In Proceedings of
the Thirty-Second Annual Meeting of the Highway Research Board, Washington, DC, USA, 13–16 January 1953; pp. 285–297.
7. Powers, T.C.; Willis, T.F. The Air Requirement of Frost Resistant Concrete. Highw. Res. Board Proc. 1950, 29, 184–211.
8. Fagerlund, G. Critical Degrees of Saturation at Freezing of Porous and Brittle Materials, Report 34; Division of Building Technology,
Lund Institute of Technology: Lund, Sweden, 1972; p. 408.
9. Scherer, G.W. Crystallization in pores. Cement. Concr. Res. 1999, 29, 1347–1358. [CrossRef]
10. Setzer, M.J. Micro-ice-lens formation in porous solid. J. Colloid. Interf. Sci. 2001, 243, 193–201. [CrossRef]
11. Setzer, M.J. Mechanical stability criterion, triple-phase condition, and pressure differences of matter condensed in a porous matrix.
J. Colloid. Interf. Sci. 2001, 235, 170–182. [CrossRef]
12. Valenza, J.J.; Scherer, G.W. A review of salt scaling: I. Phenomenology. Cem. Concr. Res. 2007, 37, 1007–1021. [CrossRef]
13. Coussy, O. Poromechanics of freezing materials. J. Mech. Phys. Solids 2005, 53, 1689–1718. [CrossRef]
14. Liu, L.; Shen, D.; Chen, H.; Sun, W.; Qian, Z.; Zhao, H.; Jiang, J. Analysis of damage development in cement paste due to ice
nucleation at different temperatures. Cem. Concr. Comp. 2014, 53, 1–9. [CrossRef]
15. Gong, F.; Jacobsen, S. Modeling of water transport in highly saturated concrete with wet surface during freeze/thaw. Cem. Concr.
Res. 2019, 115, 294–307. [CrossRef]
16. Eriksson, D.; Wahlbom, D.; Malm, R.; Fridh, K. Hygro-thermo-mechanical modeling of partially saturated air-entrained concrete
containing dissolved salt and exposed to freeze–thaw cycles. Cem. Concr. Res. 2021, 141, 106314. [CrossRef]
17. Wang, Y.; Li, J.H.; Ueda, T.; Zhang, D.W.; Deng, J. Meso-scale mechanical deterioration of mortar subjected to freeze thaw cycles
and sodium chloride attack. Cem. Concr. Comp. 2021, 117, 103906. [CrossRef]
18. Mesbah, A.; Francois, M.; Cau-dit-Coumes, C.; Frizon, F.; Filinchuk, Y.; Leroux, F.; Ravaux, J.; Renaudin, G. Crystal structure of
Kuzel’s salt 3CaO center dot Al2 O3 center dot 1/2CaSO4 center dot 1/2CaCl2 center dot 11H(2)O determined by synchrotron
powder diffraction. Cem. Concr. Res. 2011, 41, 504–509. [CrossRef]
19. Wenchen, M. Behavior of Aged Reinforced Concrete Columns under High Sustained Concentric and Eccentric Loads. Ph.D.
Thesis, University of Nevada, Las Vegas, NV, USA, 2021.
20. Li, Y.; Li, Y.Q.; Guan, Z.Z.; Ding, Q.J. Elastic modulus damage model of cement mortar under salt freezing circumstance based on
X-ray CT scanning. Constr. Build. Mater. 2018, 191, 1201–1209. [CrossRef]
21. Gonzalez, D.C.; Mena, A.; Minguez, J.; Vicente, M.A. Influence of air-entraining agent and freeze–thaw action on pore structure
in high-strength concrete by using CT-Scan technology. Cold Reg. Sci. Technol. 2021, 192, 103397. [CrossRef]
22. Sokhansefat, G.; Moradian, M.; Finnell, M.; Behravan, A.; Ley, M.T.; Lucero, C.; Weiss, J. Using X-ray computed tomography to
investigate mortar subjected to freeze–thaw cycles. Cem. Concr. Comp. 2020, 108, 103520. [CrossRef]
23. Xu, F.; Yang, Z.Q.; Liu, W.Q.; Wang, S.G.; Zhang, H.G. Experimental investigation on the effect of sulfate attack on chloride
diffusivity of cracked concrete subjected to composite solution. Constr. Build. Mater. 2020, 237, 117643. [CrossRef]
24. Li, Y.; Wang, R.J.; Li, S.Y.; Zhao, Y.; Qin, Y. Resistance of recycled aggregate concrete containing low- and high-volume fly ash
against the combined action of freeze–thaw cycles and sulfate attack. Constr. Build. Mater. 2018, 166, 23–34. [CrossRef]
25. Jiang, L.; Niu, D.T.; Yuan, L.D.; Fei, Q.N. Durability of concrete under sulfate attack exposed to freeze–thaw cycles. Cold Reg. Sci.
Technol. 2015, 112, 112–117. [CrossRef]
26. Nili, M.; Ramezanianpour, A.A.; Sobhani, J. Evaluation of the effects of silica fume and air-entrainment on deicer salt scaling
resistance of concrete pavements: Microstructural study and modeling. Constr. Build. Mater. 2021, 308, 124972. [CrossRef]
27. Qiao, C.; Hosseinzadeh, N.; Suraneni, P.; Wei, S.; Rothstein, D. Petrographically quantifying the damage to field and lab-cast
mortars subject to freeze–thaw cycles and deicer application. J. Infrastruct. Preserv. Resil. 2021, 2, 9. [CrossRef]
Buildings 2022, 12, 1317 31 of 36

28. Niu, D.T.; Jiang, L.; Fei, Q.N. Deterioration Mechanism of Sulfate Attack on Concrete under Freeze-thaw Cycles. J. Wuhan Univ.
Technol. 2013, 28, 1172–1176. [CrossRef]
29. Wang, D.Z.; Zhou, X.M.; Meng, Y.F.; Chen, Z. Durability of concrete containing fly ash and silica fume against combined
freezing-thawing and sulfate attack. Constr. Build. Mater. 2017, 147, 398–406. [CrossRef]
30. Wang, Y.Z.; Liu, Z.; Fu, K.; Li, Q.M.; Wang, Y.C. Experimental studies on the chloride ion permeability of concrete considering the
effect of freeze–thaw damage. Constr. Build. Mater. 2020, 236, 117556. [CrossRef]
31. Zhang, X.; Wang, L.; Zhang, J. Mechanical behavior and chloride penetration of high strength concrete under freeze–thaw attack.
Cold Reg. Sci. Technol. 2017, 142, 17–24. [CrossRef]
32. Hosseinzadeh, N.; Suraneni, P. Synergistic effects of air content and supplementary cementitious materials in reducing damage
caused by calcium oxychloride formation in concrete. Cem. Concr. Comp. 2021, 122, 104170. [CrossRef]
33. Jin, S.S.; Zheng, G.P.; Yu, J. A micro freeze–thaw damage model of concrete with fractal dimension. Constr. Build. Mater. 2020, 257,
119434. [CrossRef]
34. Li, S.G.; Chen, G.X.; Ji, G.J.; Lu, Y.H. Quantitative damage evaluation of concrete suffered freezing-thawing by DIP technique.
Constr. Build. Mater. 2014, 69, 177–185. [CrossRef]
35. Xiao, Q.H.; Li, Q.; Cao, Z.Y.; Tian, W.Y. The deterioration law of recycled concrete under the combined effects of freeze–thaw and
sulfate attack. Constr. Build. Mater. 2019, 200, 344–355. [CrossRef]
36. Yu, H.; Ma, H.; Yan, K. An equation for determining freeze–thaw fatigue damage in concrete and a model for predicting the
service life. Constr. Build. Mater. 2017, 137, 104–116. [CrossRef]
37. Xiao, Q.H.; Cao, Z.Y.; Guan, X.; Li, Q.; Liu, X.L. Damage to recycled concrete with different aggregate substitution rates from the
coupled action of freeze–thaw cycles and sulfate attack. Constr. Build. Mater. 2019, 221, 74–83. [CrossRef]
38. Wang, B.X.; Pan, J.J.; Fang, R.C.; Wang, Q. Damage model of concrete subjected to coupling chemical attacks and freeze–thaw
cycles in saline soil area. Constr. Build. Mater. 2020, 242, 118205. [CrossRef]
39. Hang, M.; Cui, L.; Wu, J.; Sun, Z. Freezing-thawing damage characteristics and calculation models of aerated concrete. J. Build.
Eng. 2020, 28, 101072. [CrossRef]
40. Chen, F.L.; Qiao, P.Z. Probabilistic damage modeling and service-life prediction of concrete under freeze–thaw action. Mater.
Struct. 2015, 48, 2697–2711. [CrossRef]
41. Dahmani, L.; Khenane, A.; Kaci, S. Behavior of the reinforced concrete at cryogenic temperatures. Cryogenics 2007, 47, 517–525.
[CrossRef]
42. Jiang, Z.W.; He, B.; Zhu, X.P.; Ren, Q.; Zhang, Y. State-of-the-art review on properties evolution and deterioration mechanism of
concrete at cryogenic temperature. Constr. Build. Mater. 2020, 257, 119456. [CrossRef]
43. Zeng, Q.; Li, K.; Fen-chong, T.; Dangla, P. In A study of the Behaviors of Cement-Based Materials Subject to Freezing. In
Proceedings of the 2010 International Conference on Mechanic Automation and Control Engineering, Wuhan, China, 26–28 June
2010; pp. 1611–1616.
44. Liu, Z.; Zhang, Y.; Jiang, Q.; Zhang, W.; Wu, J. Solid Phases Percolation and Capillary Pores Depercolation in Hydrating Cement
Pastes. J. Mater. Civil. Eng. 2014, 26, 04014090. [CrossRef]
45. Sun, Z.; Scherer, G.W. Effect of air voids on salt scaling and internal freezing. Cem. Concr. Res. 2010, 40, 260–270. [CrossRef]
46. Rønning, T.F. Freeze–Thaw Resistance of Concrete: Effect of: Curing Conditions, Moisture Exchange and Materials. Ph.D. Thesis,
The Norwegian Institute of Technology, Trondheim, Norway, 2001.
47. Washburn, E.W. The dynamics of capillary flow. Phys. Rev. 1921, 17, 273. [CrossRef]
48. Sun, M.; Xin, D.B.; Zou, C.Y. Damage evolution and plasticity development of concrete materials subjected to freeze–thaw during
the load process. Mech. Mater. 2019, 139, 103192. [CrossRef]
49. Smith, S.H.; Qiao, C.Y.; Suraneni, P.; Kurtis, K.E.; Weiss, W.J. Service-life of concrete in freeze–thaw environments: Critical degree
of saturation and calcium oxychloride formation. Cem. Concr. Res. 2019, 122, 93–106. [CrossRef]
50. Fagerlund, G. The Long Time Water Absorption in the Air-Pore Structure of Concrete; Division of Building, Lund Institute of
Technology: Lund, Sweden, 1993.
51. Masoodi, R.; Pillai, K.M. Wicking in Porous Materials: Traditional and Modern Modeling Approaches; CRC Press: Boca Raton, FL, USA,
2012.
52. Liu, L.; Qin, G.; Qin, S.N.; Tao, G.H. Simulation of the volumetric deformation and changes in the pore structure of unsaturated
cement-based materials subjected to freezing/thawing. Constr. Build. Mater. 2020, 230, 116964. [CrossRef]
53. Valenza, J.J.; Scherer, G.W. A review of salt scaling: II. Mechanisms. Cem. Concr. Res. 2007, 37, 1022–1034. [CrossRef]
54. De Kock, T.; Boone, M.A.; De Schryver, T.; van Stappen, J.; Derluyn, H.; Masschaele, B.; De Schutter, G.; Cnudde, V. A Pore-Scale
Study of Fracture Dynamics in Rock Using X-ray Micro-CT Under Ambient Freeze–Thaw Cycling. Environ. Sci. Technol. 2015, 49,
2867–2874. [CrossRef]
55. Deprez, M.; De Kock, T.; De Schutter, G.; Cnudde, V. A review on freeze–thaw action and weathering of rocks. Earth Sci. Rev.
2020, 203, 103143. [CrossRef]
56. Bluhm, J.; Setzer, M.J.; Kruschwitz, J. Modeling of ice formation in porous media. In IUTAM Symposium on Physicochemical
and Electromechanical Interactions in Porous Media; Huyghe, J.M., Raats, P., Cowin, S.C., Eds.; Symposium on the Mechanics of
Physicochemical and Electromechanical Interactions in Porous Media: New York, NY, USA, 2005; Volume 125, pp. 329–334.
Buildings 2022, 12, 1317 32 of 36

57. Rosenqvist, M.; Fridh, K.; Hassanzadeh, M. Macroscopic ice lens growth in hardened concrete. Cem. Concr. Res. 2016, 88, 114–125.
[CrossRef]
58. Valenza, J.J.; Scherer, G.W. Mechanism for salt scaling of a cementitious surface. Mater. Struct 2007, 40, 259–268. [CrossRef]
59. Valenza, J.J.; Scherer, G.W. Mechanisms of salt scaling. Mater. Struct. 2005, 38, 479–488. [CrossRef]
60. Valenza, J.J.; Scherer, G.W. Characterization of saturated porous bodies. Mater. Struct. 2004, 37, 21–30.
61. Coussy, O.; Monteiro, P. Poroelastic model for concrete exposed to freezing temperatures. Cem. Concr. Res. 2008, 38, 40–48.
[CrossRef]
62. Dong, Y.J.; Su, C.; Qiao, P.Z.; Sun, L.Z. A thermal-hydraulic-mechanical coupling model for freezing process simulation of
cementitious materials with entrained air voids. Constr. Build. Mater. 2020, 243, 118253. [CrossRef]
63. Mayercsik, N.P.; Vandamme, M.; Kurtis, K.E. Assessing the efficiency of entrained air voids for freeze–thaw durability through
modeling. Cem. Concr. Res. 2016, 88, 43–59. [CrossRef]
64. Gou, Y.; Zhang, L.; Liu, C.; Zhang, H.; Wei, C.; Cai, X.; Yang, H.; Guan, Q.; Zhai, S.; Liu, L. Investigation of freeze–thaw mechanism
for crumb rubber concrete by the online strain sensor. Measurement 2021, 174, 109080. [CrossRef]
65. Qiao, C.; Chen, X.; Suraneni, P.; Weiss, W.J.; Rothstein, D. Petrographic analysis of in-service cementitious mortar subject to
freeze–thaw cycles and deicers. Cem. Concr. Compos. 2021, 122, 104112. [CrossRef]
66. Qiao, C.; Suraneni, P.; Weiss, J. Flexural strength reduction of cement pastes exposed to CaCl2 solutions. Cem. Concr. Compos.
2018, 86, 297–305. [CrossRef]
67. Li, W.; Pour-Ghaz, M.; Castro, J.; Weiss, J. Water Absorption and Critical Degree of Saturation Relating to Freeze–Thaw Damage
in Concrete Pavement Joints. J. Mater. Civ. Eng. 2012, 24, 299–307. [CrossRef]
68. Song, Q.; Nie, J.; Wu, D.K.; Hu, Y.R.; Chen, Y.X. Effect of SO4 2− , Cl− and Mg2+ on the system of C-S-H and Ca(OH)2 . Constr.
Build. Mater. 2021, 285, 122955. [CrossRef]
69. Birnin-Yauri, U.A.; Glasser, F.P. Friedel’s salt, Ca2 Al(OH)6 center dot 2H2 O: Its solid solutions and their role in chloride binding.
Cem. Concr. Res. 1998, 28, 1713–1723. [CrossRef]
70. Qiao, C.; Suraneni, P.; Weiss, J. Damage in cement pastes exposed to NaCl solutions. Constr. Build. Mater. 2018, 171, 120–127.
[CrossRef]
71. Farnam, Y.; Dick, S.; Wiese, A.; Davis, J.; Bentz, D.; Weiss, J. The influence of calcium chloride deicing salt on phase changes and
damage development in cementitious materials. Cem. Concr. Compos. 2015, 64, 1–15. [CrossRef]
72. Qiao, C.Y.; Suraneni, P.; Weiss, J. Phase Diagram and Volume Change of the Ca(OH)2 CaCl2 H2 O System for Varying
Ca(OH)2 /CaCl2 Molar Ratios. J. Mater. Civil. Eng. 2018, 30, 04017281. [CrossRef]
73. Xie, N.; Dang, Y.; Shi, X. New insights into how MgCl2 deteriorates Portland cement concrete. Cem. Concr. Res. 2019, 120, 244–255.
[CrossRef]
74. Sutter, L.; Peterson, K.; Touton, S.; Van Dam, T.; Johnston, D. Petrographic evidence of calcium oxychloride formation in mortars
exposed to magnesium chloride solution. Cem. Concr. Res. 2006, 36, 1533–1541. [CrossRef]
75. Ghazy, A.; Bassuoni, M. Resistance of concrete to different exposures with chloride-based salts. Cem. Concr. Res. 2017, 101,
144–158. [CrossRef]
76. Nadelman, E.; Kurtis, K. Durability of Portland-limestone cement-based materials to physical salt attack. Cem. Concr. Res. 2019,
125, 105859. [CrossRef]
77. Lee, B.Y.; Kurtis, K.E. Effect of pore structure on salt crystallization damage of cement-based materials: Consideration of w/b and
nanoparticle use. Cem. Concr. Res. 2017, 98, 61–70. [CrossRef]
78. Li, B.; Mao, J.; Nawa, T.; Liu, Z. Mesoscopic chloride ion diffusion model of marine concrete subjected to freeze–thaw cycles.
Constr. Build. Mater. 2016, 125, 337–351. [CrossRef]
79. Zhu, P.H.; Hao, Y.L.; Liu, H.; Wang, X.J.; Gu, L. Durability evaluation of recycled aggregate concrete in a complex environment.
J. Clean Prod. 2020, 273, 122569. [CrossRef]
80. Wang, D.Z.; Zhou, X.M.; Fu, B.; Zhang, L.R. Chloride ion penetration resistance of concrete containing fly ash and silica fume
against combined freezing-thawing and chloride attack. Constr. Build. Mater. 2018, 169, 740–747. [CrossRef]
81. Yazdchi, M.; Asl, A.F.; Talatahari, S.; Gandomi, A.H. Evaluation of the Mechanical Properties of Normal Concrete Containing
Nano-MgO under Freeze–Thaw Conditions by Evolutionary Intelligence. Appl. Sci. 2021, 11, 2529. [CrossRef]
82. Qiu, W.L.; Teng, F.; Pan, S.S. Damage constitutive model of concrete under repeated load after seawater freeze–thaw cycles.
Constr. Build. Mater. 2020, 236, 117560. [CrossRef]
83. Wang, Y.Z.; Liu, Z.; Zhang, B.H.; Fu, K. A time-dependent diffusive model for the simulation of chloride penetration in concrete
considering the effect of natural salt freeze–thaw cycles. Cold Reg. Sci. Technol. 2022, 201, 103622. [CrossRef]
84. Hou, R.; Qi, Z.; Li, T.; Fu, Q.; Meng, F.; Liu, D.; Li, Q.; Zhao, H.; Yu, P. Mechanism of snowmelt infiltration coupled with salt
transport in soil amended with carbon-based materials in seasonally frozen areas. Geoderma 2022, 420, 115882. [CrossRef]
85. Luo, S.; Bai, T.; Guo, M.; Wei, Y.; Ma, W. Impact of Freeze–Thaw Cycles on the Long-Term Performance of Concrete Pavement and
Related Improvement Measures: A Review. Materials 2022, 15, 4568. [CrossRef]
86. Kunther, W.; Lothenbach, B.; Skibsted, J. Influence of the Ca/Si ratio of the C–S–H phase on the interaction with sulfate ions and
its impact on the ettringite crystallization pressure. Cem. Concr. Res. 2015, 69, 37–49. [CrossRef]
87. Kunther, W.; Lothenbach, B.; Scrivener, K. Influence of bicarbonate ions on the deterioration of mortar bars in sulfate solutions.
Cem. Concr. Res. 2013, 44, 77–86. [CrossRef]
Buildings 2022, 12, 1317 33 of 36

88. Zhao, N.; Wang, S.; Wang, C.; Quan, X.; Yan, Q.; Li, B. Study on the durability of engineered cementitious composites (ECCs)
containing high-volume fly ash and bentonite against the combined attack of sulfate and freezing-thawing (F–T). Constr. Build.
Mater. 2019, 233, 117313. [CrossRef]
89. Hime, W.G.; Mather, B. “Sulfate attack,” or is it? Cem. Concr. Res. 1999, 29, 789–791. [CrossRef]
90. Li, C.; Jiang, Z.W.; Myers, R.J.; Chen, Q.; Wu, M.X.; Li, J.Q.; Monteiro, P. Understanding the sulfate attack of Portland cement-based
materials exposed to applied electric fields: Mineralogical alteration and migration behavior of ionic species. Cem. Concr. Comp.
2020, 111, 103630. [CrossRef]
91. Wang, K.; Guo, J.; Yang, L. Effect of dry–wet ratio on sulfate transport-reaction mechanism in concrete. Constr. Build. Mater. 2021,
302, 124418. [CrossRef]
92. Bayraktar, O.Y.; Eshtewi, S.; Benli, A.; Kaplan, G.; Toklu, K.; Gunek, F. The impact of RCA and fly ash on the mechanical and
durability properties of polypropylene fibre-reinforced concrete exposed to freeze–thaw cycles and MgSO4 with ANN modeling.
Constr. Build. Mater. 2021, 313, 125508. [CrossRef]
93. Tosun-Felekoğlu, K. The effect of C3A content on sulfate durability of Portland limestone cement mortars. Constr. Build. Mater.
2012, 36, 437–447. [CrossRef]
94. Steiger, M.; Asmussen, S. Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2 SO4 –H2 O and the
generation of stress. Geochim. Cosmochim. Acta 2008, 72, 4291–4306. [CrossRef]
95. Al-Amoudi, O.S.B. Attack on plain and blended cements exposed to aggressive sulfate environments. Cem. Concr. Compos. 2002,
24, 305–316. [CrossRef]
96. Bensted, J. Thaumasite—Background and nature in deterioration of cements, mortars and concretes. Cem. Concr. Comp. 1999, 21,
117–121. [CrossRef]
97. Sotiriadis, K.; Hlobil, M.; Viani, A.; Mácová, P.; Vopálenský, M. Physical-chemical-mechanical quantitative assessment of the
microstructural evolution in Portland-limestone cement pastes exposed to magnesium sulfate attack at low temperature. Cem.
Concr. Res. 2021, 149, 106566. [CrossRef]
98. Piasta, W.; Marczewska, J.; Jaworska, M. Durability of air entrained cement mortars under combined sulphate and freeze–thaw
attack. In Proceedings of the 7th Scientific-Technical Conference Material Problems in Civil Engineering (MATBUD), Cracow
University of Technology, Cracow, Poland, 22–24 June 2015; Tracz, T., Hager, I., Eds.; Volume 108, pp. 55–62.
99. Ren, J.G.; Lai, Y.M. Study on the durability and failure mechanism of concrete modified with nanoparticles and polypropylene
fiber under freeze–thaw cycles and sulfate attack. Cold Reg. Sci. Technol. 2021, 188, 103301. [CrossRef]
100. Farnam, Y.; Bentz, D.; Sakulich, A.; Flynn, D.; Weiss, J. Measuring freeze and thaw damage in mortars containing deicing salt
using a low-temperature longitudinal guarded comparative calorimeter and acoustic emission. Adv. Civ. Eng. Mater. 2014, 3,
316–337. [CrossRef]
101. Sun, H.F.; Jiang, C.; Cao, K.; Yu, D.; Liu, W.; Zhang, X.G.; Xing, F.; Zhao, D.D. Monitoring of steel corrosion and cracking in
cement paste exposed to combined sulfate-chloride attack with X-ray microtomography. Constr. Build. Mater. 2021, 302, 124345.
[CrossRef]
102. Wu, J.; Wei, J.; Huang, H.; Hu, J.; Yu, Q. Effect of multiple ions on the degradation in concrete subjected to sulfate attack. Constr.
Build. Mater. 2020, 259, 119846. [CrossRef]
103. Du, J.; Tang, Z.; Li, G.; Yang, H.; Li, L. Key inhibitory mechanism of external chloride ions on concrete sulfate attack. Constr. Build.
Mater. 2019, 225, 611–619. [CrossRef]
104. Chen, D.; Deng, Y.; Shen, J.; Sun, G.; Shi, J. Study on damage rules on concrete under corrosion of freeze–thaw and saline solution.
Constr. Build. Mater. 2021, 304, 124617. [CrossRef]
105. Qingli, D.; Ng, K. Transmission X-Ray Microscope Nanoscale Characterization and 3D Micromechanical Modeling of Internal
Frost Damage in Cement Paste. J. Nanomech. Micromech. 2014, 4, A4013005–A4013010.
106. Du, W.; Liu, Q.T.; Lin, R.S. Effects of toluene-di-isocyanate microcapsules on the frost resistance and self-repairing capability of
concrete under freeze–thaw cycles. J. Build. Eng. 2021, 44, 102880. [CrossRef]
107. Wen, Y.; Sun, H.; Hu, S.D.; Xu, G.M.; Wu, X.Z.; Song, C.C.; Liu, Z.; Li, Z.J. Microstructure and life prediction model of steel slag
concrete under freezing-thawing environment. Nanotechnol. Rev. 2021, 10, 1776–1788. [CrossRef]
108. Sakr, M.R.; Bassuoni, M.T. Silane and methyl-methacrylate based nanocomposites as coatings for concrete exposed to salt
solutions and cyclic environments. Cem. Concr. Comp. 2021, 115, 103841. [CrossRef]
109. Huang, X.; Wang, T.; Pang, J.; Song, F. Experimental Study on the Effect of Freeze–Thaw Cycles on the Apparent and Mechanical
Properties of Rubber Concrete Under Chloride Environment. Arab. J. Sci. Eng. 2022, 47, 4133–4153. [CrossRef]
110. Tian, W.; Gao, F.F. Damage and Degradation of Concrete under Coupling Action of Freeze–Thaw Cycle and Sulfate Attack. Adv.
Mater. Sci. Eng. 2020, 2020, 8032849. [CrossRef]
111. Wang, R.; Hu, Z.; Li, Y.; Wang, K.; Zhang, H. Review on the deterioration and approaches to enhance the durability of concrete in
the freeze–thaw environment. Constr. Build. Mater. 2022, 321, 126371. [CrossRef]
112. Jia, P.; Li, L.; Zhou, J.; Zhang, D.; Guan, Z.W.; Dong, J.F.; Wang, Q.Y. Performance Evolution of Recycled Aggregate Concrete
under the Coupled Effect of Freeze–Thaw Cycles and Sulfate Attack. Appl. Sci. 2022, 12, 6950. [CrossRef]
113. Divanedari, H.; Eskandari-Naddaf, H. Insights into surface crack propagation of cement mortar with different cement fineness
subjected to freezing/thawing. Constr. Build. Mater. 2020, 233, 117207. [CrossRef]
Buildings 2022, 12, 1317 34 of 36

114. Xie, R.F.; Lu, L.J.; Qiao, P.Z.; Zhou, Z.D. Nanoindentation-based micromechanical characterisation of ultra-high-performance
concrete exposed to freezing-thawing. Mag. Concr. Res. 2022, 74, 162–176. [CrossRef]
115. Liu, M.X.; Liu, D.X.; Qiao, P.Z.; Sun, L.Z. Characterization of microstructural damage evolution of freeze–thawed shotcrete by an
integrative micro-CT and nanoindentation statistical approach. Cem. Concr. Comp. 2021, 117, 103909. [CrossRef]
116. Lyu, Z.; Shen, A.; Wang, W.; Lin, S.; Guo, Y.; Meng, W. Salt frost resistance and micro characteristics of polynary blended concrete
using in frost areas. Cold Reg. Sci. Technol. 2021, 191, 103374. [CrossRef]
117. Zhang, J.; Wang, Y.; Pang, J.; Lu, Y.; Bu, Y. Experimental Study on Damage Characteristics of Solidified Mud under Coupling
Action of Freeze–Thaw Cycle and Chloride Salt. Geofluids 2022, 2022, 6050432. [CrossRef]
118. Ji, R.; Li, T.; Yang, J.; Xu, J. Sulfate Freeze–Thaw Resistance of Magnesium Potassium Phosphate Cement Mortar according to
Hydration Age. Materials 2022, 15, 4192. [CrossRef]
119. Ebrahimi, K.; Daiezadeh, M.J.; Zakertabrizi, M.; Zahmatkesh, F.; Korayem, A.H. A review of the impact of micro- and nanoparticles
on freeze–thaw durability of hardened concrete: Mechanism perspective. Constr. Build. Mater. 2018, 186, 1105–1113. [CrossRef]
120. Wang, J.B.; Niu, D.T.; He, H. Frost durability and stress-strain relationship of lining shotcrete in cold environment. Constr. Build.
Mater. 2019, 198, 58–69. [CrossRef]
121. Wang, Y.; Zhang, S.H.; Niu, D.T.; Fu, Q. Quantitative evaluation of the characteristics of air voids and their relationship with the
permeability and salt freeze–thaw resistance of hybrid steel-polypropylene fiber-reinforced concrete composites. Cem. Concr.
Comp. 2022, 125, 104292. [CrossRef]
122. Xu, F.; Wang, S.L.; Li, T.; Liu, B.; Zhao, N.; Liu, K.N. The mechanical properties and resistance against the coupled deterioration of
sulfate attack and freeze–thaw cycles of tailing recycled aggregate concrete. Constr. Build. Mater. 2021, 269, 121273. [CrossRef]
123. Zhang, B.; Li, Q.B.; Niu, X.J.; Yang, L.; Hu, Y.; Zhang, J.L. Influence of a novel hydrophobic agent on freeze–thaw resistance and
microstructure of concrete. Constr Build. Mater. 2021, 269, 121294. [CrossRef]
124. Zhang, P.; Wittmann, F.H.; Vogel, M.; Muller, H.S.; Zhao, T.J. Influence of freeze–thaw cycles on capillary absorption and chloride
penetration into concrete. Cem. Concr. Res. 2017, 100, 60–67. [CrossRef]
125. Sun, M.; Zou, C.Y.; Xin, D.B. Pore structure evolution mechanism of cement mortar containing diatomite subjected to freeze–thaw
cycles by multifractal analysis. Cem. Concr. Comp. 2020, 114, 103731. [CrossRef]
126. Zheng, X.; Liu, F.; Luo, T.; Duan, Y.; Yi, Y.; Hua, C. Study on Durability and Pore Characteristics of Concrete under Salt Freezing
Environment. Materials 2021, 14, 7228. [CrossRef]
127. Tian, W.; Han, N. Pore characteristics (>0.1 mm) of non-air entrained concrete destroyed by freeze–thaw cycles based on CT
scanning and 3D printing. Cold Reg. Sci. Technol. 2018, 151, 314–322. [CrossRef]
128. Chen, J.; Deng, X.; Luo, Y.; He, L.; Liu, Q.; Qiao, X. Investigation of microstructural damage in shotcrete under a freeze–thaw
environment. Constr. Build. Mater. 2015, 83, 275–282. [CrossRef]
129. Wang, Y.; Yang, W.; Ge, Y.; Liu, P.; Zhang, A. Analysis of freeze–thaw damage and pore structure deterioration of mortar by
low-field NMR. Constr. Build. Mater. 2021, 319, 126097. [CrossRef]
130. Jia, H.L.; Ding, S.; Zi, F.; Dong, Y.H.; Shen, Y.J. Evolution in sandstone pore structures with freeze–thaw cycling and interpretation
of damage mechanisms in saturated porous rocks. Catena 2020, 195, 104915. [CrossRef]
131. Liu, T.; Zhang, C.; Zhou, K.; Tian, Y. Freeze-thaw cycling damage evolution of additive cement mortar. Eur. J. Environ. Civ. Eng.
2021, 25, 2089–2110. [CrossRef]
132. Zhang, K.; Zhou, J.; Yin, Z. Experimental Study on Mechanical Properties and Pore Structure Deterioration of Concrete under
Freeze–Thaw Cycles. Materials 2021, 14, 6568. [CrossRef] [PubMed]
133. Shen, Y.; Wang, Y.; Wei, X.; Jia, H.; Yan, R. Investigation on meso-debonding process of the sandstone-concrete interface induced
by freeze–thaw cycles using NMR technology. Constr. Build. Mater. 2020, 252, 118962. [CrossRef]
134. Sypek, M.; Latawiec, R.; Lazniewska-Piekarczyk, B.; Pichor, W. Impact of Surfactant and Calcium Sulfate Type on Air-Entraining
Effectiveness in Concrete. Materials 2022, 15, 985. [CrossRef] [PubMed]
135. He, B.; Xie, M.; Jiang, Z.; Zhang, C.; Zhu, X. Temperature field distribution and microstructure of cement-based materials under
cryogenic freeze–thaw cycles. Constr. Build Mater. 2020, 243, 118256. [CrossRef]
136. Yao, H.; Xie, Z.; Huang, C.; Yuan, Q.; Yu, Z. Recent progress of hydrophobic cement-based materials: Preparation, characterization
and properties. Constr. Build. Mater. 2021, 299, 124255. [CrossRef]
137. Zeng, W.; Ding, Y.; Zhang, Y.; Dehn, F. Effect of steel fiber on the crack permeability evolution and crack surface topography of
concrete subjected to freeze–thaw damage. Cement Concrete Res. 2020, 138, 106230. [CrossRef]
138. Sanchez, L.F.M.; Drimalas, T.; Fournier, B.; Mitchell, D.; Bastien, J. Comprehensive damage assessment in concrete affected by
different internal swelling reaction (ISR) mechanisms. Cem. Concr. Res. 2018, 107, 284–303. [CrossRef]
139. Soroushian, P.; Elzafraney, M. Damage effects on concrete performance and microstructure. Cem. Concr. Comp. 2004, 26, 853–859.
[CrossRef]
140. Yang, X.L.; Shen, A.Q.; Guo, Y.C.; Zhou, S.B.; He, T.Q. Deterioration mechanism of interface transition zone of concrete pavement
under fatigue load and freeze–thaw coupling in cold climatic areas. Constr. Build. Mater. 2018, 160, 588–597. [CrossRef]
141. Liu, M.; Qiao, P.; Sun, L. Dependence of chloride ion diffusivity on evolution of pore-structures in freeze–thawed shotcrete:
Multiscale characterization and modeling. Cem. Concr. Comp. 2021, 123, 104222. [CrossRef]
142. Shields, Y.; Garboczi, E.; Weiss, J.; Farnam, Y. Freeze-thaw crack determination in cementitious materials using 3D X-ray computed
tomography and acoustic emission. Cem. Concr. Comp. 2018, 89, 120–129. [CrossRef]
Buildings 2022, 12, 1317 35 of 36

143. Liu, M.X.; Qiao, P.Z.; Sun, L.Z. Multiscale modeling of damage and fracture in freeze–thawed shotcrete. Int. J. Damage Mech. 2022,
31, 142–162. [CrossRef]
144. Dong, Y.; Su, C.; Qiao, P.; Sun, L.Z. Microstructural damage evolution and its effect on fracture behavior of concrete subjected to
freeze–thaw cycles. Int. J. Damage Mech 2018, 27, 1272–1288. [CrossRef]
145. Dong, Y.J.; Su, C.; Qiao, P.Z.; Sun, L.Z. Microstructural crack segmentation of three-dimensional concrete images based on deep
convolutional neural networks. Constr. Build. Mater. 2020, 253, 119185. [CrossRef]
146. Luo, Q.; Liu, D.X.; Qiao, P.Z.; Feng, Q.G.; Sun, L.Z. Microstructural damage characterization of concrete under freeze–thaw action.
Int. J. Damage Mech. 2018, 27, 1551–1568. [CrossRef]
147. Zou, D.J.; Wang, Z.Z.; Shen, M.M.; Liu, T.J.; Zhou, A. Improvement in freeze–thaw durability of recycled aggregate permeable
concrete with silane modification. Constr. Build. Mater. 2021, 268, 121097. [CrossRef]
148. Wu, K.; Han, H.; Li, H.; Dong, B.; Liu, T.; De Schutter, G. Experimental study on concurrent factors influencing the ITZ effect on
mass transport in concrete. Cem. Concr. Compos. 2021, 123, 104215. [CrossRef]
149. Wu, K.; Shi, H.; Xu, L.; Ye, G.; De Schutter, G. Microstructural characterization of ITZ in blended cement concretes and its relation
to transport properties. Cem. Concr. Res. 2015, 79, 243–256. [CrossRef]
150. Maruyama, I.; Sasano, H.; Lin, M. Impact of aggregate properties on the development of shrinkage-induced cracking in concrete
under restraint conditions. Cem. Concr. Res. 2016, 85, 82–101. [CrossRef]
151. Cwirzen, A.; Penttala, V. Aggregate-cement paste transition zone properties affecting the salt-frost damage of high-performance
concretes. Cem. Concr. Res. 2005, 35, 671–679. [CrossRef]
152. Lizarazo-Marriaga, J.; Higuera, C.; Claisse, P. Measuring the effect of the ITZ on the transport related properties of mortar using
electrochemical impedance. Constr. Build. Mater. 2014, 52, 9–16. [CrossRef]
153. Zheng, X.; Wang, Y.; Zhang, S.; Xu, F.; Zhu, X.; Jiang, X.; Zhou, L.; Shen, Y.; Chen, Q.; Yan, Z.; et al. Research progress of the
thermophysical and mechanical properties of concrete subjected to freeze–thaw cycles. Constr. Build. Mater. 2022, 330, 127254.
[CrossRef]
154. Hao, L.; Liu, Y.; Wang, W.; Zhang, J.; Zhang, Y. Effect of salty freeze–thaw cycles on durability of thermal insulation concrete with
recycled aggregates. Constr. Build. Mater. 2018, 189, 478–486. [CrossRef]
155. Zhou, Z.; Xie, R.; Qiao, P.; Lu, L. On the modeling of tensile behavior of ultra-high performance fiber-reinforced concrete with
freezing-thawing actions. Compos. Part B Eng. 2019, 174, 106983. [CrossRef]
156. Pang, B.; Zhou, Z.; Cheng, X.; Du, P.; Xu, H. ITZ properties of concrete with carbonated steel slag aggregate in salty freeze–thaw
environment. Constr. Build. Mater. 2016, 114, 162–171. [CrossRef]
157. Sicat, E.; Gong, F.; Ueda, T.; Zhang, D. Experimental investigation of the deformational behavior of the interfacial transition zone
(ITZ) in concrete during freezing and thawing cycles. Constr. Build. Mater. 2014, 65, 122–131. [CrossRef]
158. Siamardi, K.; Shabani, S. Evaluation the effect of micro-synthetic fiber on mechanical and freeze–thaw behavior of non-air-
entrained roller compacted concrete pavement using response surface methodology. Constr. Build. Mater. 2021, 295, 123628.
[CrossRef]
159. Petersen, L.; Lohaus, L.; Polak, M.A. Influence of freezing-and-thawing damage on behavior of reinforced concrete elements. ACI
Mater. J. 2007, 104, 369–378.
160. Nili, M.; Azarioon, A.; Hosseinian, S.M. Novel Internal-Deterioration Model of Concrete Exposed to Freeze–Thaw Cycles. J.
Mater. Civ. Eng. 2017, 29, 04017132. [CrossRef]
161. Guan, X.; Chen, J.; Qiu, J.; Gao, Y.; Gao, J. Damage evaluation method based on ultrasound technique for gangue concrete under
freezing-thawing cycles. Constr. Build. Mater. 2020, 246, 118437. [CrossRef]
162. Guan, X.; Qiu, J.; Song, H.; Qin, Q.; Zhang, C. Stress–strain behaviour and acoustic emission characteristic of gangue concrete
under axial compression in frost environment. Constr. Build. Mater. 2019, 220, 476–488. [CrossRef]
163. Azarsa, P.; Gupta, R.; Biparva, A. Assessment of self-healing and durability parameters of concretes incorporating crystalline
admixtures and Portland Limestone Cement. Cem. Concr. Compos. 2019, 99, 17–31. [CrossRef]
164. Hasholt, M.T.; Christensen, K.U.; Pade, C. Frost resistance of concrete with high contents of fly ash—A study on how hollow fly
ash particles distort the air void analysis. Cem. Concr. Res. 2019, 119, 102–112. [CrossRef]
165. Xiao, Q.H.; Niu, D.T.; Zhu, W.P. Strength degradation model and durability service life prediction of concrete in freezing-thawing
circumstance. Build. Struct. 2011, 41, 203–207.
166. Yu, H.; Sun, W.; Ma, H.; Zhang, Y.; Miao, C.; Jin, Z.; Liu, J. Predicting method of concrete service life based on damage development
equation. J. Archit. Civil. Eng. 2012, 29, 1–7.
167. Mu, R. Durability and Service Life Prediction of Concrete Subjected to the Combined Action of Freezing-Thawing, Sustained
External Flexural Stress and Salt Solution. Ph.D. Thesis, Southeast University, Nanjing, China, 2000.
168. Zhang, F.; Li, S.; Li, S. Three-dimensional Random Damage Prediction Model of Concrete Caused by Freeze-thaw. J. Civil. Archit.
Environ. Eng. 2011, 33, 31–35.
169. Cho, T. Prediction of cyclic freeze–thaw damage in concrete structures based on response surface method. Constr. Build. Mater.
2007, 21, 2031–2040. [CrossRef]
170. Li, B.; Mao, J.; Nawa, T.; Han, T. Mesoscopic damage model of concrete subjected to freeze–thaw cycles using mercury intrusion
porosimetry and differential scanning calorimetry (MIP-DSC). Constr. Build. Mater. 2017, 147, 79–90. [CrossRef]
Buildings 2022, 12, 1317 36 of 36

171. Zhang, C.; Ma, W.; Liu, X.; Tian, Y.; Orton, S.L. Effects of high temperature on residual punching strength of slab-column
connections after cooling and enhanced post-punching load resistance. Eng. Struct. 2019, 199, 109580. [CrossRef]
172. Xu, W.-H.; Zhang, Q.-N.; Ma, W.-C.; Wang, E.-H. Response of Two Unequal-Diameter Flexible Cylinders in A Side-by-Side
Arrangement: Characteristics of FIV. China Ocean Eng. 2020, 34, 475–487. [CrossRef]
173. Chen, X.; Wang, D.Y.; Tang, J.B.; Ma, W.C.; Liu, Y. Geotechnical stability analysis considering strain softening using micro-polar
continuum finite element method. J. Cent. South Univ. 2021, 28, 297–310. [CrossRef]