materials

Article
Potential for Recycling Metakaolin/Slag-Based Geopolymer
Concrete of Various Strength Levels in Freeze–Thaw Conditions
Mengtong Liu 1 , Hui Liu 1, * , Minqi Hua 2 , Chunhong Chen 1 , Xinjie Wang 1 , Xiang Guo 1 and Tianyu Ma 1

1 School of Urban Construction, Changzhou University, 21 Gehu Middle Road, Wujin District,
Changzhou 213164, China; [email protected] (M.L.); [email protected] (C.C.);
[email protected] (X.W.); [email protected] (X.G.); [email protected] (T.M.)
2 School of Civil Engineering & Architecture, Wuhan University of Technology, Wuhan 430070, China;
[email protected]
* Correspondence: [email protected]; Tel.: +86-173-9683-5171

Abstract: Geopolymer concrete (GPC) represents an innovative green and low-carbon construction
material, offering a viable alternative to ordinary Portland cement concrete (OPC) in building appli-
cations. However, existing studies tend to overlook the recyclability aspect of GPC for future use.
Various structural applications necessitate the use of concrete with distinct strength characteristics.
The recyclability of the parent concrete is influenced by these varying strengths. This study exam-
ined the recycling potential of GPC across a spectrum of strength grades (40, 60, 80, and 100 MPa,
marked as C40, C60, C80, and C100) when subjected to freeze–thaw conditions. Recycling 5–16 mm
recycled geopolymer coarse aggregate (RGAs) from GPC prepared from 5 to 16 mm natural coarse
aggregates (NAs). The cementitious material comprised 60% metakaolin and 40% slag, with natural
gravel serving as the NAs, and the alkali activator consisting of sodium hydroxide solution and
sodium silicate solution. The strength of the GPC was modulated by altering the Na/Al ratio. After
350 freeze–thaw cycles, the GPC specimens underwent crushing, washing, and sieving to produce
RGAs. Subsequently, their physical properties (apparent density, water absorption, crushing index,
and attached mortar content and microstructure (microhardness, SEM, and XRD) were thoroughly
examined. The findings indicated that GPC with strength grades of C100, C80, and C60 were capable
Citation: Liu, M.; Liu, H.; Hua, M.; of enduring 350 freeze–thaw cycles, in contrast to C40, which did not withstand these conditions.
Chen, C.; Wang, X.; Guo, X.; Ma, T. RGAs derived from GPC of strength grades C100 and C80 complied with the criteria for Class II
Potential for Recycling recycled aggregates, whereas RGAs produced from GPC of strength grade C60 aligned with the
Metakaolin/Slag-Based Geopolymer Class III level. A higher-strength grade in the parent concrete correlated with enhanced performance
Concrete of Various Strength Levels in characteristics in the resulting recycled aggregates.
Freeze–Thaw Conditions. Materials
2024, 17, 1944. https://doi.org/
Keywords: geopolymer concrete; recycling potential; strength levels; freeze–thaw resistance; recycled
10.3390/ma17091944
geopolymer aggregates; physical properties
Academic Editor: F. Pacheco Torgal

Received: 31 March 2024

Revised: 20 April 2024
1. Introduction
Accepted: 20 April 2024
Published: 23 April 2024 Elevated carbon emissions contribute to rising global temperatures and intensify the
greenhouse effect [1,2]. Cement, as a fundamental consumable in the construction indus-
try, necessitates mining and high-temperature calcination processes. These activities not
only cause environmental degradation but also result in substantial CO2 emissions [3,4].
Copyright: © 2024 by the authors. Geopolymer, an emerging green building material, is predominantly an inorganic polymer
Licensee MDPI, Basel, Switzerland. featuring a three-dimensional network structure. It is synthesized through the depolymer-
This article is an open access article ization and polycondensation reactions of silicon–aluminum oxides found in materials such
distributed under the terms and as fly ash, metakaolin, and red mud, under the action of activators, including acids, alkalis,
conditions of the Creative Commons
and salts [5]. Geopolymer is considered an excellent substitute for traditional ordinary
Attribution (CC BY) license (https://
Portland cement (OPC), thanks to its superior qualities, including high strength, robust
creativecommons.org/licenses/by/
stability, good acid and corrosion resistance, and fire resistance [6–8]. Its manufacturing
4.0/).

Materials 2024, 17, 1944. https://doi.org/10.3390/ma17091944 https://www.mdpi.com/journal/materials

Materials 2024, 17, 1944 2 of 17

process emits negligible CO2 , making it an environmentally friendly option. Producing

1 ton of traditional Portland cement emits approximately 900–1000 kg of CO2 , while pro-
ducing 1 ton of geopolymer cement only emits 200–300 kg of CO2 , which means that using
geopolymer instead of traditional Portland cement can reduce carbon emissions by about
70% [9,10].
Cold regions refer to areas where the average temperature of the coldest month meets
−10 ◦ C–0 ◦ C every year, and the number of days with a daily average temperature of
≤5 ◦ C is 90–145 days every year [11]. Cold regions are widely distributed across the world,
encompassing approximately 25% of the land area [12]. These regions are primarily located
in the northern parts of North America, Europe, and Asia, as well as in Central Asia,
Antarctica, and its surrounding islands. In China, the cold regions account for about 40% of
the country’s total area [13]. Therefore, frost resistance becomes one of the most important
durability characteristics for concrete structures in these regions [14]. In such an environ-
ment, concrete constructions have a longer setting time, slower strength development, and
a reduced dehydration rate [15], as well as water that penetrates the concrete and under-
goes freezing and melting to generate expansion pressure, which escalates the quantity of
internal cracks and voids within the concrete, thus reducing its durability [16,17]. With
the influence of recurrent freeze–thaw cycles, the structure of buildings in cold regions
transitions from compact to porous, markedly reducing the buildings’ service life. Research
on the frost resistance of OPC concrete indicates that incorporating air-entraining agents
(AEAs) and fibers can markedly boost its durability against freeze–thaw cycles [18–20].
AEAs work by creating micro air bubbles of 20 to 50 µm, offering space for water to freeze
and expand, which in turn lowers the internal pressure of the concrete [21,22]. Meanwhile,
fibers serve to prevent the spread of cracks and reduce stress concentration at the tips
of cracks [23–25]. However, it has been established in existing research that AEAs and
fibers provide limited benefits in enhancing the frost resistance of geopolymer concrete
(GPC) [26–28]. Pilehvar et al. [29] prepared GPC with a strength of around 80 MPa, using
fly ash and slag, and found that, after 28 freeze–thaw cycles, its compressive strength loss
was within 5%. Aiken et al. [30] prepared fly ash-based GPC with a strength range of
15–60 MPa and found that, as the slag content increased, the compressive strength and frost
resistance of GPC gradually improved. After 56 freeze–thaw cycles, the mass loss of GPC
with slag content of 40% and 70% was only 2.6% and 0.2%, respectively. Fu et al. [31] used
alkaline activator to prepare slag-based GPC with a strength of about 90 MPa. It was found
that, after 300 freeze–thaw cycles, its RDEM reached 90%, and the mass loss was only 0.12%.
Consequently, to explore the applicability of GPC in cold regions, this study utilized slag
as an admixture to formulate a metakaolin/slag-based binary system geopolymer concrete.
When building structures reach the end of their service life or need to be demolished
for reconstruction, many construction and demolition wastes (C&DWs) are generated.
Converting this solid waste into recycled aggregates for structural use is a preferred solution
to address the waste issue. Figiela et al. [32] used clay bricks and concrete fragments to
partially replace metakaolin and fly ash in the production of geopolymers, resulting in
geopolymers with better mechanical properties. Korniejenko [33] used mining waste
coal shale as a precursor to prepare geopolymer and found that its compressive and
bending strength met the requirements of buildings, such as foundations, walls, and
columns. Alhawat et al. [34] found that geopolymers have broad application prospects
in the construction field, and it is possible to produce GPC with properties comparable
to OPC using C&DW-based materials. Current practices for C&DWs’ disposal fail to
consider the influence of the parent concrete’s performance on the quality of subsequent
recycled aggregates. This oversight results in variability and inconsistency in the quality of
the recycled materials, which hinders their potential for effective reuse. By assessing the
recyclability of concrete at the design stage, materials of varying quality can be promptly
recycled and precisely utilized after the end of a building’s lifespan, greatly reducing
resource waste and advancing sustainable development. Building on prior research, GPC
is believed to possess promising recycling potential. Akbarnezhad et al. [35] observed that
Materials 2024, 17, 1944 3 of 17

recycled geopolymer aggregates (RGAs) exhibited greater wear resistance than traditional
recycled aggregates. Zhu et al. [36] reported that the properties of geopolymer mortar made
from recycled geopolymer fine aggregates with a replacement ratio of less than 50% were
comparable to those made with natural fine aggregates. Additionally, Mesgari et al. [37]
discovered that recycled geopolymer aggregates (RGAs) demonstrated superior bonding
performance with geopolymer mortar compared to recycled cement concrete aggregates.
Hence, exploring the influence of parent GPC on the properties of RGAs and contemplating
the sustainable reuse of waste concrete from the design phase are of paramount importance.
Metakaolin, produced through the low-temperature calcination of ultrafine kaolin, is
an amorphous aluminum silicate that is known for its significant pozzolanic activity. This
makes it a frequently utilized precursor in the manufacture of geopolymers [38]. Granulated
blast-furnace slag is a by-product of the blast furnace ironmaking process; it is often used as
a mineral admixture due to its high activity [39]. In this study, metakaolin combined with
40% slag and crushed stone aggregates was used to prepare GPC. Considering that different
building structures in practice require GPC of varying strength levels, and the strength of
the parent GPC directly impacts the performance of the resulting RGAs, it is inadequate
to examine only a single strength grade of GPC. Therefore, GPC with strengths of 40, 60,
80, and 100 MPa was formulated to evaluate its frost resistance and the recycling potential
after reaching a designed service life of 50 years. The aim of this study was to explore the
frost resistance of GPC with different strength levels, analyze the performance differences
of RGAs, reveal their differential mechanisms, and evaluate their recycling potential. The
novelty of this study is related to the recycling potential of GPC with different strength
levels, as it has not been studied before.

2. Materials and Methods

2.1. Materials and Reagents
2.1.1. Metakaolin and Slag
The metakaolin (MK) was sourced from Gongyi Oushang Refractory Materials Co.,
Ltd. (Gongyi, China), and the slag (SL) came from Longze Water Purification Materials Co.,
Ltd. (Zhengzhou, China). It is S95-grade slag and was obtained by granulating the molten
material from blast furnace smelting through water quenching and cooling. The chemical
compositions of both metakaolin and slag are shown in Table 1. It can be seen from Table 1
that the metakaolin contains 48.88% SiO2 and 43.39% Al2 O3 . This large amount of silicon
aluminum oxide is beneficial to the formation of silicon oxygen tetrahedron and aluminum
oxygen tetrahedron in the geopolymer gel [40]. The slag contains 40.57% CaO, which
helps to consume water in the geopolymer system, making the geopolymer structure more
compact and conducive to strength and frost resistance [41].

Table 1. Chemical compositions of MK and SL determined by XRF.

wt/% SiO2 Al2 O3 CaO Fe2 O3 P2 O5 K2 O TiO2 SO3 MgO Na2 O

MK 48.88 43.39 0.983 3.77 0.072 0.141 2.452 0.044 - -
SL 30.54 15.27 40.57 0.26 - 0.416 0.747 2.03 9.01 0.548

2.1.2. Alkali Activator

The sodium silicate (Na2 SiO3 ) solution, featuring a modulus of 2.31 and a mass fraction
of 42%, was purchased from Wuxi City Yatai United Chemical Co., Ltd. (Wuxi, China).
The solid sodium hydroxide (NaOH) was obtained from Kunshan Jincheng Reagent Co.,
Ltd. (Kunshan, China). Its solution with a concentration of 12 mol/L was prepared using
distilled water. It was allowed to stand for 24 h prior to usage.

2.1.3. Aggregate
The coarse aggregate utilized in this study was natural crushed stone, characterized by
a particle size of 5–16 mm and an apparent density of 2738 kg/m3 . For the fine aggregate,
 2.1.3. Aggregate
The coarse aggregate utilized in this study was natural crushed stone, characterized
Materials 2024, 17, 1944 by a particle size of 5–16 mm and an apparent density of 2738 kg/m3. For the fine aggre-
4 of 17
gate, river sand was used, which has a fineness modulus of 2.8 and an apparent density
of 2606 kg/m3. The aggregate gradations are shown in Figure 1. These aggregates complied
river
with thesand was used,
continuous which has
gradation a fineness modulus
requirements specifiedof by
2.8 standards
and an apparent density of [42]
GB/T 14684-2022
2606 kg/m3 . The aggregate gradations are shown in Figure 1. These aggregates complied
and GB/T 14685-2022 [43] (relevant international standard refers to ASTM C33/C33M-23
with the continuous gradation requirements specified by standards GB/T 14684-2022 [42] and
[44]).
GB/T 14685-2022 [43] (relevant international standard refers to ASTM C33/C33M-23 [44]).

Figure 1. 1.
Figure The aggregate
The aggregategradation: (a)coarse
gradation: (a) coarseaggregate
aggregate and
and (b)(b)
finefine aggregate.
aggregate.

2.2. Methods
2.2. Methods
2.2.1. Preparation of GPC and RGA
2.2.1. Preparation of GPC and RGA
Four groups of GPCs with varying strength grades (40, 60, 80, and 100 MPa) were
Four groups
developed, of GPCs
designated with varying
as GPC-C40, strength
GPC-C60, grades
GPC-C80, and(40, 60, 80, respectively.
GPC-C100, and 100 MPa) were
developed, designated
Referring as GPC-C40,
to previous GPC-C60,
studies to design GPC-C80,
the mix andaGPC-C100,
ratio [45–48], respectively.
consistent mass of 450 g
forReferring
the cementitious material was maintained, and the mass ratio of NaOH and
to previous studies to design the mix ratio [45–48], a consistent mass Na 2 SiO3of 450
solution was fixed at 1:1.6. The strength of GPC was modulated by varying
g for the cementitious material was maintained, and the mass ratio of NaOH and Na2SiO3 the Na/Al
ratio, with pre-experiment conducted for adjustment and optimization. The determined
solution was fixed at 1:1.6. The strength of GPC was modulated by varying the Na/Al
mix proportions are presented in Table 2.
ratio, with pre-experiment conducted for adjustment and optimization. The determined
mix proportions
Table are presented
2. Mix proportions in Table
of 1 m3 GPC 2. (kg).
specimen

Table Grade
2. Mix proportions River Na2 SiO3 NaOH
Metakaolin of 1Slag
m3 GPC specimen
Gravel (kg). Water
Sand Solution Solution
C100 270 180 1210 River
650 Na2SiO3
206 129NaOH 0
Grade
C80 Metakaolin
270 Slag
180 Gravel
1210 650 184 115 15 Water
C60 270 180 1210 650Sand Solution
162 Solution
101 30
C40
C100 270
270 180
180 1210
1210 650 650 131 206 81 129 0 53

C80 270 180 1210 650 184 115 15

C60 The preparation
270 process
180of GPC was
1210executed according
650 to the
162 following
101 sequence
30
of steps: Initially, the cementitious material and aggregate were mixed and stirred for
C40 270 180 1210 650 131 81 53
approximately 90 s. Subsequently, the NaOH solution, Na2 SiO3 solution, and water were
added. After thorough stirring for about 120 s, the mixture was transferred into the mold.
Thethe
Once preparation
surface had process of hardened,
sufficiently GPC wasthe executed
mold was according
wrapped into plastic
the following
and placedsequence
in
of steps: Initially,
a standard curingthe cementitious
room, material
where it was and aggregate
maintained were
at a constant mixed and
temperature ± 2 ◦C
stirred
of 20 for ap-
proximately 90 humidity
and a relative s. Subsequently,
exceedingthe NaOH
95%. solution,
Twenty-four Na2post-casting,
hours SiO3 solution,theand water were
specimens
were After
added. demolded,
thoroughsealed in air-tight
stirring bags, 120
for about ands,placed in an environment
the mixture maintained
was transferred into theatmold.
80 ◦the
Once C for an additional
surface 24 h. After
had sufficiently this high-temperature
hardened, the mold wascuring phase,
wrapped in the specimens
plastic and placed
in a standard curing room, where it was maintained at a constant temperature3 of
were relocated to the standard curing room to continue the curing process until d, 720d,± 2 °C
14 d, and 28 d. Cubic specimens with dimensions of 100 mm × 100 mm × 100 mm
and a relative humidity exceeding 95%. Twenty-four hours post-casting, the specimens
were employed for assessing mechanical properties, while prismatic specimens measuring
100 mm × 100 mm × 400 mm were used for the frost-resistance test.
Post-freeze–thaw cycling, the GPC specimens were subjected to crushing with a jaw
crusher to yield recycled geopolymer aggregates (RGAs). These were correspondingly la-
Materials 2024, 17, 1944 5 of 17

beled as RGA-C40, RGA-C60, RGA-C80, and RGA-C100, in alignment with their originating
GPC-strength grades.

2.2.2. Test Methods

The compressive strength (fc) and splitting tensile (ft) strength of GPC at 3 d, 7 d, 14 d,
and 28 d was tested in accordance with the specified standard GB/T 50081-2019 [49] (relevant
international standards refer to ASTM C39/C39M-23 [50] and ASTM C496/C496M-17 [51]). A
microcomputer-controlled pressure testing machine (c) manufactured by Wuxi Xinluda In-
strument Equipment Co., Ltd. (Wuxi, China) was used to test the fc and ft of the specimens,
with the average value calculated from three specimens in each group.
In accordance with the rapid freeze–thaw cycle method outlined in standard
GB/T 50082-2009 [52] (relevant international standard refers to ASTM C666/C666M-15 [53]),
the frost resistance of GPC was evaluated based on the relative dynamic modulus of elasticity
(RDEM) and mass loss. The average of three samples in each group was taken as the final
result. A rapid freeze–thaw cycle testing machine (TDR-3F48) manufactured by Shanghai
Sanhao Refrigeration Equipment Factory (Shanghai, China) was employed to assess frost
resistance. The test was concluded once the number of freeze–thaw cycles reached 350, the
mass loss attained 5%, or when the RDEM fell below 60%.
The apparent density, water absorption, and crushing index of the RGAs were assessed
in accordance with the guidelines set forth in GB/T 14685-2022 [43] (relevant international
standards refer to ASTM C127-15 [54] and EN 1097-2: 2020 [55]). Thermal treatment
methods were used to determine the attached mortar content of RGAs [56]. The average of
three samples in each group was taken as the final result. Referring to GB/T 25177-2010 [57],
RGAs are classified according to Table 3.

Table 3. RGAs’ classification standards.

Apparent Density Water Absorption

Crushing Index (%)
(kg/m3 ) Rate (%)
Class I >2450 <3 <12
Class II >2350 <5 <20
Class III >2250 <8 <30

SEM (Zeiss SUPRA55) manufactured by Carl Zeiss AG (Oberkochen, Germany) was

employed to examine the microstructural morphology of GPC and RGAs. An electric
grinder was used to select samples with dimensions of 5 mm × 5 mm × 3 mm from
GPC and RGA, which contained mortar and aggregate. The bottom surface was ground
flat, and then it was baked in a 60 ◦ C oven for 24 h. Before testing, the samples were
sprayed with gold. The microhardnesses of the RGA’s interfacial transition zone (ITZ) and
attached mortar were measured using a digital Vickers microhardness tester (HVS-1000SS)
manufactured by Shanghai Precision Instrument Co., Ltd. (Shanghai, China), with a load
of 10 g and a loading time of 10 s. XRD (D/Max2500) manufactured by Rigaku (Tokyo,
Japan) was utilized to characterize the mineral compositions of the attached mortar on the
RGA. After extracting the attached mortar, a mortar was used to grind it into a flour shape,
and then it was baked in a 60 ◦ C oven for 24 h.

3. Results and Discussion

3.1. Compressive Strength of GPC
The compressive strength evolution of the four GPC specimen groups at 3 d, 7 d,
14 d, and 28 d, before undergoing the freeze–thaw cycles, is depicted in Figure 2. Regardless
of the strength grade, all the compressive strengths of the GPC showed a rapid increase
within the initial seven days, subsequently experiencing a gradual slowdown. By the 7th
day, the specimens across all four groups had essentially achieved their anticipated strength
levels. The 7-day compressive strengths of GPC-C100, GPC-C80, GPC-C60, and GPC-C40
attained 94.9%, 94.3%, 93.8%, and 94.6% of their respective 28-day compressive strengths,
 Early in the curing process, the presence of high levels of active ingredients in the
cementitious materials, combined with alkali activators, fosters swift dissolution of silico-
aluminate components [60]. This action swiftly triggers hydration and geopolymerization
reactions, leading to the formation of polymer gels, which fill the pores within the mate-
Materials 2024, 17, 1944 rial, significantly enhancing its density and strength [61]. Consequently, this sequence of
6 of 17
events is instrumental in contributing to the rapid escalation of early strength. But over
time, these reactions slow down as the material approaches its final structure and proper-
ties. With the decrease in alkali dosage, the final strength of GPC decreases, indicating
which was attributed to the application of high-temperature curing. By curing at 80 ◦ C for
that the dosage of the alkali activator will affect the strength of GPC. The higher the
a single day, the efficiency of the polymerization reaction was markedly improved, which
amount ofthe
shortened alkali activator,
overall curingthe faster the
duration silicon–aluminum
for GPC oxide
and significantly in the cementitious
enhanced ma-
its early strength
terial will be dissolved, and the more complete the polymerization reaction will
development [58,59]. Beyond the initial 7 d, the increase rate of compressive strength in be [62],
resulting
GPC began into
the formation
taper off. of more geopolymer gels and higher strength.

Figure 2.
Figure 2. Compressive
Compressive strength
strength development
development of
of GPC
GPC specimens.
specimens.

3.2. Splitting
Early inTensile Strength
the curing of GPC
process, the presence of high levels of active ingredients in the
cementitious materials,
The splitting tensilecombined
strength with
of thealkali activators,
samples before fosters swift dissolution
freeze–thaw of7silico-
cycles at 3 d, d, 14
aluminate components [60]. This action swiftly triggers hydration and geopolymerization
d, and 28 d is shown in Figure 3. As the age increases, the splitting tensile strength in-
reactions, leadingintothe
creases rapidly theinitial
formation
stageofand
polymer gels, which
gradually fill the in
slows down pores
the within the material,
later stage. The 7d
significantly enhancing its density and strength [61]. Consequently,
splitting tensile strength of GPC-C100, GPC-C80, GPC-C60, and GPC-C40 reached this sequence of events
87.2%,
is instrumental
94.3%, 93.8%, and in contributing
91.1% of theirto the rapidsplitting
28-day escalation of early
tensile strength.
strength, But over time,
respectively. The these
split-
reactions
ting tensileslow down as
strength thecompressive
and material approaches
strengthitsarefinal structure
positively and properties.
correlated. With the
GPC-C100 has
decrease in alkali dosage, the final strength of GPC decreases, indicating
the highest 28-day splitting tensile strength, at 12.96 MPa, while GPC-C40 has the lowest that the dosage of
the alkali activator will affect the strength of GPC. The higher the amount of alkali activator,
28-day splitting tensile strength, at 4.15 MPa. The content of calcium oxide and the amount
the faster the silicon–aluminum oxide in the cementitious material will be dissolved, and
the more complete the polymerization reaction will be [62], resulting in the formation of
more geopolymer gels and higher strength.

3.2. Splitting Tensile Strength of GPC

The splitting tensile strength of the samples before freeze–thaw cycles at 3 d, 7 d,
14 d, and 28 d is shown in Figure 3. As the age increases, the splitting tensile strength
increases rapidly in the initial stage and gradually slows down in the later stage. The
7 d splitting tensile strength of GPC-C100, GPC-C80, GPC-C60, and GPC-C40 reached
87.2%, 94.3%, 93.8%, and 91.1% of their 28-day splitting tensile strength, respectively. The
splitting tensile strength and compressive strength are positively correlated. GPC-C100 has
the highest 28-day splitting tensile strength, at 12.96 MPa, while GPC-C40 has the lowest
28-day splitting tensile strength, at 4.15 MPa. The content of calcium oxide and the amount
of alkali activator have an important impact on the strength of GPC. Within a certain range,
the greater the content of calcium oxide is and the greater the amount of alkali activator
is, the more conducive to the polymerization reaction [63,64]. Increasing the amount of
alkali activator will accelerate the dissolution rate of aluminosilicate, promote the fixation
of water and the formation of the structure, accelerate the rapid setting and formation
of geopolymer gel, and produce a compact and solid structure, which is conducive to
the development of early strength. At the same time, high-temperature curing will also
accelerate this process [65].
 activator is, the more conducive to the polymerization reaction [63,64]. Increasing the
amount of alkali activator will accelerate the dissolution rate of aluminosilicate, promote
the fixation of water and the formation of the structure, accelerate the rapid setting and
formation of geopolymer gel, and produce a compact and solid structure, which is con-
Materials 2024, 17, 1944 7 of 17
ducive to the development of early strength. At the same time, high-temperature curing
will also accelerate this process [65].

Figure 3.
Figure 3. Splitting
Splitting tensile
tensile strength
strength development
development of
of GPC
GPC specimens.
specimens.

3.3.
3.3. Frost
Frost Resistance
Resistance of of GPC
GPC
3.3.1. Visual Appearance
3.3.1. Visual Appearance
Figure 4 illustrates the degradation process of the four GPC specimen groups when
Figure 4 illustrates the degradation process of the four GPC specimen groups when
exposed to freeze–thaw cycles. The figure reveals a trend where the damage to the GPC
exposed to freeze–thaw cycles. The figure reveals a trend where the damage to the GPC
specimens intensifies with diminishing strength grades. By the 100th cycle, the surface
specimens intensifies with diminishing strength grades. By the 100th cycle, the surface
geopolymer mortar of GPC-C100 and GPC-C80 showed minor peeling, while GPC-C60
geopolymer mortar of GPC-C100 and GPC-C80 showed minor peeling, while GPC-C60
and GPC-C40 experienced more pronounced peeling. Upon reaching the 200th cycle, a
and GPC-C40 experienced more pronounced peeling. Upon reaching the 200th cycle, a
significant portion of the surface mortar on GPC-C100 and GPC-C80 had peeled away,
significant portion of the surface mortar on GPC-C100 and GPC-C80 had peeled away,
revealing small areas of aggregate, whereas most of the aggregate in GPC-C60 and GPC-C40
revealing small areas of aggregate, whereas most of the aggregate in GPC-C60 and GPC-
had become exposed. After 350 cycles, all specimens except for GPC-100 showed severe
C40 had become exposed. After 350 cycles, all specimens except for GPC-100 showed se-
peeling of the geopolymer mortar. As depicted in the figure, the freeze–thaw damage
vere peeling of the geopolymer mortar. As depicted in the figure, the freeze–thaw damage
process for GPC is characterized by continual surface peeling, with an initial tendency
for slowfor
process GPC isprogression
damage characterized bylater
that continual surfaceAs
accelerates. peeling,
shownwith an initial
in the figure,tendency for
the freeze–
slow damage
thaw damage process
progressionof GPCthatis later accelerates.
characterized by As shown insurface
continuous the figure, the Initially,
peeling. freeze–thaw
the
damage process of GPC is characterized by continuous surface
damage progressed slowly, but it later accelerated, and the damage at both ends waspeeling. Initially, the more
dam-
age progressed
severe than in the slowly,
middle. butIt itis later
worth accelerated,
noting thatand the damage
no cracks at both ends
were observed in allwas more
samples
severe than in the middle.
during the freeze–thaw stage. It is worth noting that no cracks were observed in all samples
duringThethe freeze–thaw
findings indicatedstage.
that higher strength correlated with a denser concrete struc-
ture, The findings
making it moreindicated that higher
challenging strength
for water correlated
to infiltrate. with a denser
Furthermore, concrete struc-
a stronger bond
ture, making it more challenging for water to infiltrate. Furthermore,
between the aggregate and mortar enhanced the concrete’s capacity to withstand the ex- a stronger bond be-
tween the aggregate and mortar enhanced the concrete’s capacity to
pansive pressure exerted by freezing water, thereby reducing the likelihood of crack and withstand the expan-
sive pressure
pore formation. exerted by freezing water, thereby reducing the likelihood of crack and pore
formation.
3.3.2. RDEM and Mass Loss
The RDEM and mass loss of the four groups of specimens after the freeze–thaw cycles
are shown in Figure 5. The trend of RDEM and mass loss is consistent with the freeze–thaw
damage process. As the number of freeze–thaw cycles increased, the RDEM and mass
loss for GPC-C40 exhibited a swift decline. After 350 cycles, the RDEM dipped below
60%, and the mass loss exceeded 5%, signifying that GPC-C40 fell short of the durability
criteria necessary for a projected 50-year lifespan in cold climates. The subpar performance
of GPC-C40 was primarily due to an insufficient polymerization reaction, which was
a consequence of the minimal alkali activator present, resulting in a lower quantity of
geopolymer gel. The unreacted metakaolin in the composition led to increased porosity,
which allowed for quicker water absorption. Consequently, once cracks began to form,
they rapidly widened, interconnected, and progressed into larger and more severe fissures.
Therefore, an appropriate amount of alkaline activator has an important impact on the
performance of GPC.
 Materials 2024, 17, 1944
x FOR PEER REVIEW 8 8of
of 18
17

Materials 2024, 17, x FOR PEER REVIEW 9 of 18

pronounced. This
Figure 4. Visual led to the
appearance formation
of GPC of larger
specimens: pores and
(a) GPC-C100, wider cracks
(b) GPC-C80, within
(c) GPC-C60, andthe
(d) GPC,
Figure 4. Visual appearance of GPC specimens: (a) GPC-C100, (b) GPC-C80, (c) GPC-C60, and
thereby accelerating the decline in RDEM and the increase in mass loss.
GPC-C40.
(d) GPC-C40.

3.3.2. RDEM and Mass Loss

The RDEM and mass loss of the four groups of specimens after the freeze–thaw cycles
are shown in Figure 5. The trend of RDEM and mass loss is consistent with the freeze–
thaw damage process. As the number of freeze–thaw cycles increased, the RDEM and
mass loss for GPC-C40 exhibited a swift decline. After 350 cycles, the RDEM dipped below
60%, and the mass loss exceeded 5%, signifying that GPC-C40 fell short of the durability
criteria necessary for a projected 50-year lifespan in cold climates. The subpar perfor-
mance of GPC-C40 was primarily due to an insufficient polymerization reaction, which
was a consequence of the minimal alkali activator present, resulting in a lower quantity of
geopolymer gel. The unreacted metakaolin in the composition led to increased porosity,
which allowed for quicker water absorption. Consequently, once cracks began to form,
they rapidly widened, interconnected, and progressed into larger and more severe fis-
sures. Therefore, an appropriate amount of alkaline activator has an important impact on
the performance of GPC.
The GPC-C100, GPC-C80, and GPC-C60 exhibited minimal changes in RDEM and
mass
Figure
Figure5.loss at thedynamic
Relative
5. Relative 200-cycle mark. Specifically,
dynamicmodulus
modulus of
ofelasticity the RDEM
(RDEM)
elasticity (RDEM) values
andmass
and masslosswere
loss 91.5%,
rates
rates of of
GPC 88.6%,
GPC and
specimens:
specimens:
83.4%,
(a) (a)
RDEM,
RDEM, respectively,
(b)(b)mass
massloss while
lossrates.
rates. the corresponding mass loss rates were 0.32%, 0.41%, and
1.63%. Following 200 cycles, the RDEM and mass loss for the specimens began to decline
swiftly.
AsThe By the 350th
GPC-C100,
illustrated cycle,
GPC-C80,
in the the RDEM
Figure and figures
GPC-C60
5, the had
thefallen
greaterexhibited
GPC’s to ability
75.2%,changes
minimal 68.4%,
to and
resistinthe63.1%,
RDEM re-
and
expansion of
spectively,
mass loss and
at themass loss
200-cycle had increased
mark. to 1.3%,
Specifically, 2.16%,
the RDEMand 3.96%,
values
pores and cracks, the slower the rate of decline in RDEM and mass loss. GPC-C100, GPC- respectively.
were 91.5%, This
88.6%, trend
and
could
83.4%,be attributed to the initially dense structure
massandlosshigh strength of the concrete, which
C80, andrespectively,
GPC-C60 all while the corresponding
demonstrated the potential torates were 0.32%,
withstand 0.41%,
50 years ofand 1.63%.
service in the
impeded
Followingmoisture penetration,
200 cycles, the RDEMresulting
and massinlossa gradual change in RDEM
for the specimens began to and mass swiftly.
decline loss in
cold-climate regions.
the early
By the stages.
350th However,
cycle, the RDEM as the freeze–thaw
figures had fallen process progressed
to 75.2%, and63.1%,
68.4%, and the surface mortar
respectively,
of
and themass
GPCloss started
hadtoincreased
peel off, the strength
to 1.3%, diminished,
2.16%, andrespectively.
and 3.96%, moisture ingress Thisbecame more
trend could
3.3.3. SEM Analysis
The SEM images of GPC with different strength levels before and after freeze–thaw
cycles are shown in Figure 6, indicating that the macroscopic strength differences are re-
flected at the microscopic level. Before freeze–thaw cycles, the three groups of samples
were relatively dense and uniform, and the ITZ between aggregate and mortar was rela-
Materials 2024, 17, 1944 9 of 17

be attributed to the initially dense structure and high strength of the concrete, which
impeded moisture penetration, resulting in a gradual change in RDEM and mass loss in
the early stages. However, as the freeze–thaw process progressed and the surface mortar of
the GPC started to peel off, the strength diminished, and moisture ingress became more
pronounced. This led to the formation of larger pores and wider cracks within the GPC,
thereby accelerating the decline in RDEM and the increase in mass loss.
As illustrated in the Figure 5, the greater the GPC’s ability to resist the expansion
of pores and cracks, the slower the rate of decline in RDEM and mass loss. GPC-C100,
GPC-C80, and GPC-C60 all demonstrated the potential to withstand 50 years of service in
the cold-climate regions.

3.3.3. SEM Analysis

The SEM images of GPC with different strength levels before and after freeze–thaw
cycles are shown in Figure 6, indicating that the macroscopic strength differences are re-
flected at the microscopic level. Before freeze–thaw cycles, the three groups of samples were
relatively dense and uniform, and the ITZ between aggregate and mortar was relatively
tight, because the addition of slag made the geopolymer react to generate new geopolymer
gel, filling the pores. As the number of freeze–thaw cycles increased, the microstructure of
the three specimens showed different changes. After 350 freeze–thaw cycles, GPC-C100
continued to maintain its dense mortar structure and ITZ, which slightly widened. Only
a small number of fine cracks appeared in the mortar, indicating that the effect of the
freeze–thaw cycles had the smallest impact on it. The microstructure images of GPC-C80
and GPC-C60 show that, after 350 freeze–thaw cycles, their ITZ was further widened,
resulting in cracks and pores of different sizes and quantities; also, some cracks penetrated
the pores, and this may be the reason for the drastic changes in their RDEM. It shows that
the strength grade will affect the effect of freezing and thawing. The higher the strength,
the stronger the GPC’s ability to resist crack and pore expansion. This is because it has
sufficient geopolymer gel, which is tightly combined, thus making it difficult for crack and
pore expansion. ITZ with lower strength has more unreacted metakaolin particles, which
can increase the porosity of GPC and increase harmful pores, which is unfavorable for frost
resistance [66].

3.4. Properties of RGA

3.4.1. RGA Gradation
To explore the recycling potential of GPC after enduring freeze–thaw cycles equivalent
to a 50-year service life, GPC specimens that survived 350 such cycles were crushed to
produce RGA. Given that GPC-C40 exhibited failure following 350 freeze–thaw cycles and
considering that failed concrete was not deemed suitable for recycling into aggregates,
this concrete was not used to produce RGA-C40 within the scope of the experiment. After
undergoing cleaning and screening, the gradations of the other three RGA groups were
determined, as depicted in Figure 7. Notably, their gradations significantly diverged from
that of natural aggregates (NAs).
The RGA-C100 and RGA-C80 specimens contained a greater proportion of large
particle-size aggregates compared to NAs. This was attributed to the stronger bond be-
tween the mortar and the aggregate in these parent geopolymer concretes, which inhibited
their separation and led to a higher mortar content, thus contributing to an increase in
particle size. Conversely, RGA-C60 showcased a higher quantity of fine particle-size aggre-
gates relative to natural aggregates. This was because the bonding force of the attached
mortar and the aggregate was weak, which allowed the mortar to detach more easily
under the action of extrusion force. Consequently, the strength level of the parent con-
crete had a significant impact on the particle size distribution of the next generation of
recycled aggregates.
Materials 2024, 17, 1944 Materials 2024, 17, x FOR PEER REVIEW 10 of 17 10 of

Materials 2024, 17, x FOR PEER REVIEW 11 of 18

Figure
Figure 6. SEM images 6. SEM
of GPC images
before of after
and GPC before and after
freeze–thaw freeze–thaw
cycles: cycles: (a)
(a) GPC-C100, GPC-C100,
(b) GPC-C80,(b)and
GPC-C80, an
(c) GPC-C60.
(c) GPC-C60.
3.4. Properties of RGA
3.4.1. RGA Gradation
To explore the recycling potential of GPC after enduring freeze–thaw cycles equiva
lent to a 50-year service life, GPC specimens that survived 350 such cycles were crushe
to produce RGA. Given that GPC-C40 exhibited failure following 350 freeze–thaw cycle
and considering that failed concrete was not deemed suitable for recycling into aggre
gates, this concrete was not used to produce RGA-C40 within the scope of the experimen
After undergoing cleaning and screening, the gradations of the other three RGA group
were determined, as depicted in Figure 7. Notably, their gradations significantly diverge
from that of natural aggregates (NAs).

Figure 7.
Figure 7. The
The RGA
RGA gradation.
gradation.

The RGA-C100 and RGA-C80 specimens contained a greater proportion of large par-
ticle-size aggregates compared to NAs. This was attributed to the stronger bond between
the mortar and the aggregate in these parent geopolymer concretes, which inhibited their
separation and led to a higher mortar content, thus contributing to an increase in particle
size. Conversely, RGA-C60 showcased a higher quantity of fine particle-size aggregates
relative to natural aggregates. This was because the bonding force of the attached mortar
and the aggregate was weak, which allowed the mortar to detach more easily under the
 Materials 2024, 17, 1944 11 of 17

3.4.2. Physical Properties of RGA

Variations in aggregate gradation can result in considerable disparities in its perfor-
Materials 2024, 17, x FOR PEER REVIEW mance. To facilitate a more accurate comparison of their properties, the performance of the
12 of 18
RGA was assessed after their gradations were reconfigured to match that of NA through
sieving. The physical properties of the RGA are depicted in Figure 8.

Figure 8. Physical
Figure properties
8. Physical propertiesofof
NA,
NA,RGA-C100,
RGA-C100,RGA-C80,
RGA-C80, and
and RGA-C60: (a) apparent
RGA-C60: (a) apparentdensity,
density, (b)
24 h(b)water absorption, (c) crushing index, (d) adhesive mortar content.
24 h water absorption, (c) crushing index, (d) adhesive mortar content.

Compared with
3.5. Microstructure NAs, the apparent density of RGA-C100, RGA-C80, and RGA-C60
of RGA
diminished by 3.03%, 4.2%, and 7.1%, respectively. Concurrently, the 24-h water absorption
3.5.1. Microhardness
rates were elevated by 1.95, 2.23, and 3.61 times, while the crushing indices escalated
byThe hardness
29.2%, 51.9%, values for RGA
and 112%, in thatfrom
order.ITZ to attached
Despite mortar are
these changes, the shown
apparent in densities
Figure 9. The
of all three RGAs
microhardness still meet the
of RGA-C100 andcriteria
RGA-C80 for Class
shows I recycled aggregate
a slow change laidatout
trend in GB/T
0–10 µm, while
25177-2010 [57]. The water absorption rate and crushing index for RGA-C100
the microhardness of RGA-C60 shows a slow change at 0–20 µm, indicating that it should and RGA-C80
satisfied in
be located thethe
criteria
ITZ offorRGA,
Class and
II recycled aggregate,
the slight changewhereas
may beRGA-C60
due to the aligned
contact with thepores
with
Class III recycled aggregate standards.
or cracks during the measurement process. RGA-C100 and RGA-C80 showed a significant
This demonstrated that all three GPC groups possessed potential for recycling. The
increase in microhardness at 10–40 µm, while RGA-C60 showed a significant increase in
freeze–thaw cycles contributed to an increased prevalence of wide cracks and micro-pores
microhardness at 20–50
in the geopolymer µm,and
mortar indicating that this should
ITZ, concurrently weakening be located in theforce
the bonding junction between
between
ITZtheand
mortar and aggregate [67]. Such changes led to a reduction in the performance of RGA.mor-
the geopolymer mortar, which is jointly affected by ITZ and the geopolymer
tar.Notably,
As theadistance increases,
higher strength of thethe portion
parent borne bywith
GPC correlated thegreater
geopolymer
strengthmortar increases;
in the mortar
and ITZthe
therefore, of the RGA [68], thusvalues
microhardness enhancing the overall
increase. performance of the
The microhardness recycled
tends product.
to flatten at 50–80
µm, indicating that it should be located in the geopolymer mortar. The average micro-
hardness values of the ITZs for RGA-C100, RGA-C80, and RGA-C60 were 58.1, 49.3, and
35.8, while the attached mortar exhibited average values of 72.8, 64.6, and 51.2, respec-
tively. The microhardness of the GPC’s ITZs corresponded to 79.8%, 76.3%, and 68.5% of
the attached mortar’s, respectively. This indicated that the higher the strength of the par-
ent GPC, the greater the strength of both the ITZs and attached mortar in the RGA, and
the narrower the gap between the strength of the ITZs and the attached mortar.
Materials 2024, 17, 1944 12 of 17

3.5. Microstructure of RGA

3.5.1. Microhardness
The hardness values for RGA from ITZ to attached mortar are shown in Figure 9.
The microhardness of RGA-C100 and RGA-C80 shows a slow change trend at 0–10 µm,
while the microhardness of RGA-C60 shows a slow change at 0–20 µm, indicating that
it should be located in the ITZ of RGA, and the slight change may be due to the contact
with pores or cracks during the measurement process. RGA-C100 and RGA-C80 showed
a significant increase in microhardness at 10–40 µm, while RGA-C60 showed a signifi-
cant increase in microhardness at 20–50 µm, indicating that this should be located in the
junction between ITZ and the geopolymer mortar, which is jointly affected by ITZ and
the geopolymer mortar. As the distance increases, the portion borne by the geopolymer
mortar increases; therefore, the microhardness values increase. The microhardness tends
to flatten at 50–80 µm, indicating that it should be located in the geopolymer mortar. The
average microhardness values of the ITZs for RGA-C100, RGA-C80, and RGA-C60 were
58.1, 49.3, and 35.8, while the attached mortar exhibited average values of 72.8, 64.6, and
51.2, respectively. The microhardness of the GPC’s ITZs corresponded to 79.8%, 76.3%, and
68.5% of the attached mortar’s, respectively. This indicated that the higher the strength
Materials 2024, 17, x FOR PEER REVIEW 13 of of
18
the parent GPC, the greater the strength of both the ITZs and attached mortar in the RGA,
and the narrower the gap between the strength of the ITZs and the attached mortar.

Figure 9.
Figure 9. Microhardness
Microhardness distribution
distribution of
of RGA
RGA from
fromITZ
ITZto
togeopolymer
geopolymermortar.
mortar.

3.5.2.The
SEM Analysis
higher strength of the parent GPC resulted in a denser and more homogenously
distributed
Figurestructure within
10 displays SEM the ITZs and
images attached
of the RGA, mortar. Subsequently,
revealing a variety of this enhanced
cracks the
and pores
bonding force with the aggregate, leading to a closer alignment in strength between
within the attached mortar. Some of these cracks interweaved, creating a networked struc- the
ITZs and the
ture that attachedwith
intersected mortar
the [69].
ITZ. This interconnectivity was a contributing factor to the
observed reduction in RGA performance. Under the action of freeze–thaw cycles, the wa-
3.5.2. SEM Analysis
ter within the pores was repeatedly frozen and thawed, generating cyclic expansion pres-
sure.Figure 10 displays
This process led toSEM
the images of theevolution
progressive RGA, revealing a varietyand
of microcracks of cracks and pores
small pores [70],
within the attached mortar. Some of these cracks interweaved, creating a networked
and this further intensified after crushing. Eventually, these microcracks and small pores
structure that intersected
interconnected with the
and expanded intoITZ. This
larger interconnectivity
cracks wasphysical
and pores. The a contributing factor to
performance of
the observed reduction in RGA performance. Under the action of freeze–thaw
RGA was inversely proportional to the number of cracks and pores presented. The fewer cycles, the
water withinthe
the defects, themore
pores was repeatedly
superior frozen and
the performance thawed,
of RGA. generating
RGA-C100 cyclicthe
exhibited expansion
narrow-
pressure. This process led to the progressive evolution of microcracks and small pores [70],
est ITZ width, suggesting that its attached mortar was more securely bonded to the aggre-
and this further intensified after crushing. Eventually, these microcracks and small pores
gate and possessed the most robust resistance to damage. This result was consistent with
interconnected and expanded into larger cracks and pores. The physical performance of
the macroscopic performance observed.
RGA was inversely proportional to the number of cracks and pores presented. The fewer
the defects, the more superior the performance of RGA. RGA-C100 exhibited the narrowest
ITZ width, suggesting that its attached mortar was more securely bonded to the aggregate
 sure. This process led to the progressive evolution of microcracks and small pores [70],
and this further intensified after crushing. Eventually, these microcracks and small pores
interconnected and expanded into larger cracks and pores. The physical performance of
RGA was inversely proportional to the number of cracks and pores presented. The fewer
Materials 2024, 17, 1944 13 of 17
the defects, the more superior the performance of RGA. RGA-C100 exhibited the narrow-
est ITZ width, suggesting that its attached mortar was more securely bonded to the aggre-
gate
andand possessed
possessed the the
mostmost robust
robust resistance
resistance to damage.
to damage. Thiswas
This result result was consistent
consistent with the with
themacroscopic
macroscopic performance observed.
performance observed.

Figure 10. SEM images of RGA: (a) RGA-C100, (b) RGA-C80, and (c) RGA-C60.
Figure 10. SEM images of RGA: (a) RGA-C100, (b) RGA-C80, and (c) RGA-C60.
Materials 2024, 17, x FOR PEER REVIEW 14 of 18
3.5.3.
3.5.3. XRDXRD Analysis
Analysis
Figure
Figure 1111presents
presentsthethe XRD
XRD analysis
analysisofofthe
theattached
attached mortar
mortar on on
RGAs, illustrating
RGAs, that, that,
illustrating
while the diffraction peaks for the three group specimens are similarly positioned, their
while the diffraction
modify thevary. peaks for◦the facilitating
cementitious three group thespecimens are of
similarly positioned,
into C- their
intensities At 2θ = products,
27.46 , the characteristic transformation
diffraction peak N-A-S-H
of hydratedgelscalcium
intensities
A-S-H and vary. At 2θ
C-S-H gels.= This
27.46°, the characteristic
conversion can lead diffraction
to 2θ
enhancements peakboth
of hydrated calcium sil-
silicate aluminate (C-A-S-H) was observed, and at = 29.42◦ , thein the strength
peak corresponding and
to
icate aluminate (C-A-S-H)
durabilitycalcium
hydrated of the geopolymer was observed,
matrix
silicate (C-S-H) and
[72,73].
became apparent.at 2θ = 29.42°, the peak corresponding to
hydrated calcium silicate (C-S-H) became apparent.
It was indicated that the incorporation of slag results in the formation of higher-
strength C-A-S-H and C-S-H. As the compressive strength increases, so does the height of
the diffraction peaks, signifying that the sample exhibits high crystallinity and a substan-
tial number of crystalline substances [71]. Calcium components play a pivotal role in the
microstructure of geopolymers, and an optimal concentration of these components can

Figure 11.
Figure 11. XRD
XRD analysis
analysis of
of RGA
RGA geopolymer
geopolymermortar.
mortar.

4. Conclusions
It was indicated that the incorporation of slag results in the formation of higher-
strength C-A-S-H
Through theand C-S-H. As the
examination compressive
of the strengthand
frost resistance increases, so does
recycling the height
potential of
of me-
the diffraction peaks,
takaolin-based signifying
GPC with thatstrength
different the sample exhibits
grades, thehigh crystallinity
following and a are
conclusions substantial
drawn:
number of crystalline substances [71]. Calcium components play a pivotal role in the
(1) A high-temperature (80 °C) curing and the addition of 40% slag accelerated the
microstructure of geopolymers, and an optimal concentration of these components can
polymerization reaction, so that the 7-day compressive strengths of GPC-C100, GPC-
modify the cementitious products, facilitating the transformation of N-A-S-H gels into
C80, GPC-C60, and GPC-C40 attained 94.9%, 94.3%, 93.8%, and 94.6% of their respec-
C-A-S-H and C-S-H gels. This conversion can lead to enhancements in both the strength
tive 28-day compressive strengths. With the exception of GPC-C100, concretes of
and durability of the geopolymer matrix [72,73].
lower-strength grades generally achieve their designated strength targets more read-
ily within 7 days. The development trend of splitting tensile strength is similar to
4. Conclusions
compressive
Through strength. The
the examination of 7-day splitting
the frost tensile
resistance and strength
recyclingof GPC-C100,
potential GPC-C80,
of metakaolin-
GPC-C60, and GPC-C40 reached 87.2%, 94.3%, 93.8%, and 91.1%
based GPC with different strength grades, the following conclusions are drawn: of their 28-day split-
ting tensile strength, respectively.
(1) A high-temperature (80 ◦ C) curing and the addition of 40% slag accelerated the poly-
(2) High-strength GPC exhibited superior frost-resistance durability. GPC-C100, GPC-
merization reaction, so that the 7-day compressive strengths of GPC-C100, GPC-C80,
C80, and GPC-C60 showed the capability to endure more than 350 freeze–thaw cy-
GPC-C60, and GPC-C40 attained 94.9%, 94.3%, 93.8%, and 94.6% of their respec-
cles, suggesting that their lifespan in cold regions extended beyond 50 years. By the
tive 28-day compressive strengths. With the exception of GPC-C100, concretes of
350th cycle, the RDEM had fallen to 75.2%, 68.4%, and 63.1%, respectively, and mass
loss had increased to 1.3%, 2.16%, and 3.96%, respectively. In contrast, GPC-C40 ex-
perienced failure after 300 cycles. The SEM image shows that the GPC sample has a
dense ITZ.
(3) The apparent densities of RGA-C100, RGA-C80, and RGA-C60 are 2655 kg/m3, 2623
kg/m3, 2542 kg/m3, respectively, with water absorption rates of 3.54%, 3.88%, and
Materials 2024, 17, 1944 14 of 17

lower-strength grades generally achieve their designated strength targets more read-
ily within 7 days. The development trend of splitting tensile strength is similar to
compressive strength. The 7-day splitting tensile strength of GPC-C100, GPC-C80,
GPC-C60, and GPC-C40 reached 87.2%, 94.3%, 93.8%, and 91.1% of their 28-day
splitting tensile strength, respectively.
(2) High-strength GPC exhibited superior frost-resistance durability. GPC-C100, GPC-
C80, and GPC-C60 showed the capability to endure more than 350 freeze–thaw cycles,
suggesting that their lifespan in cold regions extended beyond 50 years. By the 350th
cycle, the RDEM had fallen to 75.2%, 68.4%, and 63.1%, respectively, and mass loss had
increased to 1.3%, 2.16%, and 3.96%, respectively. In contrast, GPC-C40 experienced
failure after 300 cycles. The SEM image shows that the GPC sample has a dense ITZ.
(3) The apparent densities of RGA-C100, RGA-C80, and RGA-C60 are 2655 kg/m3 ,
2623 kg/m3 , 2542 kg/m3 , respectively, with water absorption rates of 3.54%, 3.88%,
and 5.53%, and crushing indices of 13.95%, 16.4%, and 22.9%, respectively. The met-
rics for RGA-C100 and RGA-C80 aligned with Class II recycled aggregate standards,
whereas RGA-C60 conformed to Class III criteria. The higher the strength grade, the
better the physical properties of the RGAs, indicating a linear correlation between the
strength grade of the parent concrete and the performance of the subsequent genera-
tion of recycled aggregates. The microhardness of the GPC’s ITZs corresponded to
79.8%, 76.3%, and 68.5% of the attached mortar’s, respectively. This indicated that the
higher the strength of the parent GPC, the greater the strength of both the ITZs and
attached mortar in the RGA, and the narrower the gap between the strength of the
ITZs and the attached mortar.
(4) The attached mortar and ITZ of RGA exhibited numerous microcracks and pores,
which accounted for the deterioration of its physical properties. Moreover, a higher-
strength grade of RGA corresponded to a narrower ITZ width, suggesting a more
robust resistance to separation. The XRD results showed that the polymerization
reaction generated C-S-H and C-A-S-H, which is one of the reasons for their great
recycling potential.

Author Contributions: Conceptualization, X.W.; Methodology, M.H., C.C., X.G. and T.M.; Software,
X.G.; Formal analysis, M.H. and X.W.; Investigation, M.L. and C.C.; Resources, C.C.; Data curation,
M.L., X.W. and T.M.; Writing—original draft, M.L.; Writing—review & editing, H.L. and M.H.;
Supervision, H.L.; Project administration, H.L.; Funding acquisition, H.L. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by the Youth science and technology talent lifting project program
from Jiangsu and Changzhou Science and Technology Association (TJ-2023-024) and Postgraduate
Research and Practice Innovation Program of Jiangsu Province (KYCX22_3081).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

References
1. Ghezelbash, A.; Khaligh, V.; Fahimifard, S.H.; Liu, J.J. A Comparative Perspective of the Effects of CO2 and Non-CO2 Greenhouse
Gas Emissions on Global Solar, Wind, and Geothermal Energy Investment. Energies 2023, 16, 3025. [CrossRef]
2. Adamolekun, G. Carbon Price and Firm Greenhouse Gas Emissions. J. Environ. Manag. 2024, 349, 119496. [CrossRef] [PubMed]
3. Sousa, V.; Bogas, J.A. Comparison of Energy Consumption and Carbon Emissions from Clinker and Recycled Cement Production.
J. Clean. Prod. 2021, 306, 127277. [CrossRef]
4. Lin, B.; Zhang, Z. Carbon Emissions in China’s Cement Industry: A Sector and Policy Analysis. Renew. Sustain. Energy Rev. 2016,
58, 1387–1394. [CrossRef]
5. Davidovits, J. Geopolymers: Inorganic Polymeric New Materials. J. Therm. Anal. Calorim. 1991, 37, 1633–1656. [CrossRef]
Materials 2024, 17, 1944 15 of 17

6. Lingyu, T.; Dongpo, H.; Jianing, Z.; Hongguang, W. Durability of Geopolymers and Geopolymer Concretes: A Review. Rev. Adv.
Mater. Sci. 2021, 60, 1–14. [CrossRef]
7. Zhuang, X.Y.; Chen, L.; Komarneni, S.; Zhou, C.H.; Tong, D.S.; Yang, H.M.; Yu, W.H.; Wang, H. Fly Ash-Based Geopolymer: Clean
Production, Properties and Applications. J. Clean. Prod. 2016, 125, 253–267. [CrossRef]
8. Hassan, A.; Arif, M.; Shariq, M. Influence of Microstructure of Geopolymer Concrete on Its Mechanical Properties—A Review. In
Advances in Sustainable Construction Materials and Geotechnical Engineering; Shukla, S.K., Barai, S.V., Mehta, A., Eds.; Lecture Notes
in Civil, Engineering; Springer: Singapore, 2020; Volume 35, pp. 119–129. [CrossRef]
9. Teh, S.H.; Wiedmann, T.; Castel, A.; De Burgh, J. Hybrid Life Cycle Assessment of Greenhouse Gas Emissions from Cement,
Concrete and Geopolymer Concrete in Australia. J. Clean. Prod. 2017, 152, 312–320. [CrossRef]
10. Liu, X.; Yang, L.; Du, J.; Zhang, H.; Hu, J.; Chen, A.; Lv, W. Carbon and Air Pollutant Emissions Forecast of China’s Cement
Industry from 2021 to 2035. Resour. Conserv. Recycl. 2024, 204, 107498. [CrossRef]
11. Hu, Z.; Kuenzer, C.; Dietz, A.J.; Dech, S. The Potential of Earth Observation for the Analysis of Cold Region Land Surface
Dynamics in Europe—A Review. Remote. Sens. 2017, 9, 1067. [CrossRef]
12. Syvitski, J.P.M.; Syvitski, J.P.M.; Zhang, T.; Crawford, R.M.M. Let Heroes Speak: Antarctic Explorers, 1772–1922, Dangerous
Crossings: The First Modern Polar Expedition, 1925, Geocryology in China, Die Höhengrenze Der Gebirgswalder [The Altitudinal
Limits of Mountain Forests]. Arct. Antarct. Alp. Res. 2001, 33, 244–247. [CrossRef]
13. Chen, R.; Kang, E.; Ji, X.; Yang, J.; Yang, Y. Cold Regions in China. Cold Reg. Sci. Technol. 2006, 45, 95–102. [CrossRef]
14. Nilimaa, J.; Zhaka, V. An Overview of Smart Materials and Technologies for Concrete Construction in Cold Weather. Eng 2023,
4, 1550–1580. [CrossRef]
15. Nilimaa, J.; Zhaka, V. Material and Environmental Aspects of Concrete Flooring in Cold Climate. Constr. Mater. 2023, 3, 180–201.
[CrossRef]
16. Qin, Y.; Deng, S.; Zhang, X. Frost Resistance of Recycled Concrete. J. Central South Univ. Technol. 2007, 14, 409–413. [CrossRef]
17. Yang, C.; Zhang, J.; Wang, J.; Guo, M. Post-Evaluation of Frost Resistance of Cement Concrete Entities Based on Pore Spacing
Factors of Hardened Concrete. Constr. Build. Mater. 2024, 411, 134342. [CrossRef]
18. Zhang, Y.; Si, Z.; Huang, L.; Yang, C.; Du, X. Experimental Study on the Properties of Internal Cured Concrete Reinforced with
Steel Fibre. Constr. Build. Mater. 2023, 393, 132046. [CrossRef]
19. Zhi, D.; Gong, F.; Wang, Z.; Zhao, Y.; Ueda, T. RBSM-Based Mesoscale Study of Frost Deterioration for Recycled Concrete
Considering Air-Entrainment in Old and New Mortar. J. Build. Eng. 2023, 68, 106210. [CrossRef]
20. Wang, Y.; Kang, A.-H.; Wu, Z.-G.; Xiao, P.; Gong, Y.-F.; Sun, H.-F. Investigation of the Basalt Fiber Type and Content on
Performances of Cement Mortar and Concrete. Constr. Build. Mater. 2023, 408, 133720. [CrossRef]
21. Jianxun, C.; Xizhong, Z.; Yanbin, L.; Xianghui, D.; Qin, L. Investigating Freeze-Proof Durability of C25 Shotcrete. Constr. Build.
Mater. 2014, 61, 33–40. [CrossRef]
22. González, D.C.; Mena, Á.; Mínguez, 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]
23. Li, W.; Liu, H.; Zhu, B.; Lyu, X.; Gao, X.; Liang, C. Mechanical Properties and Freeze–Thaw Durability of Basalt Fiber Reactive
Powder Concrete. Appl. Sci. 2020, 10, 5682. [CrossRef]
24. Yuan, X.; Dai, M.; Gao, Y.; Liu, F.; Zhang, M. Pore Morphology Based on Graphene Oxide Modified Steel Fibre Concrete for
Freeze–Thaw Resistance. Constr. Build. Mater. 2023, 409, 133877. [CrossRef]
25. Zeng, Y.; Li, X.; Tang, A.; Zhao, N.; Li, L.; Jia, S. Axial Compressive Behavior of Basalt and Polyacrylonitrile Fibers Reinforced
Lightweight Aggregate Concrete with Industrial Waste Ceramsite-Lytag after Freeze-Thaw Cycles. J. Build. Eng. 2023, 76, 107402.
[CrossRef]
26. Sun, P.; Wu, H.-C. Chemical and Freeze–Thaw Resistance of Fly Ash-Based Inorganic Mortars. Fuel 2013, 111, 740–745. [CrossRef]
27. Brooks, R.; Bahadory, M.; Tovia, F.; Rostami, H. Properties of Alkali-Activated Fly Ash: High Performance to Lightweight. Int. J.
Sustain. Eng. 2010, 3, 211–218. [CrossRef]
28. Yuan, Y.; Zhao, R.; Li, R.; Wang, Y.; Cheng, Z.; Li, F.; John Ma, Z. Frost Resistance of Fiber-Reinforced Blended Slag and Class F Fly
Ash-Based Geopolymer Concrete under the Coupling Effect of Freeze-Thaw Cycling and Axial Compressive Loading. Constr.
Build. Mater. 2020, 250, 118831. [CrossRef]
29. Pilehvar, S.; Szczotok, A.M.; Rodríguez, J.F.; Valentini, L.; Lanzón, M.; Pamies, R.; Kjøniksen, A.-L. Effect of Freeze-Thaw Cycles
on the Mechanical Behavior of Geopolymer Concrete and Portland Cement Concrete Containing Micro-Encapsulated Phase
Change Materials. Constr. Build. Mater. 2018, 200, 94–103. [CrossRef]
30. Aiken, T.A.; Kwasny, J.; Sha, W.; Tong, K.T. Mechanical and Durability Properties of Alkali-Activated Fly Ash Concrete with
Increasing Slag Content. Constr. Build. Mater. 2021, 301, 124330. [CrossRef]
31. Fu, Y.; Cai, L.; Yonggen, W. Freeze–Thaw Cycle Test and Damage Mechanics Models of Alkali-Activated Slag Concrete. Constr.
Build. Mater. 2011, 25, 3144–3148. [CrossRef]
32. Figiela, B.; Brudny, K.; Lin, W.-T.; Korniejenko, K. Investigation of Mechanical Properties and Microstructure of Construction- and
Demolition-Waste-Based Geopolymers. J. Compos. Sci. 2022, 6, 191. [CrossRef]
33. Korniejenko, K.; Figiela, B.; Pławecka, K.; Bulut, A.; Şahin, B.; Azizağaoğlu, G.; Łach, M. Characterization of a Coal Shale from
Marcel Mining as Raw Material for Geopolymer Manufacturing. In Proceedings of the 10th MATBUD’s 2023 Scientific-Technical
Conference, Cracow, Poland, 19–21 April 2023; p. 21. [CrossRef]
Materials 2024, 17, 1944 16 of 17

34. Alhawat, M.; Ashour, A.; Yildirim, G.; Aldemir, A.; Sahmaran, M. Properties of Geopolymers Sourced from Construction and
Demolition Waste: A Review. J. Build. Eng. 2022, 50, 104104. [CrossRef]
35. Akbarnezhad, A.; Huan, M.; Mesgari, S.; Castel, A. Recycling of Geopolymer Concrete. Constr. Build. Mater. 2015, 101, 152–158.
[CrossRef]
36. Zhu, P.; Hua, M.; Liu, H.; Wang, X.; Chen, C. Interfacial Evaluation of Geopolymer Mortar Prepared with Recycled Geopolymer
Fine Aggregates. Constr. Build. Mater. 2020, 259, 119849. [CrossRef]
37. Mesgari, S.; Akbarnezhad, A.; Xiao, J.Z. Recycled Geopolymer Aggregates as Coarse Aggregates for Portland Cement Concrete
and Geopolymer Concrete: Effects on Mechanical Properties. Constr. Build. Mater. 2019, 236, 117571. [CrossRef]
38. Rashad, A.M. Metakaolin as Cementitious Material: History, Scours, Production and Composition–A Comprehensive Overview.
Constr. Build. Mater. 2013, 41, 303–318. [CrossRef]
39. Liu, W.; Pang, Z.; Zheng, J.; Yin, S.; Zuo, H. The Viscosity, Crystallization Behavior and Glass-Ceramics Preparation of Blast
Furnace Slag: A Review. Ceram. Int. 2024, 50, 18090–18104. [CrossRef]
40. Duxson, P.; Mallicoat, S.W.; Lukey, G.C.; Kriven, W.M.; Van Deventer, J.S.J. The Effect of Alkali and Si/Al Ratio on the Development
of Mechanical Properties of Metakaolin-Based Geopolymers. Colloids Surf. A Physicochem. Eng. Asp. 2007, 292, 8–20. [CrossRef]
41. Zhang, K.; Xu, H.; Kong, X.; Zhang, C.; Lu, H.; He, D. Study on the Influence Mechanism of Micro-Mechanical Properties of
Heterogeneous Geopolymer Gels. J. Build. Eng. 2023, 76, 107164. [CrossRef]
42. GB/T14684-2022; Standard for Sand for Construction. Standardization Administration of China: Beijing, China, 2022.
43. GB/T14685-2022; Standard for Pebble and Crushed Stone for Construction. Standardization Administration of China: Beijing,
China, 2022.
44. ASTM C33/C33M-23; Standard Specification for Concrete Aggregates. American Society for Testing Materials: West Conshohocken,
PA, USA, 2023.
45. Luan, C.; Shi, X.; Zhang, K.; Utashev, N.; Yang, F.; Dai, J.; Wang, Q. A Mix Design Method of Fly Ash Geopolymer Concrete Based
on Factors Analysis. Constr. Build. Mater. 2020, 272, 121612. [CrossRef]
46. Albidah, A.; Alghannam, M.; Abbas, H.; Almusallam, T.; Al-Salloum, Y. Characteristics of Metakaolin-Based Geopolymer
Concrete for Different Mix Design Parameters. J. Mater. Res. Technol. 2020, 10, 84–98. [CrossRef]
47. Parveen, P.; Singhal, D. Development of Mix Design Method for Geopolymer Concrete. Adv. Concr. Constr. 2017, 5, 377–390.
[CrossRef]
48. Verma, M.; Dev, N. Effect of Ground Granulated Blast Furnace Slag and Fly Ash Ratio and the Curing Conditions on the
Mechanical Properties of Geopolymer Concrete. Struct. Concr. 2021, 23, 2015–2029. [CrossRef]
49. GB/T50081-2019; Standard for Test Methods of Concrete Physical and Mechanical Properties. Standardization Administration of
China: Beijing, China, 2019.
50. ASTM C39/C39M-23; Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens. American Society for
Testing Materials: West Conshohocken, PA, USA, 2023.
51. ASTM C496/C496M-17; Standard Test Method for Splitting Tensile Strength of Cylindrical Concrete Specimens. American Society
for Testing Materials: West Conshohocken, PA, USA, 2017.
52. GB/T50082-2009; Standard for Test Methods of Long-Term Performance and Durability of Ordinary Concrete. Standardization
Administration of China: Beijing, China, 2009.
53. ASTM C666/C666M-15; Standard Test Method for Resistance of Concrete to Rapid Freezing and Thawing. American Society for
Testing Materials: West Conshohocken, PA, USA, 2015.
54. ASTM C127-15; Standard Test Method for Relative Density (Specific Gravity) and Absorption of Coarse Aggregate. American
Society for Testing Materials: West Conshohocken, PA, USA, 2015.
55. BS EN 1097-2:2020; Tests for Mechanical and Physical Properties of Aggregates Methods for the Determination of Resistance to
Fragmentation. British Standards Institution: London, UK, 2020.
56. Pepe, M.; Toledo Filho, R.D.; Koenders, E.A.B.; Martinelli, E. Alternative Processing Procedures for Recycled Aggregates in
Structural Concrete. Constr. Build. Mater. 2014, 69, 124–132. [CrossRef]
57. GB/T25177-2010; Standard for Recycled Coarse Aggregate for Concrete. Standardization Administration of China: Beijing, China,
2010.
58. Bakharev, T. Geopolymeric Materials Prepared Using Class F Fly Ash and Elevated Temperature Curing. Cem. Concr. Res. 2005,
35, 1224–1232. [CrossRef]
59. Castel, A.; Foster, S.J.; Ng, T.; Sanjayan, J.G.; Gilbert, R.I. Creep and Drying Shrinkage of a Blended Slag and Low Calcium Fly
Ash Geopolymer Concrete. Mater. Struct. 2015, 49, 1619–1628. [CrossRef]
60. Çetintaş, R.; Soyer-Uzun, S. Relations between Structural Characteristics and Compressive Strength in Volcanic Ash Based
One–Part Geopolymer Systems. J. Build. Eng. 2018, 20, 130–136. [CrossRef]
61. Jiang, T.; Liu, Z.; Tian, X.; Wu, J.; Wang, L. Review on the Impact of Metakaolin-Based Geopolymer’s Reaction Chemistry,
Nanostructure and Factors on Its Properties. Constr. Build. Mater. 2024, 412, 134760. [CrossRef]
62. Allali, F.; Joussein, E.; Kandri, N.I.; Rossignol, S. The Influence of Calcium Content on the Performance of Metakaolin-Based
Geomaterials Applied in Mortars Restoration. Mater. Des. 2016, 103, 1–9. [CrossRef]
63. Kaur, M.; Singh, J.; Kaur, M. Synthesis of Fly Ash Based Geopolymer Mortar Considering Different Concentrations and
Combinations of Alkaline Activator Solution. Ceram. Int. 2018, 44, 1534–1537. [CrossRef]
Materials 2024, 17, 1944 17 of 17

64. Görhan, G.; Kürklü, G. The Influence of the NaOH Solution on the Properties of the Fly Ash-Based Geopolymer Mortar Cured at
Different Temperatures. Compos. Part B Eng. 2014, 58, 371–377. [CrossRef]
65. Liew, Y.; Kamarudin, H.; Al Bakri, A.M.; Bnhussain, M.; Luqman, M.; Nizar, I.K.; Ruzaidi, C.; Heah, C. Optimization of
solids-to-liquid and alkali activator ratios of calcined kaolin geopolymeric powder. Constr. Build. Mater. 2012, 37, 440–451.
[CrossRef]
66. Ranjbar, N.; Kuenzel, C.; Spangenberg, J.; Mehrali, M. Hardening Evolution of Geopolymers from Setting to Equilibrium: A
Review. Cem. Concr. Compos. 2020, 114, 103729. [CrossRef]
67. Liu, D.; Tu, Y.; Sas, G.; Elfgren, L. Freeze-Thaw Damage Evaluation and Model Creation for Concrete Exposed to Freeze–Thaw
Cycles at Early-Age. Constr. Build. Mater. 2021, 312, 125352. [CrossRef]
68. Taheri, B.M.; Ramezanianpour, A.M.; Sabokpa, S.; Gapele, M. Experimental Evaluation of Freeze-Thaw Durability of Pervious
Concrete. J. Build. Eng. 2020, 33, 101617. [CrossRef]
69. Liu, Y.; Ren, P.; Garcia-Troncoso, N.; Mo, K.H.; Ling, T.-C. Roles of Enhanced ITZ in Improving the Mechanical Properties of
Concrete Prepared with Different Types of Recycled Aggregates. J. Build. Eng. 2022, 60, 105197. [CrossRef]
70. Gao, S.; Guo, X.; Ban, S.; Ma, Y.; Yu, Q.; Sui, S. Influence of Supplementary Cementitious Materials on ITZ Characteristics of
Recycled Concrete. Constr. Build. Mater. 2023, 363, 129736. [CrossRef]
71. Xu, H.; Van Deventer, J.S.J. The Geopolymerisation of Alumino-Silicate Minerals. Int. J. Miner. Process. 2000, 59, 247–266.
[CrossRef]
72. Yip, C.K.; Lukey, G.C.; Provis, J.L.; Van Deventer, J.S.J. Effect of Calcium Silicate Sources on Geopolymerisation. Cem. Concr. Res.
2008, 38, 554–564. [CrossRef]
73. Temuujin, J.; Van Riessen, A.; Williams, R. Influence of Calcium Compounds on the Mechanical Properties of Fly Ash Geopolymer
Pastes. J. Hazard. Mater. 2009, 167, 82–88. [CrossRef] [PubMed]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.