Rev. Adv. Mater. Sci.

2021; 60:1–14

Review Article

Tian Lingyu, He Dongpo, Zhao Jianing, and Wang Hongguang*

Durability of geopolymers and geopolymer

concretes: A review
https://doi.org/10.1515/rams-2021-0002
Received Mar 08, 2020; accepted May 05, 2020
1 Introduction
Abstract: Geopolymers are green materials with three- Concrete has become the primary global building mate-
dimensional silicon and aluminum tetrahedral structures rial, but the carbon dioxide emissions of the construction
that can be serving as environmentally friendly construc- industry where concrete is the main material are tremen-
tion materials and therefore have the potential to contribute dous, accounting for only 5% to 7% of the global total [1, 2].
to sustainable development. In this paper, the mechanism Compared with ordinary Portland cement concrete (OPC),
and research progress regarding the carbonation resistance, geopolymers are more environmentally friendly because
structural fire resistance, corrosion resistance, permeation it can reduce the pathway of carbon generated by exces-
properties and frost resistance of geopolymer concretes sive use of OPC [3, 4]. The amount of CO2 produced by
are reviewed, and the main problems with the durabil- the comparative concrete containing 100% OPC binder was
ity of geopolymer concretes are discussed. Geopolymers about 9% higher than that of geopolymer concrete (GPC) [5].
possess the superb mechanic property and their compres- Therefore geopolymers are suitable binders for OPC to man-
sion strengths could be higher than 100 MPa. Generally, ufacture green concretes.
the higher the GPC strength, the better the carbonation- Geopolymers are the three-dimensional networks
resistant. GPC has excellent fire resistance, due to geopoly- made by reacting materials containing alumina and silica
mers are acquired an inorganic skeleton which is affected by with alkaline liquids [6]. Due to Al3+ of (AlO4 )−1 is four-fold
the alkali content, alkali cation, and Si/Ai ratio. There are coordination, Na+ in the alkaline activating solution bal-
a large number of Al-O and Si-O structures in geopolymers. ances the surplus negative charge [7]. Water of geopolymer
Geopolymers do not react with acids at room temperature as a catalyst generally does not participate in the reaction.
and can be used to make acid-resistant materials. Besides, Water of calcium silicate hydrate gel is totally different. It
GPC owning low porosity volume shows good resistance to creates a part of C-S-H. Through Figure 1, it could be found
permeability. The freezing-thawing failure mechanism of the schematic structure of OPC and geopolymer [8].
geopolymer concretes is mainly based on hydrostatic and One type of concrete uses geopolymer as a binder,
osmotic pressure theory. GPC has poor frost resistance, and namely geopolymer concrete. The strength of GPC resorts to
the freezing-thawing limit is less than 75 times. polymerization, while the strength of OPC comes from the
hydration of Portland cement [9]. OPC’s strength increase
Keywords: geopolymer; preparation; carbonation resis-
and hardening mechanisms are significantly different from
tance; fire resistance; corrosion resistance; permeation
those of geopolymers. Geopolymers have strong mechani-
properties
cal properties, and their compressive strength can exceed
100 MPa [10].
Being a medium of environment, the durability of con-
crete exerts an imperative part in the structure ’s service
life containing it. The structure of concrete must ensure
that the concrete can resist chemical and physical erosion
*Corresponding Author: Wang Hongguang: School of Civil Engi- and other mechanical stress during its expected service
neering, Northeast Forestry University, Harbin 150040, China; Key life [11]. It is extremely resistant to acid, alkaline silica and
Laboratory of Bio-based Material Science and Technology (Ministry fire. Geopolymers have an inorganic structure and cannot
of Education), Northeast Forestry University, Harbin 150040, China;
be burned as easily as organic polymers. Besides, geopoly-
Email: wanghongguang@nefu.edu.cn
Tian Lingyu: School of Civil Engineering, Northeast Forestry Univer- mers are non-toxic and smoke-free, and their processing
sity, Harbin 150040, China temperature is lower than other ceramic composites [12].
He Dongpo, Zhao Jianing: School of Civil Engineering, Northeast Geopolymers can be used as environmentally friendly build-
Forestry University, Harbin 150040, China

Open Access. © 2021 Tian L. et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0
License
2 | Tian L. et al.
Figure 1: Schematic molecular structure of geopolymer in contrast to OPC [8]
ing materials, which can achieve the purpose of sustainable
development. Bakharev [13, 14] found that geopolymer con-
crete has strong acid and sulfate resistance. The chloride
ion permeability of OPC and GPC was studied by Rajamane
and other scholars [15]. Sathia et al. [16] studied the resis-
tance and absorption properties of GPC to acids, and he
found that this property could improve its durability.
In this paper, the mechanism and research progress
regarding the carbonation resistance, structural fire resis-
tance, corrosion resistance, permeation properties and frost
resistance of geopolymer concretes are reviewed, and the
main problems with the durability of geopolymer concretes
are discussed.
(a) XRD of Metakaolin [20]
Figure 2
2 Sample Preparation
2.1 Materials
Geopolymers can be made by activating a variety of materi-
als rich in aluminosilicates with strong alkaline solutions at
ambient or slimly raised temperatures [17, 18]. Metakaolin
and fly ash are the main sources of aluminosilicates.
Metakaolin is an anhydrous aluminosilicate mate-
rial made from calcined natural clay mineral kaolinite
[Al2 Si2 O5 (OH)4 ]. All the while the dihydroxylation, struc-
tured water is lost. Under this condition, a naturally amor-
phous and disordered structure (metakaolin) [19] will be
formed, as shown in Figure 2a [20] and Figure 2b [21].
In alkaline earth/alkali solutions, the reactivity of this
amorphous structure is intense [22, 23]. Besides, adding
metakaolin to recycled aggregate GPC can improve the abra-
(b) SEM of Metakaolin [21]
 Durability of geopolymers and geopolymer concretes: A review | 3
Figure 3: Summary of CO2-e for Grade 40 concrete mixtures with OPC and geopolymer binders [5]
sion resistance, but adding nano-SiO2 has the opposite
result [24, 25].
The main by-product of thermal power plants is fly ash.
Because fly ash consists of an amorphous alumina-silicate
framework, it has been identified as a low-cost, readily
available geopolymer polymer [26]. Fly ash-based geopoly-
mers have great advantages. For example, low shrinkage,
low permeability, high-temperature resistance, and high
mechanical strength [27, 28]. Besides, lower CO2 emission
and decreasing energy needs in the process of manufac-
ture make the fly ash-based geopolymers potential replace-
ment materials for the general Portland cement [17, 18, 29].
Figure 3 summarizes CO2 emissions of the entire manu-
facturing 1m3 concrete process [5]. It was found that fly
ash-based geopolymers look to has been extensively used
in the industry of construction [30]. The other fields ap-
plying it involve immobilization of toxic metals [30, 31],
adsorption of dyes [27, 32–34], and the adsorption of heavy
metals [26, 28, 35, 36].
2.2 Methods
There are two design methods for geopolymer:
1. Design by water binder ratio, water glass modulus,
and alkali equivalent.
2. Design by sodium aluminum ratio, silicon aluminum
ratio, and water sodium ratio.
In the design of sodium aluminum ratio, silicon alu-
minum ratio and water sodium ratio, the need for a higher
silicon aluminum ratio will lead to excessive use of alkali
activator and high cost. With the design of water binder ra-
tio, water glass modulus, and alkali equivalent, the amount
of alkali activator is less, and the best mixing ratio can be
found in the close steps.
3 Carbonation-resistant
geopolymer concrete
Carbonation of concrete is a complex physical and chemi-
cal course. It contains the diffusing of CO2 in the gaseous
stage to the pores of concrete, its dissolution in the aqueous
films on the pores, solid Ca(OH)2 dissolution in the water in
the pores, diffusing of dissolved Ca(OH)2 in the pore water,
CO2 reaction with C-S-H, its reaction with the dissolved CO2 ,
with the yet unhydrated C2 S and C3 S. What’s more, there is
a paralleling course, which contains the reduction of con-
crete porosity and the hydration of cementitious materials
[37].
The microstructure of general silicate concrete is di-
verse from that of geopolymer concrete. and it is impossi-
ble to utilize the means of analyzing the carbonation for
general concrete for the experiment [38]. Meanwhile, car-
bonation proof performance of geopolymer concrete is not
all better compared with that of general concrete.
4 | Tian L. et al.

Figure 4: Relationship between the carbonation depth of GP concrete and the elapsed time [40]

Pasupathy et al. [39] surveyed the durability of a pre-

cast fly ash-based geopolymer concrete exposed to the out-
side environment for 8 years. Major specimens from GPC
culverts were checked to decide the influence of carbon-
ation, the durability, the pore-size distribution, and the
permeation properties was contrasted with that of general
Portland cement concrete exposed to the same environ-
ment. It was discovered that the carbonation resistance of
OPC concrete is higher than that of GPC.
Li Zhuguo et al. [40] researched the carbonation depths
of wide variety of GPC and GP mortars by the test of accel-
erated carbonation at different times in the GP mortars and
Figure 5: Relationship between the a value and compressive
GP concrete, the aluminosilicate materials are composed
strength [40]
by ground blast furnace slag and fly ash. Figure 4 tells the
testing results of the relations among the elapsed time for
the concrete of GP and carbonation depth(C-depth) [40]. based on Fick’s first law [42]. Resistance of the carbonation
The depth of carbonation enhanced with the elapsing time of GPC is linked to the strength of compression. Concrete
in the first 3 weeks, but after three weeks, the increase was with an increasing strength normally probably has an in-
decreasing [40]. creased resistance of carbonation. Nevertheless, other fac-
The affecting elements for the resistance of carbona- tors are affecting the resistance of the carbonation of GPC,
tion of blast furnace slag(BFS)-based and fly ash(FA)-based including types of alkaline activator. It has shown from the
GPC were analyzed by comparatively utilizing the rate coef- results of experiment in this research that the coefficient of
ficients of carbonization. It was found that the resistance carbonation rate of BFS-based and FA-based GPC was not
of carbonation of BFS-based and FA-based GPC cured at always decreasing along with its strength of compression,
the room temperature was lower than for a typical concrete as indicated in Figure 5 [40].
that comprising general Portland cement. The resistance Metakaolin/slag-based GPC (w/b ratio 0.47) was stud-
of carbonation strengthened with increased BFS ratio in ied by Bernal et al. [43]. Through an accelerated carbona-
the active fillers, NaOH content in the active activator so- tion testing utilizing a CO2 concentration of 3.0 ± 0.2% at
∘
lution, and BFS fineness or with decreased water/AF ratio 20 C for 28 days. It was found that the strength of compres-
and AS/AF ratio. What’s more, a retarder using and heat sion was decreasing monotonically along with the process
curing benefited the resistance of carbonation of BFS-based of carbonation. The relations among the extent of carbona-
and FA-based GPC. tion and volume of the pore was as same as that of sample
The durability of fly ash geopolymer concretes was in- with different metakaolin percentages, opposite to the sam-
2+ ples of slag-based concrete. It suggested that the loss of
fluenced by the contents of Ca [41]. The popularly applied
theory is a pattern of the depth of concrete carbonation strength of a carbonated binder is not just controlled by
 Durability of geopolymers and geopolymer concretes: A review | 5
one parameter, the porosity. Because of the gel chemistry
of binder, a convoluting effect could determine the residual
level of strength after accelerated carbonation.
4 Structural fire-resistant
geopolymer concrete
It is extremely important to protect the structures from fire.
As a new material, a geopolymer can be widely used in
many fields. Compared with Portland cement adhesive, it
has superior inherent fire resistance. Geopolymers are not
as flammable as organic polymers, which rely on their inter-
nal inorganic structure [12, 44]. It has advantages over tradi-
tional ceramic composites because it has lower processing
temperatures and is non-toxic and smoke-free [45]. The rea-
son why geopolymers can withstand high temperatures is
that their performance and properties are determined by
their internal structural composition and synthetic design
[46].
In the large-scale application of geopolymers in the
construction industry as refractories, it is necessary to in-
vestigate and inspect the thermal properties of geopolymers
from macroscale, mesoscale, and microscale aspects [47].
This idea can be explained in Figure 6 [7]. Microscopically,
the transformation and phase transition of nanostructures
of geopolymers at high temperatures require precise obser-
vation. Its phase transition activity at high temperatures
has been analyzed and reported by some researchers [48–
52]. The chemical stability of geopolymers is certainly very
high [53–57]. Therefore, chemical stability is closely related
to microscopic activities, and microscopic properties are
more conducive to the stability of matter at higher scale
levels (that is, at mesoscale and macroscale). At high tem-
peratures, the thermally induced cracking ability and vol-
ume deformation ability of a substance is called moderate
thermal stability. The resistance to spalling and the ability
of materials to withstand high temperatures is related to
macro-stability [46].
The microscopic properties of geopolymers have been
reported by some researchers. It has also been found that
geopolymers are chemically more stable than OPC hydrated
products, and their chemical structure is easier to be de-
stroyed because when exposed under the temperature, OPC
will get severely deteriorated. Factors as alkali contents, al-
kali cation types and Si / Al ratio play imperative roles in
deciding the chemical structures of geopolymers when ex-
posing to the raising temperatures. These factors shall then
be tailored to accomplish a suitable mix of geopolymer for
the structural fire applications.
Figure 6: Methodology to ensure good structural performance of
geopolymers subject to high temperature heating [7]
When geopolymers are exposed to high temperatures,
thermal expansion or thermal contraction will occur, caus-
ing macroscopic cracks. It is essential that the water con-
tent of the geopolymer mixture can be controlled to adjust
for thermal deformation. For example, for processing pur-
poses, fly ash-based geopolymers require less water than
metakaolin geopolymers, so if choose a structural poly-
mer that requires high fire resistance, metakaolin-based
geopolymers are not a good answer [58]. Moreover, the ad-
dition of PVA and basalt fibers to GPC can reduce strength
and weight loss to enhance structural fire-resistant under
high-temperature environments [59, 60]. Adding microen-
capsulated phase change materials (MPCM) to GPC can
improve the porosity to enhance the performance of heat
capacity and decrease compressive strength [61, 62]. The
types of alkali metal cations and the alkali-activating solu-
tion have a huge effect on thermal deformation. For exam-
ple, comparing to using sodium as an alkali cation, thermal
shrinkage could be better reduced by using potassium as
an alkali cation [56]. When applying a mixture of geopoly-
mers at high temperatures, these factors must be carefully
considered.
Rickard et al. [63] studied the microstructure of two
geopolymer mixtures: one was a dense microstructure and
highly reactive geopolymer, and the other mixture did not
react due to the large amount of fly ash. Therefore, the
strength and density of the polymer are relatively low. Be-
cause of the dense microstructure, low-strength polymers
are stronger than high-strength polymers. Due to macro-
cracks and dehydration damage, high-strength geopoly-
mers have increased strength losses, reduced thermal per-
formance, and increased dimensional instability. Studies
have found that low-strength geopolymers will be slightly
6 | Tian L. et al.

Figure 7: Schematic depiction of the proposed micro-structural changes in geopolymer paste upon firing [63]

damaged because of dehydration, which can better adapt to

volume changes, and its strength increases when exposed
to heat. The model in Figure 7 speeds up these results [63].

5 Corrosion-resistant geopolymer
concrete
5.1 Resistance to acids

Acidic substances react with alkaline substances in

calcium-containing cement base materials, such as CaCO3 ,
CaSO4 , and ettringite, causing volume expansion, and the
gaps are created inside the matrix to make it easier for acidic
materials to enter. The damage arises from acid erosion
of the concrete. Acid erosion affects geopolymer concrete,
but there are a large number of Si-O and Al-O structures
in its structure. Therefore, acid does not easily react with
geopolymers at room temperature, so it can be used to make
acid-resistant materials.
Davidovits et al. [12] emphasized that when the sam-
Figure 8: Concentration of elements dissolved from geopolymer
ples were placed in 5% H2 SO4 solution for 30 days, the samples, (a) in acid solution; (b) in alkali solution [64]
mass loss of metakaolin-based geopolymers was found to
be 7%. According to the report, the fly ash-based geopoly-
mer microstructure can be retained for 3 months after being ash-based geopolymer slurry was placed in a 5% H2 SO4
placed in HNO3 . and 5% acetic acid solution, the performance was superior
Temuujin et al. [64] found that the alkali and acid resis- to ordinary Portland cement slurry. The formation of zeo-
tance of fly ash-based geopolymers are largely determined lites and depolymerization aluminosilicate network were
by their mineral composition. Fe, Si, and Al highly solu- closely related to the deterioration in the pastes [13].
ble ions are obtained from strong acid and alkali solutions. Hardjito et al. [65] discovered that the strength of com-
Figure 8 shows the concentration of dissolved elements pression of a fly ash-based GPC in 0.5% H2 SO4 solution was
in a geopolymer sample after being placed in an alkaline reduced by 20% when exposed for 12 months. The value
or acid solution [64]. The study found that when the fly was 65% and 52% after the samples were exposed to 2%
 Durability of geopolymers and geopolymer concretes: A review | 7

Pasupathy et al. [67] announced that the weight dam-

age in the concrete samples was less than 5% after 3 months
of exposure to a 3% H2 SO4 solution. Slag-based GPC (40
MPa) has reduced 33% strength in contrast to OPC concrete
that has reduced 47% when exposing to an acetic acid so-
lution (pH=4) for twelve months. Low calcium C-S-H with
Ca/Si ratio of 1 and slag particles seemed more stabilized
in the solution of acid in contrast to the OPC pastes con-
stituents. In the immersion of solution of 2% H2 SO4 , the
loss of strength was 11% for the GPC in contrast to 36.2%
for the concrete of OPC [68].

Figure 9: Compressive strength evolution of the geopolymer and 5.2 Resistance to seawater and sulphate
Portland cement specimens exposed to 5% acetic acid solution [13]
solutions

It was reported by Hanrahan [69] that the durability of fly

ash-based geopolymer concrete is greatly governed by the
internal configuration of aluminosilicate gel components
in extreme environments (including 5% MgSO4 solution
and 5% Na2 SO4 solution). As shown in Figure 11 [69], the
transition of alkaline species from geopolymer to the solu-
tion might be related to some fluctuations as shown by the
compression strength of OPC and GPC concrete exposed
to 5% MgSO4 and Na2 SO4 . The GPCs made with a sodium-
silicate activator are less crystalline than that those made
with sodium hydroxide. The geopolymer concrete activated
Figure 10: Compressive strength evolution of the geopolymer and
with NaOH solution only performed better than the OPC
Portland cement specimens exposed to 5% sulfuric acid solution
[13] concrete. It was reported by Criado et al. [70] that the dura-
bility and strength of the GPC improved along with the time
regardless of the kinds of chemical solutions where the
and 1% H2 SO4 solutions, separately. Erosion and pitting on samples were submerged, as shown in Figure 12 [71].
the surface of the concrete were also watched. The degra- Durability performances of fly ash geopolymer concrete
dation of the geopolymer matrix is the main cause of the have been researched by Adam [72]. One new understand-
loss of concrete strength, not the degradation of the aggre- ing of the durability and strength of GPCs have been offered
gate. The researchers found that the acid resistance of OPC
concrete is not as good as that of GPC. Figure 9 depicts the
change in compressive strength of a polymer sample when
exposed to an acetic acid solution [13]. Figure 10 shows the
change in compressive strength of polymer samples when
exposed to sulfuric acid solution [13].
Ariffin et al. [66] used a mixture of palm oil fuel and
powdered fuel to make GPC in a 2% sulfuric acid solution
for up to 18 months. It was found that OPC concrete lost 20%
of its weight and GPC lost 8% of its weight. The strength of
OPC decreased by 68% after 30 days, while the strength of
GPC decreased by 35% within 18 months, and OPC severely
deteriorated after 18 months. N-A-S-H has no obvious ef-
fect on the structure of GPC, but C-S-H is harmful to OPC Figure 11: Compressive strength of fly ash activated with sodium
concrete. silicate solution and NaOH, and OPC specimens, exposed to 5% of
Na2 SO4 and MgSO4 [69]
8 | Tian L. et al.
Figure 12: Mechanical strength of fly ash mortars (a) NaOH-
activated, and (b) water glass-activated [71]
on the chloride and carbonation resistance and the effects
of the dosage of Na2 O on the compression strength of sam-
ples of GPC. Both activator modulus and Na2O dosage play
crucial parameters for the GPC production. It was discov-
ered that fly ash geopolymer concrete shows a strength
compared to that of concrete of OPC. Nevertheless, the prop-
erties of the durability of fly ash geopolymer concrete were
watched to be good on the chloride and carbonation resis-
tance than those for the concrete of OPC.
6 Permeation properties of
geopolymer concrete
The permeating performance influenced by the size of per-
meable pores of the concrete of geopolymer means the
performance of the microstructure of the produced matrix
[73, 74].
Figure 13: The porosity and pore size distribution of geopolymer
incorporating various content of metakaolin after 180 days of expo-
sure [77]
A decreased water permeability (2.46-4.67 × 10-11 m/s)
for a GPC (activator-fly ash ratio of 0.30–0.40 cured at 60∘ C
for 24 h) in contrast to that for OPC has been reported by
Nikraz and Olivia [75], because of its lower pore intercon-
nectivity and denser paste. It was also reported that the
most affecting parameter influencing the property of GPC
was the water-geopolymer by some researchers. Fly ash
geopolymers blended slag, because of their reduced poros-
ity volume and enhanced pore size matrix, which showed
good resistance to the permeability, which might progres-
sively be improved by raising temperature curing [76].
As talked previously, the microstructure of the geopoly-
mer matrix has been densified by metakaolin particles,
which might lower the porosity [77]. After it was exposed
to the sodium sulfate solution for 180 days, as indicated
in Figure 13 [77], the water absorption and apparent poros-
ity will be increasing along with the rising temperature.
At raising the temperature, the water included in the ma-
trix moving to the surface and produced micro-cracks that
was increasing the absorption of water. The permeability
of chloride of the concrete of the geopolymer was tested by
 Durability of geopolymers and geopolymer concretes: A review | 9

increased freeze-thaw resistance with an increased Na/Al

ratio.
The mercury intrusion porosimetry results show that
the metakaolin-based geopolymer had two types of pores.
The most likely pore diameter decreased with a high Si/Al
ratio and increased with a high Na/Al ratio. The geopolymer
presents additional small pores and an increased poros-
ity with a decreased Na/Al ratio and large pores and a de-
creased porosity with an increased Na/AI ratio. The geopoly-
mer with a weak freeze-thaw resistance shows an increased
porosity and additional pores less than 50 nm. After the
F-T cycles, an increasing number of gel pores and 200-400
Figure 14: Corrosion rate of geopolymer and PC concrete specimens,
nm pores can be observed with the geopolymer that had a
immersed in 3% NaCl solution [80]
weak resistance.
Metakaolin-based geopolymer groups with Si/Al=2.00
the Rapid chloride permeability (RCP) test as the chloride and Na/Al=0.80-1.20 in addition to Na/Al=1.05 and
of acid-soluble (total chloride), as per the ASTM C-1202 [78]. Si/Al=1.80-2.20 were conducted with a permeability test.
Part et al. [79] forecast that long time resistance of chlo- The test results show that geopolymers with increased
ride of geopolymer concrete will be lower than that of con- Si/Al ratios present a generally increased permeability, and
crete of OPC due to the lower increment of strength along geopolymers with high Na/Al ratios present a decreased per-
the time of concrete of geopolymer. The rates of corrosion meability. The permeability coefficient of the geopolymer
of PC concrete and the geopolymer in 3% sodium chloride is correlated with porosity, effective porosity, and critical
solution are indicated in Figure 14 [80]. The tried survey of pore diameter. A calculated permeability coefficient that
the long time chloride resistance of a geopolymer concrete considers pore structure parameters is proposed to predict
utilizing a fast chloride permeability testing was futile, as the water permeability of metakaolin-based geopolymers.
the specimens of geopolymer showed a fast-rising in the Metakaolin-based geopolymer concretes have poor
temperature in the testing, which is opposite to the law frost resistance, and the freezing-thawing limit is less
of Ohm and showed that RCPT is not an appropriate test than 75 times. The Na2 O equivalence content and activa-
means to assess the resistance of chloride of concrete of tor modulus have a great effect on the freeze-thaw per-
geopolymer. formance and mechanical properties of geopolymer con-
crete. A metakaolin-based geopolymer concrete with a
Na2 O equivalent weight of 16% and modulus of 1.5 was
the best herein, and the freezing-thawing limit reached 75
7 Frost-resistant geopolymer
times. The frost resistance of geopolymer concretes had
concrete a positive correlation with the Na2 O equivalent content;
the correlation coefficient was 0.845, and the correlation
Deterioration of freeze-thaw-induced concrete could be with the activator modulus and other parameters was not
contributory to the microcracks appearing at the zones of significant.
weak interfacial transition among paste/MPCM and the Slag can shorten the setting time of the geopolymer,
paste/aggregate [81]. enhance the mechanical properties of the geopolymer con-
PE-EVA-PCM and St-DVB-PCM were contained by char- crete, and strengthen the tensile strength by more than
acterization of the Microscopic Structure of the PCC and 20%. The frost resistance of geopolymer concrete increased
GPC after 0 and 28 freeze-thaw cycles were executed by with increasing slag content. The limit freeze-thaw times
tomography imaging of X-ray and SEM. SEM images of the of geopolymer concrete with a 30% slag increased from
samples after 28 freeze-thaw cycles are indicated in Fig- 43 to 135. The frost resistance of geopolymer concrete was
ure 15 [81]. Metakaolin-based geopolymers with Na/AI=1.01; improved in the decreasing order of sodium lauryl sulfate
Si/AI=2.01, 2.32 and 2.62; Si/Al=2.62; and Na/Al=1.01, 1.26, >sodium dodecyl sulfate> sodium arsenate, which had the
and 1.36 were subjected to freeze-thaw cycles. The exper- ideal mixing amounts of 0.06%, 0.08%, and 0.02%, respec-
iment shows that the geopolymer presents a decreased tively. The freezing-thawing limit for geopolymer concretes
freeze-thaw resistance with an increased Si/Al ratio and an could be increased from 36 times to 60-75 times by entrain-
ing air. Three particular air-entraining agents introduced
10 | Tian L. et al.

Figure 15: SEM images of the fracture surface of PCC and GPC [81]

bubble spaces and pore sizes exceeding 400 µm and 300

µm. Common air-entraining agents have poor compatibil-
8 Conclusions
ity in high-alkaline, high-viscosity fresh geopolymer con-
In this paper, the mechanisms and research progress regard-
cretes. Slag can improve the frost resistance of geopolymer
ing the carbonation resistance, structural fire resistance,
concretes better than air-entraining agents. There is an in-
corrosion resistance, permeation properties and frost resis-
creased improvement in the frost resistance using both slag
tance of geopolymer concretes were reviewed, and the main
and air-entraining agents.
problems with the durability of geopolymer concretes were
The degree of saturation is the most important factor
discussed. The conclusions of this review are as follows:
that influences the frost resistance of geopolymer concretes,
and the degree of saturation is greater than the rate of the 1) Durability of geopolymers and geopolymer concretes
temperature decrease. The porosity of a geopolymer con- is influenced by the materials and design meth-
crete exceeds 15%. The balance of capillary water satura- ods for geopolymer preparation. The reactivity of
tion was 0.84 to 0.92 within 12 hours. Here, the geopolymer metakaolin-based GPC structure is intense. Besides,
pores were filled with sodium silicate solution, and the con- adding metakaolin to recycled aggregate GPC can
centration of Na+ ions was very high and reached approx- improve the abrasion resistance. FA-based GPC has
imately 0.6 mol/L. The pore structure of the geopolymer great advantages, such as low shrinkage, low perme-
concrete was terrible because the pores exceeded 75% in ability, high-temperature resistance, and high me-
the SEM images, and the proportion of harmful spores in chanical strength. There are two design methods for
the freeze-thaw process was further increased. They caused geopolymer preparation. In the design of sodium
the freezing pressure and osmotic pressure to increase dur- aluminum ratio, silicon aluminum ratio and water
ing the freeze-thaw process, and even salt precipitation sodium ratio, the need for higher silicon aluminum
produced a crystallization pressure, ultimately resulting in ratio will lead to excessive use of alkali activator and
poor frost resistance. The freezing-thawing failure mech- high cost. With the design of water binder ratio, wa-
anism of geopolymer concretes is mainly based on hydro- ter glass modulus, and alkali equivalent, the amount
static and osmotic pressure theory.
 Durability of geopolymers and geopolymer concretes: A review | 11

of alkali activator is less, and the best mixing ratio 5) Because of lowered porosity volume and enhanced
can be found in the close steps. matrix of pore size, the slag mixed fly ash-based
2) The carbonization proof property of concrete is not geopolymer showed good resistance to permeability,
poorer than that of concrete of geopolymer. Usually, which might progressively be improved by the rising
the higher the GPC strength, the better the resistance temperature curing. The microstructure of the matrix
of the carbonation. Nevertheless, an alkaline acti- of geopolymer was densified by metakaolin particles,
vator also affects the resistance of the carbonation this might lower the porosity. Geopolymers with in-
of GPC. BFS-based and FA-based GPC resistance of creased Si/Al ratios generally present an increased
carbonation is influenced by BFS ratio in the active permeability, and geopolymers with increased Na/Al
fillers, NaOH content in the active activator solution ratios present a decreased permeability. The survey
and BFS fineness. The effect of metakaolin-based and of the long time chloride resistance of GPC utilizing
slag-based GPC is the gel chemistry of binders. It sug- a fast chloride permeability testing is opposite to the
gested that is not just controlled by one parameter. law of Ohm and showed that RCPT is not an appro-
Besides, due to the microstructure of OPC is diverse priate test means to assess the resistance of chloride
from that of GPC, it is impossible to utilize the same of concrete of geopolymer.
experiment to analyze the carbonation of concrete. 6) The freezing-thawing failure mechanism of geopoly-
3) There is a non-organic structure in the materials of mer concretes is mainly based on hydrostatic and os-
geopolymer and indicate fixed higher anti-fire to that motic pressure theory. Geopolymers have a decreased
of Portland cement binder. Elements as the alkali freeze-thaw resistance when they have an elevated
content, alkali cation, and Si/Ai ratio are imperative Si/Al ratio and an increased freeze-thaw resistance
and decide the chemical structure of geopolymers with an elevated Na/Al ratio because geopolymers
when exposed to the rising temperatures. Those el- with increased Si/Al ratios present a generally in-
ements shall be tailored to accomplish a suitable creased permeability, and geopolymers with high
geopolymer mix for the application in a structural Na/Al ratios present a decreased permeability. The
fire. Because FA-based GPC requires less water than frost resistance of geopolymer concretes improves
metakaolin-based GPC during processing, FA-based with increasing slag content. Besides, the Na2 O equiv-
GPC is easier to adjust for thermal deformation. Com- alence content and activator modulus have a great
paring to using sodium as an alkali cation, thermal effect on the freeze-thaw performance and mechan-
shrinkage could be better reduced by using potas- ical properties of GPC. The degree of saturation is
sium as an alkali cation. Besides, low-strength GPC the most important factor that influences the frost
thermal performance is better than high-strength resistance of geopolymer concretes and causes the
GPC. Due to macro-cracks and dehydration damage, freezing pressure and osmotic pressure to increase
high-strength geopolymers have increased strength during the freeze-thaw process, and even salt precip-
losses and increased dimensional instability. Low- itation produced a crystallization pressure.
strength geopolymers will be slightly damaged be-
cause of dehydration, which can better adapt to vol- Acknowledgement: The research in this paper has been
ume changes, and its strength increases when ex- supported by the National Natural Science Foundation of
posed to heat. China (Grant No. 51708092) and China Postdoctoral Science
4) There are a large number of Al-O and Si-O structures Fund Project (Grant No. 2018M631894).
in geopolymers. Geopolymers do not react with acids
at room temperature and can be used to make acid- Conflict of Interests: The authors declared that they have
resistant materials. The durability of fly ash-based no conflicts of interest to this work.
GPC is observed to be better in terms of chloride re-
sistance than OPC. The alkali and acid resistance of
fly ash-based geopolymers are largely determined by
their mineral composition to form an aluminosilicate
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