Yu et al.

Int J Concr Struct Mater (2023) 17:32 International Journal of Concrete

https://doi.org/10.1186/s40069-023-00591-7
Structures and Materials

RESEARCH Open Access

Examination of sulfate resistance

of nano‑alumina added ordinary Portland
cement paste, focusing on the two different
crystallinity of nano‑aluminas
Juan Yu1, Sungwon Sim1, Haemin Song1, Dohoon Kim1, Kyungcheol Jang1, Dongho Jeon1, Seung Cho1,2 and
Jae Eun Oh1*   

Abstract
This study examined the influence of the crystallinity of added nano-alumina on the sulfate resistance of ordinary
Portland cement (OPC) paste. Two crystalline types of nano-aluminas (α-and γ-phase) were incorporated in cement
pastes, which were exposed to sulfate solution. In the results, both paste samples having α- and γ-phase aluminas
had accelerated compressive strength loss and increased length expansion compared to the sample without alumina
addition. In particular, the rapidly decreased dynamic elastic modulus of the nano-alumina added samples postulates
the greatly increased internal stress likely by the increased formation of volume expansive reaction products, such
as ettringite, which was supported by the XRD and TG results. The greater ettringite formation in the nano-alumina
added samples was likely due to reactive ­AH3 (=Al(OH)3) gel formation as the higher consumption degree of port-
landite in the alumina added samples indirectly indicates the active A ­ H3 gel formation, resulting in additional ettrin-
gite formation from the reaction of ­AH3 with N ­ a2SO4 solution. A further degree of sulfate attack was observed in the
γ-alumina added sample for the long-term ­Na2SO4 exposure (180 days) mainly due to the greater degree of gypsum
formation inducing more internal expansive stress compared to the α-alumina added sample.
Keywords Nano-alumina, Ordinary Portland cement, Degree of crystallinity, Alumina dissolution, Sulfate attack, α-
and γ-alumina

1 Introduction
The pulverization of micro-sized spherical materi-
als (e.g., ­SiO2, ­TiO2, ­Al2O3, or ­Fe2O3) into nano-scale
materials has continued to gain research interest in
the construction material field as it introduces sev-
Journal information: ISSN 1976-0485 / eISSN 2234-1315 eral benefits when incorporated, such as morphologi-
*Correspondence: cal rearrangement of cementitious materials on the
Jae Eun Oh nanometer scale (Mukhopadhyay, 2011). Nanometer-
[email protected]
1
School of Urban and Environmental Engineering, Ulsan National
sized alumina ­(Al2O3) (hereafter referred to as nano-
Institute of Science and Technology (UNIST), UNIST‑gil 50, Ulju‑gun, alumina) is one of them, and the nano-alumina addition
Ulsan 44919, Republic of Korea
2
can improve the mechanical properties and durability
Division for Structural Engineering and Civil Engineering
Informatics, Department of Civil Engineering, Stellenbosch University,
of cementitious materials, as reported by other studies
Stellenbosch 7600, South Africa (Chen et al., 2018; Farzadnia et al., 2013; Li et al., 2017;
Maagi et al., 2019; Mohseni et al., 2019; Shahrajabian

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Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 2 of 11

& Behfarnia, 2018; Zhan et al., 2019). In general, alu- The late ettringite formation can cause severe vol-
mina is categorized into two classes: (1) α-alumina: ume expansion in the cementitious binders, resulting
crystalline alumina with lower surface areas, (2) η- or in crack propagation and disintegration. (Dyer 2014;
γ-alumina: poorly crystalline alumina having high sur- Mehta and Monteiro, 2014).
face areas (Acikgoz et al., 2018; Maciver et al., 1963; On the other hand, if the binders become denser
Newsome et al., 1960). through pore refinement by nano-alumina incorpora-
The influence of nano-alumina incorporation on tion, the sulfur penetration in the binder matrix could
cementitious binders depends on the crystallinity of be inhibited, which leads to a reduction in the expansive
nano-alumina. Shao and Zhou et al. (Shao et al., 2019; crack propagation (Zhan et al., 2019). In a similar case,
Zhou et al., 2019) investigated the influence of nano- nano-silica played a role in preventing sulfur leaching
sized γ-alumina on OPC at short- and long-term curing by making the pores of the binder denser and enhanc-
periods and found that the incorporated nano-alumina ing the anti-cracking effect (Huang et al., 2020; Qudoos
was dissolved in alkaline conditions (pH =  ~ 13), result- et al., 2019; Xie et al., 2019a). Gopalakrishnan et al.
ing in increasing the quantity of aluminum-bearing (Gopalakrishnan & Jeyalakshmi, 2020) evaluated the sul-
hydration products such as ettringite, monosulfate fate resistance of nano-alumina added OPC mortar and
­[Ca4Al2O6(SO4)·14H2O], and monocarboaluminate found that the improved sulfate resistance of the mor-
­[Ca4Al2O7(CO2)·11H2O]. Another study showed that tars by nano-alumina addition. However, this study could
the amorphous nano-alumina accelerated the silicate not correctly validate the influence of nano-alumina
and aluminate phases reactions in OPC and reduced incorporation in pure OPC binders exposed to sulfur
macropores, resulting in early strength improve- sources primarily because of the presence of other poz-
ment (Zhan et al., 2019). In the case of CaO-activated zolanic materials, i.e., fly ash, in that OPC mortar, which
GGBFS binder, it was found that the higher dissolu- can be a sulfate resistance improving factor (Dyer 2014;
tion rate of amorphous nano-alumina (i.e., γ-alumina) Gopalakrishnan & Jeyalakshmi, 2020; Xie et al., 2019b).
increased the amount of hydration products formation, From this point of view, in this study, the following two
such as calcium silicate hydrate (C-S-H) and ettringite aspects of nano-alumina must be addressed to encour-
­[Ca6Al(SO4)3(OH)12·26H2O], which improved the com- age the application of nano-alumina in practice: (1) the
pressive strength (Yu et al., 2021). variation of the dissolution rate of nano-alumina due to
In addition, the sulfuric content in the nano-alumina the different crystallinity reacting with ingressing sulfate
added cementitious binders affected the type of reac- causing internal volume expansion; (2) the prospect of
tion hydrates (Shao et al., 2019; Yu et al., 2021; Zhou cementitious matrix densification to disrupt sulfur pen-
et al., 2019). In CaO-activated GGBFS binders, for etration. This study employed two different crystalline
instance, the formation of monosulfate was dominant, types of nano-aluminas, i.e., α- and γ-aluminas, on OPC
and the leftover of dissolved alumina turned into amor- paste. Various mechanical tests (compressive strength
phous ­AH3 gel when enough sulfur was not supplied test, visual inspection, length change measurement,
(Yu et al., 2021). However, in high sulfur concentration longitudinal dynamic elastic moduli of cement paste),
conditions, the ­AH3 gel reacted with the sulfur and cal- and chemical analyses [powder X-ray diffraction (XRD),
cium from calcium oxide resulting in a high amount of and thermogravimetry (TG) with derivative of thermo-
ettringite formation (Yu et al., 2021). Similarly, in OPC gravimetry (DTG)] were conducted to discuss the effect
binders, the dissolved alumina accelerated gypsum con- of nano-alumina inclusion towards the sulfate attack
sumption which led to a rapid ettringite formation at an resistance.
early age (Zhou et al., 2019). In the long-term period,
the monosulfate formation was dominated instead of 2 Experimental Procedure
ettringite formation, and the dissolved alumina also 2.1 Raw Materials
increased the monocarboaluminate content which was OPC was obtained from Sampyo Cement Co., Ltd.,
possibly formed by atmospheric ­CO2 (Shao et al., 2019). Seoul, Republic of Korea. Nano-aluminas (α and γ types
It is widely known that the chemical characteristics of of nano-aluminas) were sourced from the Lumi-M Co.
amorphous nano-alumina may enhance the mechanical (Seoul, Republic of Korea).
properties of cementitious binders (Shao et al., 2019; Yu The raw OPC was analyzed with the X-ray fluores-
et al., 2021; Zhan et al., 2019; Zhou et al., 2019). How- cence (XRF) using an S8 Tiger wavelength dispersive
ever, it may raise potential durability issues, particularly XRF spectrometer (Bruker, Billerica, MA, USA). The
the sulfate attack; the residual ­AH3 gel conversion to oxide chemical composition of the raw OPC is pre-
ettringite can occur when sulfur is ingressed from the sented in Table 1, which shows the dominance of CaO
outside, such as in a sewer or seawater environment. and ­SiO2 (i.e., the sum of CaO and ­SiO2 was 81.68
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 3 of 11

Table 1 Oxide chemical composition of raw ordinary Portland cement (wt%)

CaO SiO2 Al2O3 MgO SO3 Fe2O3 K2O TiO2 Na2O P2O5 Others

63.51 18.17 4.43 4.01 3.83 3.44 1.54 0.29 0.18 0.16 0.44

100 1.0
Cumulative distribution

Cumulative distribution (%)

90 0.9
Distribution density
80 0.8

Distribution density
70 0.7
60 0.6
50 0.5
OPC
40 0.4
30 0.3
Reference patterns of identified phases 20 0.2
10 0.1
0 0.0
0.1 1 10 100 1000
Particle size (μm)
3CaO·SiO2 (98-002-2501)
Fig. 2 Particle size distribution of raw ordinary Portland cement
2CaO·SiO2 (98-001-6616)

3CaO·Al2O3 (98-015-1369)
­CaCO3). The cement contained mostly alite (3CaO·SiO2),
4CaO·Al2O3·Fe2O3 (98-009-8833) belite (2CaO·SiO2), and a relatively low amount of
aluminum-bearing cement compounds (3CaO·Al2O3
and 4CaO·Al2O3·Fe2O3), agreeing with the XRF result.
CaSO4·2H2O (98-024-6242)
Around five wt% of calcite ­(CaCO3) was present as an
admixture following the ASTM C150/C150M.
CaCO3 (01-072-1937)
Particle size distributions of the raw OPC were meas-
ured with a laser diffraction particle size analyzer
10 20 30 40 50 60
Position [‚2Theta] (Copper (Cu))
(HELOS (HI199) and RODOS; Sympatec, Clausthal-
Zellerfeld, Lower Saxony, Germany). Fig. 2 presents the
Fig. 1 XRD pattern of raw ordinary Portland cement
particle size distributions of the raw OPC, which had a
median particle size of 11.61 μm.
The raw nano-aluminas were examined using the pre-
wt%). ­Al2O3 and ­ SO3 contents mainly contribute to vious study’s same methods and instruments (Maciver
sulfate attack resistance performance by determin- et al., 1963). In addition, a scanning electron microscope
ing the amount of 3CaO·Al2O3 ­(C3A) and gypsum (SEM) was further employed to monitor the particle dis-
­(CaSO4·2H2O) production. The low contents of A ­ l 2O 3 tribution because the nano-aluminas easily agglomerate
and ­SO3 in Table 1 may imply high sulfate attack resist- with each other, which led to overestimating the particle
ance due to the low proportion of ­C3A and gypsum in size distribution measured by the laser diffraction par-
the cement (Dyer 2014; Mehta and Monteiro, 2014). ticle analyzer (Yu et al., 2021). Briefly, the XRD patterns
Fig. 1 displays the powder XRD diffraction patterns for of α-alumina showed sharped crystalline peaks, while
the raw OPC, which were measured by an X-ray diffrac- that of γ-alumina had an amorphous hump with five
tometer (D8 Advance; Bruker AXS, Fitchburg, WI, USA) broad peaks, and the nano-aluminas’ particle sizes were
with an incident beam of Cu-Kα radiation (λ = 1.5418 Å) approximately 20 nm (Yu et al., 2021).
for a 2θ scanning range of 5–60°. The XRD patterns
were analyzed by using the X’pert High-Score Plus pro-
gram (PANalytical, 2012) with the International Center 2.2 Sample Preparations and Test Methods
for Diffraction Data (ICDD) PDF-2 database (Andersen Table 2 presents the mixture proportions of paste sam-
et al., 2003; Wooster, 1930) and the Inorganic Crystal ples in the study. Each nano-alumina added sample con-
Structure Database (ICSD) (Allmann & Hinek, 2007). tains five wt% of each nano-alumina mixed with OPC.
In the result of XRD, the raw OPC consisted of six In the study, no dispersing agent for nano-aluminas was
types of cement compounds (3CaO·SiO2, 2CaO·SiO2, used to eliminate the possibility of unwanted chemical
3CaO·Al2O3, 4CaO·Al2O3·Fe2O3, ­CaSO4·H2O, and reactions between nano-aluminas and chemical agents.
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 4 of 11

Table 2 Mixture proportions of paste samples (wt%)

Sample labels Binder Water w/b
OPC α-alumina γ-alumina Total

OPC-0 (control) 100 0 0 100 40 0.4

OPC-A 95 5 0 100 40 0.4
OPC-G 95 0 5 100 40 0.4
OPC ordinary Portland cement, w/b water-to-binder weight ratio

The dry constituents were initially dry-mixed for 5 min in Lx − Li

an enclosed chamber to improve dispersion of nano-alu- L =
Lg
× 100 (1)
mina, and then water was added to obtain w/b = 0.4. Fresh
paste samples were cast in three different molds (the size where ΔL = change in length at x age [%]; L ­ x = compara-
of 50 mm × 50 mm × 50 mm, 25 mm × 25 mm × 285 mm, tor reading of specimen at the age of x days—reference
and 40 mm × 40 mm × 160 mm) and cured at 35 °C and bar comparator reading at the age of x days; L ­ i = initial
99.9% relative humidity for one day. After 1 day of cur- comparator reading of specimen—reference bar compar-
ing, the samples were demolded and immersed under ator reading, at the same time; and L ­ g = nominal gauge
­Na2SO4 solution (352 mol of ­Na2SO4 per ­m3) until tested. length, 250 mm.
The ­Na2SO4 solution was renewed, as per ASTM C1012/ The longitudinal dynamic elastic moduli of cement paste
C1012M, at one, two, three, four, eight, 13, 15, 16, and were measured according to ASTM C215-19 to compare
24 weeks. the samples’ decreasing rate of dynamic elastic moduli to
Compressive strength tests were carried out for each ettringite and gypsum content, which could lead to internal
mixture proportion using triplicate samples with sizes of expansion under sulfate exposure (Zhu et al., 2013). The bar
50 mm × 50 mm × 50 mm after 1 day of curing and 28, samples with the size of 40 × 40 × 160 mm in N ­ a2SO4 solu-
91, and 180 days of ­Na2SO4 exposure. After the mechani- tion were wiped gently with a dry cloth, and then an accel-
cal test, the fragments of the fractured samples were erometer was installed at the sample end surface. The other
ground with isopropanol for XRD and TG tests. In this end surface of the samples was impacted with a steel impac-
study, the observation of ettringite is crucial to identify tor five times to obtain reliable data. The data sampling rate
the cause of sulfate attack (Dyer 2014; Mehta and Mon- was 50 kHz, and the dynamic Young’s modulus of elasticity
teiro, 2014). Since ettringite is easily deformed at a tem- in pascals from the fundamental longitudinal frequency was
perature above 40 °C, the process of hydration stoppage calculated as follows:
for each sample should be carefully treated (Winnefeld  2
et al., 2016). Thus, the samples were immersed in isopro- Dynamic E = DM n′ (2)
panol for one hour, filtered with diethyl ether as a second
solvent exchange, and oven-dried at 40 °C for 10 min where: D = 4 (L/bt) ­[m−1]; L = length of specimen [m];
(Failed xxxx). Visual inspection was undertaken before b = dimension of prism cross-section perpendicular to t
compressive strength tests (one day of curing and 28, 91, [m]; t = dimension of prism cross-section in the direction
and 180 days of N­ a2SO4 exposure). the prism is impacted [m]; M = mass of specimen [kg];
and n = fundamental longitudinal frequency [Hz].
′
Length change measurement was recorded over
time as per ASTM C1012/C1012M at every N ­ a2SO4 The XRD measurements were conducted with the
solution renewal. Before immersing the samples ground samples to identify reaction products exposed
in the sulfate solution, the triplicate samples with to ­Na2SO4 solution using the same instrument and setup
25 mm × 25 mm × 285 mm were measured as their initial used for measuring raw materials. The same analysis
length. The sample surface was wiped gently with a dry software and databases in the raw material analysis were
cloth on each designated measurement date, and then used to analyze the XRD patterns, but the reference pat-
the length of the samples was quickly measured using a tern of C-S-H, the main reaction product in hydrated
length comparator apparatus to avoid drying and shrink- cement and semi-amorphous to X-ray, was obtained
age of the samples. The length change can be defined as from 22-year-old β-2CaO·SiO2 (β-C2S) paste after delet-
follows: ing Ca(OH)2 from the original pattern (Mohan & Taylor,
1981).
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 5 of 11

The TG measurements (SDT Q600; TA Instruments, samples lost their compressive strength at 180 days of
New Castle, DE, USA) were undertaken. The tempera- ­Na2SO4 exposure, but the strength reductions were not
ture range for the test was 25–1000 °C with a heating rate as severe as those of the OPC-G samples. After 180 days
of 10 °C/min in a nitrogen atmosphere. This study calcu- of ­Na2SO4 exposure, the compressive strength was found
lated portlandite content using the thermo-gravimetric in the order of OPC-0 > OPC-A > OPC-G. The strength
method to compare the relationship between portlan- degradation mechanism of specimens is discussed in the
dite consumption and hydrates produced for each sam- following sections.
ple (Singh et al., 2015). The weight loss between 400 and
500 ℃ was considered as portlandite decomposition, and 3.2 Visual Inspection of Samples
portlandite content in all samples was calculated from Fig. 4 shows the visual appearances of all samples before
the TG curves using the following equation (Singh et al., and after ­Na2SO4 exposure (i.e., after 28, 91, and 180 days
2015). of ­Na2SO4 immersion). The images display no differ-
ence among samples before ­Na2SO4 exposure. It should
MW (CH)
CH (%) = WL%(CH) × (3) be noted that the sample strengths increased despite the
MW (H ) presence of microcracks on the surfaces of OPC-A and
where: CH(%) = calculated portlandite content (%); OPC-G at 28 days of N ­ a2SO4 exposure. From 28 days of
WL%(CH) = the mass loss in percentage attributable to ­Na2SO4 exposure, considerable cracks formed in OPC-A
portlandite; MW(CH) = molecular weights of portland- and OPC-G in the form of ring-shaped cracks. Notably,
ite; MW(H) = molecular weight of water. it was found that OPC-G was the most susceptible to
­Na2SO4 ingression by presenting severe disintegration. In
3 Results and Discussion contrast, the control samples (OPC-0) showed the least
3.1 Compressive Strength severe damage on all days of immersion, aligning with the
Fig. 3 shows the strength testing results for the paste compressive strength result.
samples. Before the N ­ a2SO4 solution immersion, the
γ-alumina added cement paste (OPC-G) displayed a 3.3 Length Change of Immersed Samples
slightly higher strength (by 2.0 MPa) compared to the Fig. 5 shows the length change of the samples after being
control sample (OPC-0) at the same age. In contrast, the exposed to ­Na2SO4 solution. The length change was dif-
lowest compressive strength was found in the α-alumina fered by the presence of nano-alumina in the cement
added samples (OPC-A). pastes and the crystalline type of the added nano-alu-
After ­Na2SO4 immersion, the compressive strength mina. All samples did not show a linear increase in length
of all alumina added samples increased until 28 days; until 21 days of ­Na2SO4 exposure, but the lengths steadily
however, the strength started to decrease after 28 days increased after 21 days. The OPC-A displayed a similar
of ­Na2SO4 immersion. In particular, OPC-G showed trend to OPC-0 but a slightly greater length change over
more rapid compressive strength degradation, although time. On the other hand, the OPC-G shrunk between
their greatest compressive strength among the test sets 14 and 28 days of Na2SO4 exposure significantly, and
at 28 days of N
­ a2SO4 exposure. The OPC-A and OPC-0 then their vertical length increased drastically, particu-
larly after 91 days. At 180 days of the ­Na2SO4 exposure,
OPC-G showed the most significant length change,
55.0
resulting in the complete destruction of two samples.
50.0 47.6 zero d 28 d 91 d 180 d
Compressive Strength (MPa)

45.0
39.9
40.0 38.6
36.3
34.9
36.5 3.4 Dynamic Elastic Modulus
34.5 34.4
35.0 31.0 Fig. 6 shows the longitudinal dynamic modulus of elas-
30.0 27.1
ticity of specimens before and after ­Na2SO4 exposure.
25.0 21.5
Both OPC-A and OPC-G had lower dynamic moduli
20.0
15.0 13.5 than OPC-0 during the entire experimental period.
10.0 The dynamic elastic modulus of all samples increased
5.0 gradually, but OPC-A and OPC-G showed a declina-
0.0 tion after reaching the peak dynamic modulus within
OPC-0 OPC-A OPC-G
91 days of ­ Na2SO4 exposure. The decrease in the
Fig. 3 Compressive strengths of hardened paste samples before
­Na2SO4 immersion (zero d) and after ­Na2SO4 exposure (28, 91, and
dynamic modulus of cementitious binders exposed
180 d). Error bars are the standard deviations of the measured to sulfate could be linked to length expansion (Chen
strengths for triplicate samples et al., 2020; Rocco et al., 2004; Zhu et al., 2013). A
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 6 of 11

Fig. 4 The visual appearances of specimens at zero (before immersion), 28, 91, and 180 days in N
­ a2SO4 solution

0.250
OPC-0 OPC-0
OPC-A 24.00
OPC-A
Dynamic Young's modulus

0.200 OPC-G OPC-G

of elasticity (GPa)

22.00
Length change (%)

0.150

20.00
0.100
18.00
0.050
16.00
0.000
0 14 28 42 56 70 84 98 112 126 140 154 168 182
14.00
-0.050 0 14 28 42 56 70 84 98 112 126 140 154 168 182
Exposure duration (days) Exposure duration (days)
Fig. 5 The length change of specimens after ­Na2SO4 exposure Fig. 6 Dynamic elastic modulus curves of the specimens after
­Na2SO4 exposure
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 7 of 11

significant increase in length of OPC-A and OPC-G worsened mechanical properties, such as compressive
was found after 91 days of ­Na2SO4 exposure. Notably, a strength and dynamic modulus. In chemical regard,
sharp increase point in length change and a decrease in the declination of dynamic elastic modulus is closely
dynamic modulus of OPC-G were matched at a similar related to the destructive effect of the internal stress
experimental period. Thus, the rapid length expansion due to the expansion products such as ettringite and
of OPC-G likely affected their dynamic modulus reduc- gypsum (Zhu et al., 2013), which will be discussed in
tion (Chen et al., 2020; Rocco et al., 2004; Zhu et al., XRD and TG, and DTG results.
2013). The dynamic modulus of OPC-A continuously
decreased at a slower pace than OPC-G, which aligns 3.5 XRD
with the length change result. This study found that Fig. 7 shows the XRD patterns of all samples before (zero
the nano-alumina inclusion in cement pastes adversely day) and after ­Na2SO4 exposure (28, 91, and 180 days)
increased in length under N­ a2SO4 exposure, leading to with the reference patterns from the ICDD and the ICSD

OPC-0 OPC-A OPC-G

Zero day Zero day Zero day

28 days 28 days 28 days

91 days 91 days 91 days

180 days 180 days 180 days

Reference patterns of identified phases Reference patterns of identified phases Reference patterns of identified phases
23-year old C-S-H pattern of fully hydrated β-C2S paste 23-year old C-S-H pattern of fully hydrated β-C2S paste 23-year old C-S-H pattern of fully hydrated β-C2S paste
[Ca(OH)2 peaks are removed from the original pattern] [Ca(OH)2 peaks are removed from the original pattern] [Ca(OH)2 peaks are removed from the original pattern]

20 25 30 35 40 45 50 55 60 20 25 30 35 40 45 50 55 60 20 25 30 35 40 45 50 55 60

Carbo aluminate phase (00-036-0129) Carbo aluminate phase (00-036-0129) Carbo aluminate phase (00-036-0129)

Calcite (01-072-1937) Calcite (01-072-1937) Calcite (01-072-1937)

Belite (98-001-6616) Belite (98-001-6616) Belite (98-001-6616)

Portlandite (98-020-2222)
Portlandite (98-020-2222) Portlandite (98-020-2222)

Ettringite (98-002-7039) Ettringite (98-002-7039) Ettringite (98-002-7039)

Kuzelite (01-083-1289) Kuzelite (01-083-1289) Kuzelite (01-083-1289)

Gypsum (98-010-0138) Gypsum (98-010-0138) Gypsum (98-010-0138)

10 20 30 40 50 60 10 20 30 40 50 60 10 20 30 40 50 60
Position [‚2Theta] (Copper (Cu)) Position [‚2Theta] (Copper (Cu)) Position [‚2Theta] (Copper (Cu))

exposure) with the reference patterns from the ICDD and the ICSD database. ■ Ettringite, ▲ Gypsum, ● Kuzelite, ▼ Portlandite, □ Calcite, △
Fig. 7 The XRD patterns of all samples before ­Na2SO4 exposure (zero day exposure) and after ­Na2SO4 exposure (28, 91, and 180 days of ­Na2SO4

Carbo-aluminate phase, ○ Belite

Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 8 of 11

database to identify the phases. The peak intensity scales released the free calcium ions, and a high amount of
of all reference patterns in the result were altered to sulfate from ­Na2SO4 might produce additional gypsum
resemble the identified mineral phases in the measured at 180 days of ­Na2SO4 exposure (Zhou et al., 2019).
XRD patterns. In the sulfate attack, gypsum formation causes inter-
The reaction products identified in the study were nal expansion (approximately 120% expansion) in the
carbo-aluminate phase (4CaO·Al2O3·CO2·11H2O), following chemical reactions, leading to cracking (Dyer
ettringite ­[Ca6Al(SO4)3(OH)12·26H2O], portlandite 2014; Mehta and Monteiro, 2014).
[Ca(OH)2], kuzelite ­[Ca4·Al2·4OH·12.8SO4 ·6H2O], and
gypsum ­(CaSO4·2H2O). The peaks of the carbo-alumi- Ca2+ 2−
(aq) + SO4(aq) + 2H2 O(l) → CaSO4 · 2H2 O (5)
nate phase were observed in all samples before N ­ a2SO4
exposure (zero day) but decreased after N ­ a2SO4 expo- Thus, the excessive ettringite and gypsum formation in
sure because of the transformation of the carbo-alumi- this study further contributed to the severe cracking in
nate phase into ettringite or kuzelite (Feng et al., 2015; OPC-G samples. Additionally, the time at which OPC-G
Irassar, 2009; Irassar et al., 2003). showed the drastic length change coincided with a period
Before sulfate exposure, all samples had similar peak of rapid increase in the gypsum formation, demonstrat-
intensities of ettringite, but a higher ettringite was ing that a large gypsum formation was likely responsible
observed in OPC-A and OPC-G. Higher ettringite for- for the further increase in sample length.
mation of nano-alumina incorporated samples after
28 days of N­ a2SO4 could exert internal stress due to its 3.6 TG and DTG
expansive properties (Zhu et al., 2013), resulting in vol- Fig. 8 presents the TG and DTG test results before (zero
ume expansion and a decline in dynamic elastic modu- day) and after ­Na2SO4 exposure for the total weight loss
lus and compressive strength in the study. Additionally, at a temperature range between 25 and 1000 °C.
the amount of ettringite formation differed in the crys- In the TG result, the total weight losses of all samples
tallinity degree of nano-aluminas due to different dis- gradually increased with increasing days of the N ­ a2SO4
solution rates of nano-aluminas (Shao et al., 2019; Yu exposure. Overall, OPC-G showed the greatest weight
et al., 2021; Zhou et al., 2019). Nano-alumina reacted loss in the temperature region up to 200 °C during all
with portlandite, producing ­AH3 gel in the following experimental periods. In the case of OPC-A, the weight
Eq. (4) (Zhou et al., 2019). Since ­AH3 gel is amorphous loss was similar to that of the control samples up to
and easily reacts with sulfur, forming ettringite, direct 28 days of ­Na2SO4 exposure, but the weight loss became
detection of ­AH3 gel was not possible in the study (Yu higher than that of the control sample after 28 days of
et al., 2021). However, XRD results showed that OPC-G ­Na2SO4 exposure. In the TG results above 200 °C, all
had relatively lower peak intensities of portlandite than samples showed two weight loss regions near 380–440 °C
OPC-A, indicating a high amount of A ­ H3 gel formation, and 620–720 °C in all exposure periods. The total weight
which might react with intruding sulfate after 28 days loss of all samples up to 1000 °C increased until 91 days
of ­Na2SO4 exposure. of ­Na2SO4 exposure and slightly decreased on 180 days of
A significant increase in the peak intensities of gyp- ­Na2SO4 exposure.
sum was observed in the OPC-G at 180 days of N ­ a2SO4 The DTG results display reaction products identified
exposure due to the alumina dissolution process (Zhou with reference to earlier studies (Failed, 2002; Jeong et al.,
et al., 2019). In Eq. (4), alumina transformation pro- 2016; Park et al., 2016; Song et al., 2018; Yu et al., 2021).
duces free ­Ca2+ ions, which normally react with gyp- The chemical compounds identified in the DTG results
sum, forming ettringite (Zhou et al., 2019). included C-S-H, ettringite, AFm ­ (Al2O3–Fe2O3-mono)
−
Al2 O3 · xH2 O(s) + 2CaOH(aq) phases (carbo-aluminate phases and kuzelite), gypsum,
(4) portlandite, and residual calcite consistent with the XRD
2+
↔ 2Al(OH )−
4(aq) + (x − 3)H2 O + 2Ca(aq) results. In general, two distinct DTG peaks in all samples
were observed in the pre-200 °C region. The first DTG
In the study, these free calcium ions likely reacted peak (80–100 °C) indicated dehydration of ettringite and
with ­AH3 gel, gypsum, and ­CaCO3 present in OPC, pro- C-S-H (Failed, 2002; Jeong et al., 2016; Park et al., 2016;
ducing ettringite, kuzelite, and carbo-aluminate phase Song et al., 2018). Before 28 days of ­Na2SO4 exposure,
at the early days of ­Na2SO4 exposure. Additionally, dur- all samples displayed similar intensities of the first DTG
ing the experiment, the N ­ a2SO4 solution intrusion was peaks. However, the first DTG peak in OPC-G increased
accelerated due to the increasing surface disintegra- drastically after 28 days of N­ a2SO4 exposure, compared to
tion of OPC-G, which provided a high sulfate source other samples (OPC-0 and OPC-A), due to the increased
for gypsum formation. Thus, the alumina dissolution quantities of ettringite formation.
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 9 of 11

100
OPC-0 0.30 Table 3 Portlandite content in N
­ a2SO4 solution exposed cement
OPC-0 (Zero day)
OPC-0 (28 days) paste samples (%)
90 OPC-0 (91 days) 0.25
OPC-0 (180 days)
Sample labels Na2SO4 solution exposure
80 0.20
Ettringite & C-S-H

DTG (%/Ș)
Zero-day 28 days 91 days 180 days
TG (%)

70 0.15
Ca(OH)2 OPC 10.61 12.05 11.84 11.72
60 AFm phases & Gypsum 0.10
OPC-A 10.24 11.35 11.10 10.94
CaCO3
50 0.05
Unknown OPC-G 9.62 11.19 10.57 10.04
40 0.00
0 100 200 300 400 500 600 700 800 900 1000
Temperature (Ș)
(a) Irassar, 2009; Irassar et al., 2003). OPC-A and OPC-G
OPC-A
showed greater DTG peaks than OPC-0 in that tempera-
100 0.30
OPC-A (Zero day) ture range. Mainly, the largest DTG peaks could be found
OPC-A (28 days)
90 OPC-A (91 days)
OPC-A (180 days)
0.25 in OPC-G, meaning that γ-alumina addition increased
80 Ettringite & C-S-H 0.20 the formation of carbo-aluminate phases, kuzelite, and
DTG (%/Ș)
gypsum matched with the XRD results (Shao et al., 2019;
TG (%)

70 0.15
Ca(OH)2
Yu et al., 2021; Zhou et al., 2019).
60 AFm phases & Gypsum 0.10 The DTG peaks near 450 °C indicate the dehydra-
50 CaCO3
Unknown
0.05 tion of portlandite (Singh et al., 2015; Song et al., 2018).
0.00
Table 3. presents calculated portlandite content in
40
0 100 200 300 400 500 600 700 800 900 1000 all paste samples at different days of ­Na2SO4 solution
Temperature (Ș) exposure. In the table, the portlandite in all samples
(b)
started to decrease after 28 days of N ­ a2SO4 exposure,
100
OPC-G 0.30 and its decrease occurred with an increase in hydrates
OPC-G (Zero day)
OPC-G (28 days) such as ettringite and AFm phase. Nano-alumina added
90 OPC-G (91 days) 0.25
Ettringite & C-S-H
OPC-G (180 days) sample showed lower portlandite content than the con-
80 0.20 trol sample under N ­ a2SO4 solution exposure due to
DTG (%/Ș)

(1) ­AH3 gel formation and (2) an increase in Al-bear-

TG (%)

70 0.15

AFm phases & Gypsum Ca(OH)

0.10
ing hydrates formation such as ettringite or kuzelite
60 2

(Shao et al., 2019; Yu et al., 2021; Zhou et al., 2019). The

0.05
50 CaCO3 Unknown DTG peak of A ­ H3 gel from γ-alumina could find near
40 0.00 250 °C in a low sulfur environment (Yu et al., 2021),
0 100 200 300 400 500 600 700 800 900 1000
Temperature (Ș)
but OPC-G showed no distinct DTG peak near 250 °C
during all N ­ a2SO4 exposure periods, probably due to
(c)
unexpected extra ettringite formation with intruding
Fig. 8 TG and DTG results of the hardened samples before ­Na2SO4
exposure (zero day exposure) and after ­Na2SO4 exposure (28, 91, and
­Na2SO4 solution. Lower portlandite content and higher
­ a2SO4 exposure): a TG and DTG result of the control
180 days of N DTG peak for ettringite in OPC-A than in the control
samples (OPC-0), b TG and DTG result of the α-alumina added sample support possible A ­ H3 gel transformation of
samples (OPC-A), and c TG and DTG result of the γ-alumina added α-phase nano-alumina under ­Na2SO4 exposure, which
samples (OPC-G) also generated ettringite more. The additional ettrin-
gite formation in OPC-G and OPC-A after 28 days of
­Na2SO4 exposure could not act as pore densification
The other DTG peaks (120–180 °C) were associated but rather cause volume expansion and crack propaga-
with carbo-aluminate phases, kuzelite, and gypsum tion shown in the aforementioned results.
(Jeong et al., 2016; Shao et al., 2019; Yu et al., 2021). These The DTG peak near 650 °C represented the calcite
DTG peaks split into multiple peaks with increasing decarbonization. Before ­ Na2SO4 exposure and in the
­Na2SO4 exposure time because of (1) the transformation early age of ­Na2SO4 exposure (Up to 28 days), the cal-
of carbo-aluminate into ettringite and kuzelite and (2) cite DTG peak decreased slightly, possibly because of
the formation of gypsum and kuzelite (Feng et al., 2015; the formation of carbo-aluminate phases. A high calcite
consumption in OPC-G was well-matched with the high
Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 10 of 11

amount of carbo-aluminate phases observed in the XRD deteriorates the sulfate resistance. Thus, such internal
result. expansion stress development during sulfate exposure
An unexpected increase in the calcite could be found shall be considered during material design for nano-
in the DTG result of the control samples at 91 days of alumina addition in concrete. A stoichiometric dosage
­Na2SO4 exposure because of carbon reaction during the of sulfuric source, like gypsum, can be considered as a
experimental procedure. However, the DTG results still potential mitigation towards such adverse effects as it is
implied the same conclusion: the addition of nano-alu- believed to maximize the early hydration of nano-alu-
mina accelerated the formation of ettringite and gypsum mina with supplementary gypsum content and minimize
after ­Na2SO4 exposure, resulting in severe volume expan- the late transformation into ­AH3 gel which can be stud-
sion and crack propagation. In addition, the high dis- ied in the future.
solution rate of γ-alumina accelerated the sulfate attack
Acknowledgements
degradation. Not applicable.

Author contributions
JY: Conceptualization, Investigation, Methodology, Data curating, and Writ-
4 Conclusions ing—original draft; SS: Investigation, Validation, and Writing—review and
The main objective of this study is to investigate the editing; HS: Investigation, Validation, and Writing—review and editing; DK:
impact of supplementary hydration products from nano- Investigation, Formal analysis, and Writing—review and editing; KJ: Investiga-
tion, Formal analysis, and Writing—review and editing; DJ: Data curating, and
alumina incorporation in ordinary Portland cement paste Writing—review and editing; SC: Data curating, and Writing—review and edit-
under sulfate attack. This may cause two opposite phe- ing; JEO: Conceptualization, Methodology, Writing—review and editing, and
nomena: (1) impediment of sulfate ingress through pore Funding acquisition. All authors read and approved the final manuscript.

refinement (beneficial effect); (2) internal stress induc- Authors’ information

tion from the volume expansion of excessive hydration Juan Yu is a Graduate student in Department of Urban and Environmental
product formation (adverse effect). Both nano-alumina Engineering at Ulsan National Institute of Sciences and Technology (UNIST),
Ulsan, Korea.
incorporated samples (OPC-A and OPC-G) experienced Sungwon Sim is a Postdoctoral Researcher in Department of Urban and Envi-
rapid compressive strength loss, initiating from 28 days ronmental Engineering at Ulsan National Institute of Sciences and Technology
of ­Na2SO4 solution exposure, with increasing length (UNIST), Ulsan, Korea.
Haemin Song is a Postdoctoral Researcher in Department of Urban and Envi-
expansion. At the same time, the control sample (OPC- ronmental Engineering at Ulsan National Institute of Sciences and Technology
0) showed continuous compressive strength development (UNIST), Ulsan, Korea.
up to 91 days of ­Na2SO4 exposure. Severe ring-shaped Dohoon Kim is a Graduate student in Department of Urban and Environmen-
tal Engineering at Ulsan National Institute of Sciences and Technology (UNIST),
cracks were observed in all the nano-alumina incorpo- Ulsan, Korea.
rated samples, but OPC-G remarkably showed a fur- Kyungcheol Jang is a Graduate student in Department of Urban and Environ-
ther disintegration under ­Na2SO4 exposure. On top of mental Engineering at Ulsan National Institute of Sciences and Technology
(UNIST), Ulsan, Korea.
that, a rapid descending zone of modulus was found in Dongho Jeon is a Postdoctoral Researcher in Department of Civil and Envi-
the nano-alumina incorporated samples referring to the ronmental Engineering at Seoul National University, Seoul, Korea, and was
expansion products within the cement paste instigating in Department of Urban and Environmental Engineering at Ulsan National
Institute of Sciences and Technology (UNIST), Ulsan, Korea.
internal stress. To clarify the strength loss mechanism, Seung Cho is a Postdoctoral Researcher in Department of Urban and Envi-
XRD and TG/DTG were employed. The results of OPC-A ronmental Engineering at Ulsan National Institute of Sciences and Technol-
and OPC-G showed a lower portlandite content and a ogy (UNIST), Ulsan, Korea, and was Division for Structural Engineering and
Civil Engineering Informatics, Department of Civil Engineering, Stellenbosch
higher amount of ettringite than the OPC-0. This could University, Stellenbosch 7600, South Africa
be interpreted as the chemical transformation of nano- Ja Eun Oh is a Full Professor in Department of Urban and Environmental
alumina into A ­ H3 gel by consuming portlandite, causing Engineering at Ulsan National Institute of Sciences and Technology (UNIST),
Ulsan, Korea.
extra ettringite formation during ­Na2SO4 exposure. The
higher portlandite consumption rate in the OPC-G sam- Funding
ple could imply a greater A ­ H3 gel formation than OPC- This work is supported by the Korea Agency for Infrastructure Technology
Advancement(KAIA) grant funded by the Ministry of Land, Infrastructure and
A, and this hydrate could react with intruding sulfate, Transport (Grant 21TBIP-C160574-01).
resulting in undesirable expansion products formation
such as ettringite. This could be seen as a primary fac- Availability of data and materials
Not applicable.
tor in the strength loss, length expansion and descending
zone of modulus. The aforementioned observations con-
Declarations
clude that the pore refinement action of γ-alumina would
not effectively prevent sulfate permeation but rather Ethics approval and consent to participate
increases the amount of expansive reactive hydrates such Not applicable.

as ettringite or gypsum through ­AH3 gel formation and

Yu et al. Int J Concr Struct Mater (2023) 17:32 Page 11 of 11

Consent for publication Mukhopadhyay, A. K. (2011). Next-generation nano-based concrete con-

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