Case Studies in Construction Materials 16 (2022) e00792

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Case Studies in Construction Materials

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Case study

Experimental study of the mechanical properties and

microstructure of geopolymer paste containing nano-silica from
agricultural waste and crystalline admixtures
Ar Razi Alvee a, Rizka Malinda a, Alfie Muna Akbar a, Resa Dwi Ashar a,
Cut Rahmawati a, b, *, Thamer Alomayri c, Ali Raza d, Faiz Uddin Ahmed Shaikh e
a
Department of Civil Engineering, Universitas Abulyatama, Aceh Besar, Indonesia
b
Geopolymer and Nanomaterials Research Center, Universitas Abulyatama, Aceh Besar, Indonesia
c
Physics Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
d
Department of Civil Engineering, University of Engineering and Technology Taxila, 47080, Pakistan
e
School of Civil and Mechanical Engineering, Curtin University, Perth, Australia

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

Keywords: This study explored the influence of nano-silica and Crystalline Admixture (CAs) on the me­
Geopolymer chanical properties and microstructure of geopolymer pastes. Nano-silica and CAs was added to
Crystalline admixture the mixture at 3%, 4% and 5% respectively by weight of fly ash. The bulk density, the yield stress
Nano-silica
of geopolymer paste, compressive strength, and flexural bending tests were carried out to eval­
Rice husk ash
Flexural strength
uate the effect of nano-silica and CAs effect on the geopolymer paste. Scanning Electron Micro­
Compressive strength scopy (SEM), X-ray Diffraction (XRD), Transmission Electron Microscope (TEM), and Fourier
Transform Infrared Spectroscopy (FTIR) techniques are employed to examine the microstructure
of nano-silica and geopolymerization products. The test results demonstrated that adding nano-
silica and CAs by 5% increased the bulk density by 5.32%, yield stress by 64.20%, compressive
strength by 33.63%, flexural strength and fracture toughness by 232.69% than the control
specimens, respectively. The SEM, XRD, and FTIR analysis revealed that the effect of nano-silica
and CAs on geopolymer paste occurred mainly in increasing the C–S–H bond and self-healing
products. These findings suggest that rice husk ash can be processed into nano-silica by the
sol-gel method and combined with CAs to obtain better mechanical strength.

1. Introduction

The manufacturing of cement for the construction industry is producing high carbon footprint as a by-product that is harmful for
environmental sustainability. Therefore, it is essential to minimize the use of cement in concrete construction for environmental
sustainability. World cement production increases 2.1% every year and is expected to reach 1.7 times by 2030 [1]. To overcome this
problem, geopolymer is present as an alternative binder and is applied in the construction industry [2,3]. This will lead to a sustainable
construction by replacing the cement. This solution is to reduce energy use and CO2 emissions [4]. Geopolymers are made from main
materials rich in silica and alumina such as fly ash, metakaolin, and slag. Many researchers have shown that fly ash can be used as a

* Corresponding author at: Department of Civil Engineering, Universitas Abulyatama, Aceh Besar, Indonesia.
E-mail address: cutrahmawati@abulyatama.ac.id (C. Rahmawati).

https://doi.org/10.1016/j.cscm.2021.e00792
Received 22 September 2021; Received in revised form 7 November 2021; Accepted 16 November 2021
Available online 18 November 2021
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
A.R. Alvee et al. Case Studies in Construction Materials 16 (2022) e00792

starting material for making good geopolymers [5–7].

Nano-SiO2 is most commonly used to increase the mechanical strength of geopolymers because it has pozzolanic properties and
provides a filler effect [8–11]. Nano-SiO2 particles are very pozzolanic materials because they consist of SiO2 in an amorphous form
with a high specific surface [12]. In this study, nano-silica was made in the laboratory using a rice husk ash, a waste material that is rich
in silica (80–90%) In addition, this material is very easy to obtain and people just throw it away. Utilizing waste materials will certainly
have a good impact on the environment and can increase the economic value of the waste. This is in line with the 13th Sustainable
Development Goals (SDGs), called “climate action”. The nano-silica processing method is carried out using the sol-gel method because
this method is inexpensive and is recommended by many researchers [13,14].
Ten nm nano-silica particles added to cement mortar can increase the compressive strength by about 1.26 times [15]. According to
Haruehansapong et al. [16], from the variation of 3%, 6%, 9%, and 12% nano-silica by weight of cement, it was found that the optimal
content of 9% nano-silica had the greatest compressive strength of 33.35 MPa. A previous study showed that using nano-silica at 2% by
weight of fly ash increased the compressive strength, flexural strength, and fracture toughness by 26.26 MPa, 2.62 MPa, and 0.74 MPa,
respectively [17]. The addition of 1% CAs from cement resulted in crack repair in the specimens and increased flexural strength of
5–10 MPa [18]. The use of 20% fly ash and 2% CAs to replace cement resulted in flexural strength reaching 9 MPa at 540 days [19].
Meanwhile, another property of geopolymer paste that needs improving is self-healing. Self-healing is the ability of a material to
repair cracks that occur by reducing the width of the crack to increase the durability and mechanical properties of the material [20,21].
It was found that fly ash-based geopolymer paste can produce a lot of micro-cracks under load [22]. Materials that can be used to
correct this deficiency are crystalline admixtures (CAs) because of their properties that can work to repair the cracks that occur. Its
main content of calcium and silica is very suitable when combined with other materials.
However, the use of nano-silica based on rice husk ash combined with CAs for compressive strength, flexural strength, and fracture
toughness has not been reported yet. For this reason, in this study, the effects of different content of nano-silica and CAs at concen­
trations of 3%, 4%, and 5% wt% were studied. On this basis, the effect of nano-silica synthesized in the laboratory using the sol-gel
method and CAs on bulk density and flow behavior of fresh geopolymer paste, compressive strength, flexural strength, fracture
toughness, and microstructure was studied. The results obtained are very useful for the practitioners for the understanding and
implementing this material in the future.

2. Materials and methods

2.1. Materials

The material used in this study is fly ash was taken from a power plant located in Nagan Raya District, Aceh, Indonesia. Rice husk
ash (RHA) was collected from the community’s rice mill. Rice husk ash is used to synthesize nano-silica. The chemical composition of
the nano-silica produced in the laboratory, fly ash, CAs and other references is shown in Table 1. Crystalline admixtures (CAs) were
purchased under the brand name Pentens T-308. The physical properties of the materials used are shown in Table 2.

Table 1
Chemical composition of nano-silica gel, fly ash, CAs and other references.
Chemical composition (%) Nano-silica Fly ash [23] CAs Nano-silica [24] Fly ash [25] CAs [26]

SiO2 81.41 21.07 10.33 96.59 63.13 8.10

Fe2O3 0.16 27.23 1.53 0.11 3.07 2.08
CaO 1.94 32.58 49.61 0.02 2.58 59.77
Mno 0.12 0.44 0.58 < 0.01 – –
K2 O 1.8 1.17 0.26 0.04 2.01 0.44
SO3 8.39 5.69 2.71 0.18 2.09
Cl 2.63 0.22 – – –
Ag2O 0.6 0.23 – – –
Al2O3 – 9.65 3.46 < 0.01 24.88 1.98
TiO2 – 1.68 – 0.03 – –
Yb2O3 – 0.06 – – –
Na2O – – 3.51 2.16 0.71 1.29

Table 2
Physical properties of the material.
Physical properties Materials/ Value

Fly ash RHA CAs

Color gray white gray

Average size 30 µm – 50 µm
Specific gravity 2.45 1.12 2.53

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2.2. Microstructure characterization

SEM image of fly ash and grain size analysis are shown in Fig. 1(a and b). SEM microstructural investigation of fly ash showed that
the shape of all fly ash particles are not round and tends to be irregular. This will have an impact on increasing the internal friction,
increasing the absorption ability and fluid demand. Therefore, in this study, the amount of liquid solution was increased to obtain a
good geopolymer paste workability.
SEM image and XRD analysis of the CAs material are shown in Fig. 2(a–b). CAs show a nearly crystalline form and indicate the
presence of calcite (CaCO3) and quartz (SiO2) minerals. The minerals are contained following the results of chemical composition
testing, where CAs contain 49.61% of CaO and 10.33% of SiO2.

2.3. Synthesis of nano-silica

Nano-silica from rice husk ash was synthesized by the sol-gel method. The sol-gel method is the process of converting sodium
silicate solution into a gel using a strong acid, and this method has been suggested by many researchers [27–29]. 100 g of RHA was
reacted with 60 mL of 1 N NaOH at 90 ◦ C for 1 h. Then filtering was carried out and finally, from the filtering process, 100 mL of warm
aquadest was added. Then 1 N HCl was added until the pH of the solution became 7. The gel formed was washed with distilled water
and filtered again to remove the remaining Cl-. The nano-silica gel was kept at room temperature for 18 h before used in geopolymer
pastes.

2.4. Preparation of geopolymer paste containing nano-silica

Geopolymer pastes were prepared by mixing alkaline solutions, fly ash, nano-silica, and CAs. The alkaline solution was composed of
10 M NaOH with NaOH/Na2SiO3 = 1, and the alkali/binder used ratio was 1:0.4. The 10 M NaOH solution was prepared by dissolving
40 g of NaOH in 100 mL of distilled water. The percentage of nano-silica synthesized in the laboratory was 0, 3%, 4%, and 5% by
weight of fly ash. Likewise, CAs were used at 0, 3%, 4%, and 5% by weight of fly ash. All ingredients are stirred evenly for 25 min. The

Fig. 1. Microstructure and gradation of fly ash (a) SEM image and (b) Grain size analysis.

Fig. 2. Microstructure of CAs (a) SEM image and (b) XRD spectra.

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Table 3
Mix proportion of geopolymer pastes with nano-silica and CAs.
Code Fly ash (g) NaOH (g) Water (mL) Na2SiO3 (g) Nano-silica (g) Nano-silica content (%) CAs (g) CAs content (%)

Geo-0 1000 260 650 260 0 0 0 0

Geo-1 970 260 650 260 30 3 30 3
Geo-2 960 260 650 260 40 4 40 4
Geo-3 950 260 650 260 50 5 50 5

mixing method is carried out as suggested [30]. After forming the pastes, the mixture was poured into a 50 mm × 50 mm x 50 mm
cube and 40 mm × 40 mm x 40 mm prism molds. After 24 h, the geopolymer pastes were removed from the mold and cured at room
temperature of 23 ◦ C ± 2 ◦ C. The specimens were covered with plastic sheets to maintain the treatment temperature and avoid
moisture loss. Table 3 shows the mix proportion of each ingredient used.

2.5. Testing procedures

2.5.1. Fresh properties of geopolymer paste

After preparing the geopolymer paste, flow was measured using a mini-cone test. This test was carried out according to ASTM: C-
1437 [31]. This test is based on the fact that if the shear stress in the fresh paste being tested is less than the yield stress, no flow occurs
[32–34]. Yield stress of the pastes was calculated using Eq. (1) as suggested by [35].

225. ρgV 2
τ0 = (1)
128. π2 R5

Where ρ is the density of fresh pasta, g is gravity, V is the volume of pasta, and R is the slump measured.

2.5.2. Mechanical properties of geopolymer paste

Testing of all specimens was carried out when the specimens were 28 days old. For each measured properties three specimens were
repeated. The display of the testing machine and the test schematic is shown in Fig. 3.
A three-point bending test was carried out using hydraulic testing machines (VB50-300). The prism specimen was placed on two
supports and the load was applied in the middle of the beam. Tests were carried out according to ASTM D5054 - 14 [36] with the
testing machine and schematic are shown in Fig. 4.
The flexural strength (σF) calculated from formulation (2), where Pm is the maximum load applied, S is the distance between the
support, B is the specimen width, and W is the specimen thickness. Fracture toughness (KQ) calculated from formulation (3) and (4)
based on the standard of ASTM D5045 - 14, where PQ is the maximum load and ƒ(x) is the polynomial correction factor with x = a/W.
Crack length (notch) is denoted by (a) of 20 mm according to Fig. 4(b) with a/W = 0.5.

3 Pm S
σF = (2)
2 BW 2
( )
PQ
KQ = f (x) (3)
BW 1/2

[1.99 – x(1–x)(2.15–3.93x + 2.7x2 )]

f (x) = 6x1/2 (4)
(1 + 2x)(1–x)3/2

Fig. 3. Test set-up for compressive strength (a) Testing machine and (b) Schematic of testing.

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Fig. 4. Test set-up for flexural strength and fracture toughness (a) Three-point bending test testing machine and (b) Schematic of testing.

2.5.3. Microstructure analysis

The bonding performances of nano-silica and CAs in the geopolymer matrix were evaluated by SEM Vega 3-Tescan (Czech Re­
public). The mineral composition was determined by XRD analysis using the Shimadzu XRD-7000 (Japan). The spectrum used is
1017–1020 Hz with an energy of 103–106 eV. The characteristic peaks of Si–O–Si, Al–O–Si, and O–H functional groups were tested
used FTIR (Shimadzu-IRPrestige-21) with wavenumbers 4000–400 cm− 1. The particle size of the resulting nano-silica was tested with
a Particle Size Analyzer (PSA).

3. Results and discussion

3.1. Nano-silica characterization

Table 1 shows the chemical composition of the nano-silica produced in the laboratory. The main composition of SiO2 is 81.41%.
The amount of silica produced in this study is less than the commercial silica and the one produced by other researchers such as El-
Didamony et al. [35] by 96.8%, Akhayere, Kavaz, and Vaseashta [36] by 94.1%, and Ugheoke and Mamat [37] by 98.9%. Fig. 5(a), (b)
shows photo of nano-silica and particle size distribution of the resulting nano-silica gel. In the figure, the resulting nano-silica gel is
white and shows an average grain size of 325.4 nm.
The nano-silica produced from the alkalization process by the sol-gel method is more homogeneous in size and well dispersed
compared to the nano-silica from the milling process as has been done in the previous study [17]. This result was also confirmed from
particle size analysis testing where the particle size is ranged from 193.48 to 655.76 nm with an average size of 325.4 nm. TEM images
of nano-silica are shown in Fig. 6.
Fig. 7 shows the diffraction pattern of nano-silica found in XRD analysis. The nano-silica obtained by the sol-gel method has
amorphous properties, which is indicated by a peak of 2Ɵ = 22.18◦ . This is following several previous studies which confirmed that
the silica synthesized from rice husk ash has an amorphous structure [37–40].
Fig. 8 shows the nano-silica functional groups produced through a laboratory process. The spectrum and peak intensity at
3334.92 cm− 1 indicate the presence of hydrogen bonds which are O–H and Si–OH molecules [41,42]. This bond is obtained from the
concentration of NaOH and the degradation of the amorphous part of the rice husk ash and becomes silica gel. The peak intensity at
655.80 cm− 1 shows the occurrence of Si–O–Si bonds which are the main component of silica gel [43,44]. The Si–O–Si bonds are
spread from 447.49 to 655.80 cm− 1. The peak intensity at 2112.05 cm− 1 indicates the presence of an alkaline group on the surface of
silica gel [45]. Peak intensity also appears at wave 1635.64 cm− 1 due to bending and stretching of water and silanol –OH [46,47] and
confirms that the resulting silica gel is hydrophilic surface [41]. FTIR analysis showed that nano-silica was successfully synthesized and
could be used for geopolymer cement composites.

3.2. Bulk density and flow behavior of fresh geopolymer paste

Fig. 9 shows the effect of nano-silica and CAs on bulk density of geopolymer paste. Bulk density values obtained for the composites
of each specimen were 1.45, 1.47, 1.52, 1.53 g/cm3. Bulk density showed an increase with the addition of nano-silica and CAs con­
centrations. Bulk density for geopolymer paste is ranged from 1400 to 1710 g/cm3 [48]. The increase that occurred ranged from 1.46%
to 5.32% of the control geopolymer. This indicates that the matrix is more compact after the addition of nano-silica and CAs. In alkaline
solution, nano-silica and CAs can increase calcium silicate hydrates (C–S–H) and form a three-dimensional network structure of silica
oxide tetrahedron and aluminum oxide tetrahedron [49]. This three-dimensional structure also contributes to increasing the
compressive strength [20]. The increase in bulk density does not always increase the compressive strength because there are still fly
ash particles that do not react to produce C–S–H in the matrix. However, due to the addition of silica from nano-silica and calcium from
CAs the density is increased.
Fig. 10 and Table 4 show the diameters of the mini-slump test and the yield stress values on the geopolymer paste with the addition

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Case Studies in Construction Materials 16 (2022) e00792

Fig. 5. Nano-silica characterization (a) Photo of nano-silica gel and (b) Particle distribution.
A.R. Alvee et al. Case Studies in Construction Materials 16 (2022) e00792

Fig. 6. TEM image of nano-silica gel with different scale bar (a) 20 nm, (b) 50 nm, and (c) 100 nm.

Fig. 7. XRD pattern of nano-silica.

Fig. 8. FTIR spectrum of nano-silica synthesized using sol-gel method.

of nano-silica and CAs of 0, 3%, 4%, and 5%. Yield stress τ0 is the stress required to break the interaction and separation of the particles
[32,33,35]. The yield stress values were 1.19, 1.75, 1.94, and 1.95 Pa, respectively for the Geo-0, Geo-1, Geo-2, and Geo-3 mixes. The
addition of nano-silica and CAs by 3%, 4%, and 5% increased the yield stress by 46.75%, 62.76%, and 64.20%, respectively. This is
because the viscosity value is increased, it turns out that the calcium in CAs changes the viscosity of fresh pasta to be thicker. CAs
absorb alkaline solutions.
In geopolymer paste, the interactions occur between particles through colloidal forces, such as Van der Waals, hydrogen bonds, and

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Fig. 9. Increase in bulk density of geopolymer cement with nano-silica and CAs.

Fig. 10. Flow test of geopolymer pastes with nano-silica and CAs (a) Measurement and (b) Results of yield stress.

Table 4
Results of the diameter of the mini-slump test and yield stress on geopolymer paste.
Specimen Diameter (m) τ0 (Pa)
Geo-0 0.169 ± 0.81 1.19 ± 0.27
Geo-1 0.157 ± 0.35 1.75 ± 0.20
Geo-2 0.154 ± 0.21 1.94 ± 0.13
Geo-3 0.154 ± 0.49 1.95 ± 0.30

particle interactions through friction or collisions [34]. The –OH group present in nano-silica and CAs provide hydrogen bond in­
teractions with fly ash and alkaline solutions. The increase in τ0 produced by the addition of nano-silica and CAs made the geopolymer
paste not flow easily (too dilute) [34]. The yield stress value obtained is following the research (Roussel et al. [35]) carried out on
Portland cement and study by (Gómez Hoyos et al. [34]) at 0–3 wt% of cellulose microcrystalline ranging from
0.55 ± 0.01–1.43 ± 0.02 Pa.

Fig. 11. Effect of addition of nano-silica and CAs on compressive strength and flexural strength of geopolymer pastes measured at 28 days.

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3.3. Compressive and flexural strengths

The results of the compressive strength of geopolymer pastes measured at 28 days with the addition of nano-silica and CAs are
shown in Fig. 11. The addition of nano-silica and CAs to the Geo-1, Geo-2, and Geo-3 mixes increased the compressive strength to
17.77, 22.17, and 22.69 MPa, respectively. The compressive strength is increased by 4.67%, 30.60%, and 33.63% due to the addition
of 3%, 4%, and 5% nano-silica and CAs, respectively.
In Fig. 11, it can be seen that the maximum increase in compressive strength is occurred with the addition of nano-silica and CAs of
5% each. This increase occurred because the CaCO3 contained in CAs worked as self-healing and continued to repair the micro-cracks
and pores that occurred in the geopolymer paste. Meanwhile, nano-silica plays a role in increasing the C–S–H gel needed in geopolymer
paste. The increase in compressive strength with the addition of nano-silica was also reported by other studies [17,50,51]. The addition
of nano-silica as a partial replacement of fly ash exhibited beneficial effect because nano-silica can increase the amorphous silica
content that is less in fly ash. An increase in compressive strength with the addition of CAs was also reported by others [18,26,52,53].
There was also an increase in flexural strength due to the addition of nano-silica and CAs as shown in Fig. 12 (a and b). Flexural
strength obtained was 0.91, 1.07, 2.72, and 3.02 MPa, respectively for the addition of nano-silica and CAs of 0, 3%, 4%, 5% as a partial
replacement of fly ash. This increase is due to the nano-silica produced by the sol-gel method which is amorphous, can react and form
C–S–H or C–A–S–H and N–A–S–H gels. These gels play a role to increase the mechanical properties of geopolymer paste [54,55].

3.4. Fracture toughness

The fracture toughness values obtained in this study are shown in Fig. 13. A significant increase is occurred in fracture toughness,
where the combined addition of nano-silica and CAs to the Geo-1, Geo-2, Geo-3 pastes yielded their respective values of 0.37, 0.96, and
1.07 MPa.m1/2. The percentage increase that occurred was 1.2, 3.0, 3.3 times for the combined addition of nano-silica and CAs of 3%,
4%, and 5%, respectively compared to the control specimen.
Fig. 13 shows the same trend of increasing flexural strength and fracture toughness. Crystalline admixture is believed to be able to
increase the fracture toughness, energy of fractured deflection of particles, and matrix with its self-healing property. In fracture
toughness, it is believed that CAs have good dispersion throughout the matrix and can resist crack propagation. Nano particles in nano-
silica are believed to be able to improve the microstructure of geopolymer nanocomposites [56,57]. The combined use of these two
materials plays a role and influences fracture toughness.

3.5. Microstructure of geopolymer paste

3.5.1. X-ray diffraction (XRD) analysis

XRD patterns of geopolymer paste with the addition of nano-silica and CAs are shown in Fig. 14. The diffraction spectra analysis
indicates the Quartz (Q) of crystalline peaks at 15–35◦ . The picture shows a decrease in peak when compared to the diffraction spectra
of the initial materials, which are nano-silica and CAs. All geopolymer paste specimens had the same diffraction pattern and showed no
significant change from the control samples, except for Geo-3 paste with 4% nano-silica and CAs where kyanite and quartz were still
present. The quartz, mullite, and calcite peaks of the initial materials were observed to almost disappear, indicating the degree of
geopolymerization. The XRD pattern shows that the quartz content was detected most clearly at 2Ɵ around 26.4–27◦ . Quartz content
which was also detected at 50◦ and 60◦ showed the highest amount of crystallinity and had higher compressive strength. [58]. Fly
ash-based geopolymer with crystallinity intensity will contribute to the highest compressive strength [58,59]. Other minerals that
emerged as a result of the reaction of fly ash containing Mg with nano-silica and CAs gave rise to the mineral Mullite (Al6O13Si2) which
was detected at 2Ɵ = 24.1◦ and the aluminosilicate mineral (Al2SiO5) at 2Ɵ = 32.3◦ [60,61].

3.5.2. Scanning electron microscopy (SEM)

The characterization of the microstructure of the geopolymer paste with nano-silica and CAs is shown in Fig. 15. The character­
ization of the microstructure of the material with CAs shows better performance and the hydration product is denser than the control
specimen (Geo-0). Microstructural investigation of the Geo-3 specimen showed an increase in C–S–H gel and CaCO3 because CaCO3 is a
self-healing product. The addition of nano-silica and CAs as seen in Fig. 5(e–h) showed an increase in the formation of C–S–H and
CaCO3 gels in the specimen. The addition of nano-silica and CAs made the geopolymer stronger.

3.5.3. FTIR analysis

The FTIR spectra of the nano-silica composite samples and CAs are shown in Fig. 16. The characteristic bands are shown in Table 5.
The most important bands which indicate the presence of asymmetric stretching of Si–O–T (Si– – Al or Si) confirm the presence of
C–A–S–H and N–A–S–H geopolymer bonds [62–65]. This band appeared at 970–974 cm− 1. This indicates that the silica contained in
the nano-silica and CAs have dissolved and reacted to form a geopolymer gel. In the Geo-3 sample, this band appeared to be higher
which indicates a higher degree of geopolymerization so that the mechanical strength also shows better results. These characteristic
bands are following compressive strength and flexural strength results which show an increase in strength. The bands at
1428–1431 cm− 1 belong to vibrations of O–C–O in carbonate compounds resulting from the unreacted alkalies. The bonds that occur
are carbon-oxygen bonds of CH and calcium carbonate (CaCO3) [66]. In this vibration, calcium-silicate-hydroxide crystals are formed.
CaCO3 and C–S–H in this spectra also contributed to the increase in mechanical properties. The absorption bands at 3271–3278 cm− 1
were due to the presence of O–H groups and bending vibrations of chemically bonded water molecules in the geopolymer paste

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Fig. 12. (a) Relationship of force and deflection on flexural strength testing and (b) Value of flexural strength on specimens.

Fig. 13. Fracture toughness and flexural strength of geopolymer paste with the addition of nano-silica and CAs.

Fig. 14. XRD pattern of geopolymer paste with nano-silica and CAs.

[67–69]. The FTIR spectra show that nano-silica and CAs have an effect in forming functional groups that increased mechanical
strength.

4. Conclusion

This research studied the influence of nano-silica and Crystalline Admixture (CAs) on the mechanical properties and microstructure
of geopolymer pastes. From the experimental results, conclusions could be drawn as follows:

1. The characteristics of nano-silica show good properties when combined with CAs and are suitable for use as geopolymer paste raw
materials.

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(caption on next page)

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Fig. 15. Microstructural morphology of geopolymer paste with nano-silica and CAs composites; (a,b) Geo-0, (c,d) Geo-1, (e,f) Geo-2, (g,h) Geo-3.

Fig. 16. FTIR spectra of the geopolymer paste with nano-silica and CAs composites.

Table 5
Characteristic bands of FTIR spectra from geopolymer paste with nano-silica composite and CAs.
Specimen Characteristic band (Wavenumber cm¡1)

a b c

Geo-0 970 1428 3278

Geo-1 972 1429 3278
Geo-2 974 1431 3273
Geo-3 974 1431 3271
Characteristic bands Si–O–Si and Si–O–Al stretching O–C–O stretching O–H stretching
References [62–65] [66] [67–69]

2. The addition of nano-silica and CAs by 5% increased the bulk density and yield stress by 5.32% and 64.20%, respectively, and
changed the viscosity of the fresh paste (become more viscous).
3. Meanwhile, the increase in compressive strength and flexural strength also shows the same trend. The addition of nano-silica and
CAs increased the experimental pastes compressive strength up to 33.63% and increased flexural strength and fracture toughness
up to 232.69% compared to control pastes.
4. The microstructure analysis confirmed the presence of C–S–H gel and CaCO3, which are self-healing products. FTIR transmission
spectra also show the results of the formation of Si–O–Al and Si–O–Si bonds which are geopolymerization gels. The increase in
the bonding intensity of a calcium-silicate-hydroxide gel and CaCO3 crystals indicates an increase in self-healing products of CAs,
which causes an increase in mechanical strength.
5. In the present study, it can be concluded that the nano-silica synthesized in the laboratory can increase the C–S–H gels and syn­
ergize with self-healing CAs in increasing the compressive strength, flexural strength, and fracture toughness, and densifying the
microstructure.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Acknowledgments

The author would like to thank the Ministry of Education, Culture, Research and Technology at the 2021 Student Creativity
Program (PKM) with contract number 45/LL13/PKM/2021.

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