Journal of Cleaner Production 280 (2021) 124293

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Compressive strength, modulus of elasticity and hardness of

geopolymeric cement synthetized from non-calcined natural kaolin
Fernando Pelisser Prof., Dr. Eng. (Fernando) a, *,
Adriano Michael Bernardin Prof., Dr. Eng. (Adriano) b,
Milton Domingos Michel Prof., Dr. Eng. (Milton) c,
Caroline Angulski da Luz Prof., Dr. Eng. (Caroline) d
a polis, Santa Catarina, Brazil
Civil Engineering Department, Federal University of Santa Catarina, 88040-900, Floriano
b
Graduation Program on Materials Science and Engineering, University of the Extreme South of Santa Catarina, 88806-000, Criciúma, Santa Catarina,
Brazil
c
Materials Engineering Department, State University of Ponta Grossa, 84030-900, Ponta Grossa, Parana , Brazil
d , 85501-970, Pato Branco, Parana
Civil Engineering Department, Federal Technological University of Parana , Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a natural non-calcined kaolin was used for the synthesis of a geopolymeric paste. The effect
Received 11 April 2020 of the natural kaolin characteristics and the alkaline activator ratio (Na2O.SiO2/NaOH) on the mechanical
Received in revised form behavior of the resulting geopolymeric cement was determined. The chemical and mineral composition
24 August 2020
of the kaolin were determined by XRF and XRD techniques. For the synthesis, sodium silicate and sodium
Accepted 16 September 2020
hydroxide were used in molar ratios of Na2O.SiO2/NaOH ¼ 1.0, 1.6 and 2.2 and the curing of the samples
Available online 24 September 2020
was performed at 40  C. The compressive strength of the samples was evaluated at 7 and 28 days of age.
Handling editor: Prof. Jiri Jaromir Klemes The modulus of elasticity and hardness were determined by instrumented nanoindentation. Micro-
structural analysis (SEM) combined with chemical analysis (EDS) was performed to study the
Keywords: morphology of the geopolymeric cement samples. The results showed that the natural kaolin is 95%
Geopolymeric cements amorphous (Rietveld) and shows small particle size (<5 mm, by SEM). The most efficient composition,
Natural kaolin with Na2O.SiO2/NaOH ¼ 2.2 ratio, showed a modulus of elasticity of 10 GPa, hardness of 0.4 GPa and
Sustainable materials compressive strength of 67 MPa. In the microstructural analysis, the surface of the samples showed some
Green cements
cracks, probably caused by the curing process, and small roughness, but the cured specimens did not
show visible flaws. The high strength is due to the chemical composition of the cement, with a SiO2/Al2O3
ratio of 3.5, and due to the degree of amorphism of the natural kaolin, 95%. Therefore, the use of a natural
kaolin, without further calcination, reduces costs and environmental impacts in the design of geo-
polymeric cements.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction Geopolymers are also known as alkali-activated materials, whose

use may contribute to the reduction of carbon footprint in the
The growing demand for concretes showing high-efficiency, building industry (Provis, 2013; Shia et al., 2019; Singh and
low-cost and low environmental impact, especially when Middendorf, 2020). The study of alkali-activated cements (AACs)
compared to ordinary Portland cement (OPC) concretes, has pro- is growing fast in the global research community (Provis et al.,
moted the development of clinker-free cementitious materials, 2015; Gartner and Sui, 2018).
including geopolymeric cements (Tan et al., 2020; Assi et al., 2020). The study of AACs can be considered as a challenging research
area with economic and environmental impacts. These cements can
be produced using a wide variety of raw materials (Provis et al.,
2015; Firdous et al., 2018; Shia et al., 2019), and industrial waste
* Corresponding author.
E-mail addresses: f.pelisser@ufsc.br (F. Pelisser), amb@unesc.net (Longhi et al., 2016; Tan et al., 2020; Assi et al., 2020), as they do not
(A.M. Bernardin), mdmichel@uepg.br (M.D. Michel), angulski@utfpr.edu.br require materials with a high degree of purity and uniformity. The
(C.A. da Luz).

https://doi.org/10.1016/j.jclepro.2020.124293
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

AACs show low cost of energy consumption and low emission of the mechanical properties of the produced cements, considering
carbon dioxide (CO2). AACs produced from fly ash, blast furnace the effect of the alkaline activator ratio (Na2O.SiO2/NaOH).
slag and natural pozzolans can reach up to 80% reduction of CO2 The novelty of the work is the use of a natural kaolin for the
emissions in comparison to Portland cement (Van Deventer, Provis synthesis of a geopolymeric composition. Usually, for the synthesis
and Duxson, 2012; Bajpai et al., 2020; Amran et al., 2020). of geopolymers, calcined kaolin is used to obtain metakaolin (MK).
In this way, the use of geopolymers in construction projects can MK is used because it is a metastable, non-crystalline and reactive
contribute to the reduction of CO2 emissions (carbon footprint). As mineral phase. However, is this work, a natural occurring, non-
stated, geopolymeric cements generally show lower CO2 emissions crystalline (95% amorphous) and fine (<5 mm particle size, by
e when compared to ordinary Portland cements e due to two main SEM image) kaolin was used instead of a calcined MK for the syn-
reasons. First, industrial residues can be used as raw materials, thesis of a geopolymeric composition. The mechanical behavior of
giving an adequate destination to them. And the standard meta- the composition was determined by compressive strength tests and
kaolin used for the synthesis of geopolymers is calcined at much by nanoindentation tests.
lower temperatures (700  C) than Portland cement (1450  C).
Second, there is much less emission of CO2 when preparing the 2. Materials and methods
geopolymeric cement in comparison with the decarbonation of
limestone during the production of clinker for the manufacturing of The materials used for the composition of the geopolymeric
Portland cement, thus resulting in lower CO2 emissions and energy cements were: a) natural kaolin, supplied by Esmalglass do Brasil
expenditure in the process. Some works show that the energy spent company; b) sodium silicate, from Sigma-Aldrich (SiO2 ¼ 26.5%,
to produce one ton of metakaolin is approximately 2.95 GJ, against Na2O ¼ 10.6%, and H2O ¼ 63.0%); and c) sodium hydroxide, from F
approximately 4.7 GJ for Portland cement. Approximately 175 kg of Maia company (NaOH ¼ 97%). The concentrations of the alkaline
CO2 is emitted into the atmosphere due to the production of met- activator were determined, by molar ratio, as 2.2 for K1 composi-
akaolin (Cassagnabe re et al., 2010; Bajpai et al., 2020; Amran et al., tion, 1.6 for K2 composition and 1.0 for K3 composition (Table 1).
2020) in comparison to what is emitted for clinker production To prepare the mixtures (K1, K2 and K3) of the geopolymeric
(800 kg of CO2/ton). cements, the following procedure was adopted: i) pellets of sodium
Although the work of Turner and Collins (2013), considering all hydroxide (97%) were added into the sodium silicate solution in
manufacturing and application processes, do not show this molar ratios given in Table 1, and the solutions were mixed in a
advantage, such differences depend on several factors, ranging magnetic stirrer; ii) kaolin was added to the alkaline solutions using
from the quality and costs of the starting materials in some places, a mechanical mixer; the mixing was performed for 4 min; iii) the
until the composition, production and performance of the obtained mixtures were cast into cylindrical molds (2 cm height and 4 cm
geopolymeric concretes (Medri et al., 2020; Ng et al., 2018). How- diameter) and the temperature of curing (setting) was fixed at
ever, some studies show the economic viability to produce geo- 40  C. The mixing procedure and a detail of a sample after
polymeric cements, reaching values of approximately US$ 150 per demolding is shown in Fig. 1.
cubic meter (Ozel, 2012; Shia et al., 2019; Gartner and Sui, 2018), Table 1 shows the composition of the geopolymeric cements
even considering the current restricted demand. Despite the according to the SiO2/Na2O, SiO2/Al2O3, Na2O/Al2O3 and Na2O.SiO2/
excellent performance of Portland cement in the production of NaOH ratios. The water/kaolin ratio was fixed at H2O/kaolin ¼ 0.75
concretes and mortars, the geopolymeric cements show competi- for each composition, according to the original amount of water in
tive mechanical properties and satisfactory durability (Ng et al., the sodium silicate solution. The Na2O.SiO2/NaOH ratio was ranged
2018; Firdous et al., 2018; Singh and Middendorf, 2020). considering previous mechanical results with better performance
Geopolymers are a three-dimensional network of aluminosili- (Pelisser et al., 2013), and references in the literature of existing
cates, amorphous in nature and with a semicrystalline structure. relationships to obtain better polymerization (Davidovits, 1991;
Their empirical formula can be described by: Mn[-(SiO2)z-AlO2]n.- Cassagnabe re et al., 2010; Heah et al., 2012).
wH2O, where z is 1, 2 or 3, M is an alkali metal cation, an n is the The compressive strength was determined according to the
degree of polycondensation (Davidovits, 1991; Gartner and Sui, ASTM C 1231(2010) standard and the specimens were tested at 7
2018). The complex structure of the geopolymeric system consists and 28 days of age using 3 replicates for each sample. A universal
of chains, sheets and three-dimensional networks formed by testing machine (EMIC DL 10000, Brazil) was used with a loading
several types of Q units of connected SiO4 and AlO4 tetrahedra. As a rate of 0.5 MPa/s.
source of aluminosilicates, many types of calcined clays can be used For the nanomechanical tests, an XP nanoindentator (MTS Sys-
for cement production, among which, metakaolin is frequently tem, USA) was used. The modulus of elasticity (E) and hardness (H)
used (Medri et al., 2020). were determined using a Berkovich tip.
Even if the chemical composition of the raw materials used in The procedure for the nanoindentation technique is the
the synthesis is an important factor in the performance of the controlled penetration of a diamond tip into the surface of the
geopolymeric cement, Reddy et al. (2016) showed, through a data material and the recording of the charge and depth of penetration,
search, that the best results of compressive strength were found for at a nanoscale. The maximum load is held constant for a few sec-
a chemical composition varying from 45 to 55% of SiO2, 22e28% of onds and then removed. The time, in seconds, is controlled in three
Al2O3 and 15e20% of Na2O. The authors also showed that, even stages: on loading, on full load and on unloading. The data is shown
considering the best performance range, there is a very large dif-
ference of the obtained results, as an example, for the compressive
strength, with a range of 20e60 MPa for very similar chemical Table 1
Composition, by molar ratio, of the geopolymeric cements.
compositions. Indeed, this effect is due to the reactivity of the
starting materials, that relies on the processing techniques and on Composition K1 K2 K3
the characteristics of the clay minerals used as raw materials (Ma SiO2/Na2O 6.41 6.41 6.41
et al., 2018; Medri et al., 2020; Zhang et al., 2020). SiO2/Al2O3 3.47 3.47 3.47
Therefore, this work aimed at evaluating the potential use of a Na2O/Al2O3 0.54 0.54 0.54
natural kaolin, originally used by the ceramic industry, without Na2O.SiO2/NaOH 2.20 1.60 1.00
H2O/kaolin (g/g) 0.75 0.75 0.75
calcination, to produce geopolymeric cements. The study evaluated
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F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Fig. 1. (a) Mixing procedure for the preparation of the geopolymeric samples; (b) detail of a geopolymeric sample after demolding.

as a, which describes the charge-discharge characteristic of the 4  4 points (distancing 50 mm from each other) under 2, 4, 8, 16,
material. and 32 mN loading cycles. The loading cycle was applied for 10 s,
The modulus of elasticity (E) and the hardness (H) were deter- the maximum load was kept for 5 s and the unloading was per-
mined from the load-displacement diagrams (P-h) for each sample, formed in 10 s.
according to equations (1) and (2) (Oliver and Pharr, 1992, 2004). Scanning electron microscopy and elemental microanalysis
The hardness (H) of the samples were determined by: (SEM/EDS) (Shimadzu SSX-550, Japan) was performed on the
indented regions to determine differences in morphology and in
Pmax chemical composition. The tests were performed on polished
H¼ (1)
Aðhc Þ samples of 1 cm in diameter and 5e6 mm thickness.
Chemical analysis was performed using the X-ray fluorescence
where Pmax is the maximum load and A(hc) is the projected contact technique in a S2 Ranger (Bruker, USA) analyzer on molten samples.
area considering the effect of the Berkovich tip. Crystallographic analysis was performed by X-ray diffraction in a
The modulus of elasticity (E) of the samples was determined by D2 Phaser (Bruker, USA) using powdered samples (2q from 10 to
(Brotzen, 1994): 80 , 2 /min scanning rate, 30 kV and 30 mA acceleration voltage
and CuKa1 incident radiation with l ¼ 1,5406 Å).
1  v2
E¼
 (2)
1  1v
2
3. Results and discussion
Er Ei

The chemical analysis of the natural kaolin is shown in Table 2.

where, Er is the reduced modulus of elasticity, Ei and n are the The kaolin shows a SiO2/Al2O3 ratio of 1.19. Comparing to a pure
modulus of elasticity and Poisson ratio of the indenter, and E and n kaolinite sample (Al2O3.2SiO2.2H2O) that shows as stoichiometric
are the modulus of elasticity and Poisson ratio of the sample, composition 39.5% Al2O3, 46.5% SiO2 and 14% H2O, the sample of
respectively. For a diamond tip, Ei ¼ 1141 GPa and ni ¼ 0.07 (Oliver kaolin used in this study is very pure, with low contamination. Ng
and Pharr, 1992, 2004). et al. (2018), in their review about pastes, mortars and concrete
And the reduced modulus of elasticity (Er) can be determined by geopolymers, comment on the chemical composition of natural
(Sneddon, 1965; Oliver and Pharr, 1992, 2004): raw materials used to produce geopolymeric cements. The chemi-
pffiffiffi cal composition of the natural kaolin from this work is similar to
p S
Er ¼ pffiffiffiffiffiffiffiffiffiffiffiffi (3) that of kaolin and calcined kaolin from the review. Silica an alumina
2b Aðhc Þ are the main oxides and the loss on ignition is due to the dihy-
droxylation. The chemical composition is also similar to some
where S ¼ (dP/dh) is the stiffness of the sample determined from source materials described by Assi et al. (2020).
the upper part of the unloading curve, and b is a constant, depen- The X-ray diffractometry of the natural kaolin is shown in Fig. 2.
dent on the indenter geometry, equal to 1.034 for a triangular In the XRD spectrum, an amorphous halo can be observed between
symmetry (Oliver and Pharr, 1992; Brotzen, 1994). 15 and 35 , characterizing the disordered nature of the sample
For the nanomechanical tests, samples with 5 mm thickness (Fig. 2). A peak at 27.5 is observed, ascribed to quartz (PDF file
were prepared using a low speed cutter (Buehler Isomet). The
samples surface was grinded using silicon carbide sandpaper (800
and 1200 grits). In sequence, polishing was performed using dia- Table 2
mond paste (6, 1 and 0.25 mm particle sizes) to obtain the surface Chemical composition of the natural kaolin (XRF).

finish. The samples were polished for 30 min in each diamond paste Oxide mass (%)
size. After grinding/polishing, the samples were cleaned in an ul- SiO2 46.7
trasonic bath (15 min) to remove the dust and diamond particles Al2O3 39.1
from the surface and pores. After preparation, the samples were Fe2O3 0.34
stored in a vacuum desiccator until testing. Sixteen indentations K2O 0.36
Loss on ignition 13.4
were made on the finished surface (testing area) in a pattern of
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F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Fig. 2. XRD spectrum of the natural kaolin.

number 00-046-1045), the only contamination of the sample. The the Al and Si from the aluminosilicate are dissolved by the alkaline
degree of amorphism of the kaolin sample is 95%, determined by solution and react to form complex hydroxyaluminosilicates. The
the Rietveld method. end product is the geopolymer, an alkaline aluminosilicate hydrate
The microstructure of the kaolin sample (SEM) by secondary (Na2O∙Al2O3∙2SiO2∙nH2O) with a three-dimensional structure that
electron (SE) image is shown in Fig. 3a. The particles are granular resembles zeolites on an atomic to nanometric scale (Davidovits,
and range from 1 to 5 mm. The backscattered electron (BSE) image is 1991; 2012; Firdous et al., 2018; Medri et al., 2020).
shown in Fig. 3b. Therefore, by the XRF, XRD and SEM analyzes, the The compressive strength of the geopolymeric compositions in
sample of kaolin used in this study is pure, with no contamination function of the concentrations of the activator, at the ages of 7 and
besides quartz, is amorphous in nature and shows a granular 28 days, is shown in Fig. 4. The best result, 67 MPa, was obtained for
texture. the composition K1 at 7 days of age, corresponding to the molar
The reaction mechanism when kaolin is added to the alkaline ratio Na2O.SiO2/NaOH ¼ 2.2. The compressive strength for the
solution is the alkaline activation of an aluminosilicate material. composition K2 (Na2O.SiO2/NaOH ¼ 1.6), 65 MPa, was close to K1.
When a solid with adequate ratio of reactive silicate and aluminate For the composition K3, with lower concentration of the alkaline
is mixed with a liquid with a high alkali concentration the geo- activator (1.0), a small reduction was observed (60 MPa). Firdous
polymerization process takes place. The polymerization process is et al. (2018) reviewed the use of natural pozzolans, mainly volca-
like the reactions that result in the formation of zeolites. Initially, nic ones, to produce geopolymeric systems. They stated that the

Fig. 3. Microstructure of the kaolin sample (SEM): (a) SE image; (b) BSE image.

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F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Fig. 4. Compressive strength of the geopolymeric compositions K1, K2 and K3 at the ages of 7 and 28 days.

main factors affecting the degree of geopolymerization are particle work, to verify the variation of the Na2O.SiO2/NaOH ratio on the
size, type and concentration of alkali activator, pre-treatment of strength of the geopolymeric cement, being therefore used the
raw material and curing conditions. For NaOH solutions, the three concentrations of NaOH.
compressive strength ranged from 27 to 43 MPa for concentrations In a recent study, Reddy et al. (2016) have investigated the effect
ranging from 2.5 to 10 M. The samples were cured at 40 and 60  C of the chemical composition on the mechanical performance of
and autoclaved. geopolymeric concretes. The chemical composition has a signifi-
These results are in accordance with the trend that higher cant influence on the compressive strength. For example, SiO2,
compressive strength is obtained when the Na2O.SiO2/NaOH ratio Al2O3 and CaO should be in the ranges of 45e55%, 22e28%, 15e20%,
is increased (Heah et al., 2012). A similar behavior is shown for a respectively, for the best results. However, small variations in
geopolymeric cement based on fly ash (Chindaprasirt et al., 2006), composition may exhibit large variations in strength. Although the
in which the optimum Na2O.SiO2/NaOH ratio for the maximum chemical composition points out the performance of the cement,
strength was found between 0.67 and 1.0. It must be stated that the the reactivity of the raw materials e given by the amorphous or
geopolymeric cement based on natural kaolin, in this work, shows crystalline nature of them e may explain those differences in
high compressive strength due to the amorphous nature of the strength. The geopolymeric compositions of this work are in the
material. The disordered structure of the starting material and the range studied by Reddy et al. (2016), considering the chemical
chemical composition of the mixtures can be considered the most composition of the raw materials and the geopolymeric cements
important factors for the design of a geopolymeric cement. (Table 3). Also, Davidovits (1991) and Rashad (2013) stated that a
In this work, the mechanical behavior of the geopolymeric ce- SiO2/Al2O3 molar ratio near 3 is optimal for the geopolymerization
ments synthetized with natural kaolin, determined by the nano- process. In this work, the SiO2/Al2O3 ratio is 3.0.
indentation method, was similar to that of Pelisser et al. (2013) for These results show that the XRD analysis, used to determine the
geopolymers produced with metakaolin, reaching a compressive amorphousness of the starting material, is an important quantita-
strength of 65 MPa. Geopolymeric cements showing compressive tive result for the use of different clay-minerals and industrial
strengths above 65 MPa are not usual. Longhi et al. (2016) reported wastes for the formulation of efficient geopolymeric cements.
geopolymeric compositions reaching 72 MPa of compressive In order to characterize the micro-nanomechanical behavior of
strength for a SiO2/Al2O3 molar ratio of 3.5, however, at 50  C curing
temperature, in comparison to 40  C used in this work.
Considering the Na2O.SiO2/NaOH ratio shown in Table 2 and the Table 3
Chemical analysis for compositions K1, K2 and K3, determined by EDS technique.
results of compressive strength shown in Fig. 4, the increase in this
a
ratio improved the compressive strength, and the maximum Elements Compositions (mass %)
strength was given for the intermediate ratio (K2 ¼ 1.6), but the K1 K2 K3
results for K1 and K2 are very similar. According to the literature, if
Si 44.6 30.5 42.6
the concentration of the alkaline activator increases, the polymer- Al 20.6 14.6 21.2
ization is more complete (Rashad, 2013; Reddy et al., 2016; Singh O 23.1 19.6 22.6
and Middendorf, 2020). But if there is an excess, it is impaired, Na 11.8 10.2 13.5
which is the case for the K3 ratio (¼ 2.2). This was the aim of the a
The Au element, from the sample preparation, was not considered.

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F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Fig. 5. (a) Modulus of elasticity and (b) hardness for the geopolymeric compositions K1, K2 and K3 in function of loading.

Fig. 6. Load-displacement curve for: (a) 2 mN loading; and (b) 2e32 mN loading, by nanoindentation, for cements with different Na2O.SiO2/NaOH ratios.

the geopolymeric cements, the modulus of elasticity and hardness The statistical analysis (ANOVA, 95% reliability) shows a non-
of the geopolymers were studied. The average results for the significant effect of the load used (2e32 mN). However, the
modulus of elasticity and for hardness are shown in Fig. 5 for the reduction of the modulus of elasticity with increasing load can be
compositions K1, K2 and K3. explained by the occurrence of microcracks during the loading and
The nanomechanical properties of the three geopolymeric ce- unloading cycles. It must be noted that the modulus of elasticity
ments were determined by 12 indentations. The modulus of elas- was measured during the unloading cycle, and the results were
ticity for all compositions ranged from 9.7 to 11 GPa for small recorded only in the elastic regime of the material.
loading (2 mN) until 10 GPa for higher loading (32 mN), Fig. 5a. The average and standard deviation for all 12 indentations
Regarding hardness, Fig. 5b, the variation was higher, ranging from performed on the geopolymeric cement with Na2O.SiO2/
0.4 GPa for composition K1 (2e32 mN range) to 0.6 GPa for NaOH ¼ 1.6 is shown in Table 4 for composition K2 in the load range
composition K3 at 2 mN loading. At higher loading (32 mN) the of 2e32 mN.
differences are small. SEM images of the surface where the indentation was per-
The displacement-load curves for all geopolymeric composi- formed for the composition K2 is show in Fig. 7. The surface is even
tions is shown in Fig. 6 for 2 mN loading and for the 2e32 mN and presents small roughness. An image of the nanoindentation
range. Differences in the modulus of elasticity are small and not matrix with 12 indentations is shown in Fig. 7a and the magnifi-
significant for small loading (2 mN) (Fig. 6a), as observed by the cation (4500) of the indentation area is shown in Fig. 7b. The
modulus of elasticity (Fig. 5a) curve. Differences are higher for micrographs show the homogeneity of the surface, resulting in the
higher loadings (8e32 mN), Fig. 6b, but are not significant. reliability of the measurements.

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F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Table 4
Modulus of elasticity (E, GPa) and hardness (H, GPa) for the 12 indentations performed on composition K2 (Na2O.SiO2/NaOH ¼ 1.6) in the load range of 2e32 mN. The data show
the average and standard deviation for each indentation.

Indentation Load (mN)

2 4 8 16 32 Average

E H E H E H E H E H E H

1 8.6 0.49 8.2 0.31 9.7 0.31 9.7 0.31 10.4 0.32 9.3 0.35
2 8.0 0.29 7.6 0.26 8.2 0.27 7.9 0.28 8.4 0.26 8.0 0.27
3 12.2 0.60 9.9 0.49 9.2 0.37 8.3 0.33 8.2 0.27 9.6 0.41
4 8.7 0.37 8.0 0.28 9.0 0.25 9.1 0.27 9.9 0.28 8.9 0.29
5 10.1 0.24 9.7 0.28 9.1 0.31 8.7 0.28 8.9 0.28 9.3 0.28
6 10.5 0.41 10.2 0.35 10.8 0.34 10.8 0.37 10.3 0.37 10.5 0.37
7 12.4 0.46 13.1 0.50 12.5 0.53 11.3 0.53 10.7 0.48 12.0 0.50
8 10.3 0.40 9.3 0.39 8.9 0.37 9.1 0.37 9.2 0.27 9.4 0.36
9 9.4 0.38 9.5 0.28 9.9 0.28 11.5 0.30 11.5 0.36 10.4 0.32
10 12.5 0.38 13.0 0.42 12.6 0.46 12.2 0.48 11.7 0.47 12.4 0.44
11 9.1 0.29 9.4 0.30 10.4 0.33 10.8 0.38 11.0 0.42 10.1 0.34
Average 10.2 0.39 9.8 0.35 10.0 0.35 10.0 0.35 10.0 0.34 10.2 0.39
S.D. 1.6 0.10 1.8 0.09 1.4 0.08 1.4 0.08 1.2 0.08 1.6 0.10

Fig. 7. SEM images of the surface of composition K2, Na2O.SiO2/NaOH ¼ 1.6: (a) image of the nanoindentation matrix with 12 indentations; (b) detail of one indentation.

The surfaces of compositions K1 and K3 are shown in the SEM The similarity between the mechanical behavior of both types of
images of Fig. 8. There are no significant differences in morphology cement e alkali-activated and CeSeH e enables the development
among all samples. The surfaces are even, with some cracks prob- of hybrid cements, a more efficient form of cement, as already
ably caused by the setting process and show small roughness. pointed out by Palomo et al. (2007). In general, the nanomechanical
A study on geopolymeric cements based on metakaolin and fly results are closer for hardness e for both cements e than for the
ash, activated with sodium silicate, showed results of modulus of modulus of elasticity, which shows a tendency to be lower, there-
elasticity e determined by nanoindentation e between 17 and fore typical of a more deformable material.
18 GPa (Nemecek et al., 2011). A load of 2 mN was used and a Regarding the use of kaolin as aluminosilicate precursor, Longhi
penetration-displacement of 300 nm was observed on the surface et al. (2016) have studied the use of kaolin tailings for the synthesis
of the sample. The micro-nanomechanical results for a cement of geopolymeric cements. The waste was formed mainly by
based on metakaolin were also close to the results observed in this kaolinite (~92%) contaminated with quartz and anatase. The
work (Pelisser et al., 2013). resulting geopolymer had a compressive strength of 72 MPa at 28
In this work, the results for modulus of elasticity (approximately days of age, that reduced to 62 MPa at 90 days of age for a silica/
10 GPa) and for hardness (approximately 0.4 GPa) for the geo- alumina ratio of SiO2/Al2O3 ¼ 3.0. But the kaolin waste was calcined
polymeric cements produced with natural kaolin are close to the at 750  C for 1 h, it was ground in ball mill for another 1 h, and its
results for hydrated Portland cement and for hydrated calcium curing was carried out at 50  C, differently from this work, where
silicate (CeSeH). the kaolin was not calcined nor ground.
For Portland cement, the results were 10e15 GPa for the There is no research with the synthesis of geopolymeric ce-
modulus of elasticity and 0.2e1.0 GPa for hardness, using loads ments using natural, non-processed kaolin. The references show
ranging from 2 to 32 mN (Pelisser et al., 2011). For synthetic CeSeH works using metakaolin processed from natural kaolin by calcina-
with Ca/Si ratio ¼ 2.1, the results were 15e20 GPa for the elastic tion and grounding, and modified synthesis conditions for the
modulus and 0.2e0.4 GPa for hardness (Pelisser et al., 2012). processed raw materials, and even so, the compressive strength for
Similar results were shown by Nemecek et al. (2011), when these works are not higher than that obtained in this work.
comparing the modulus of elasticity, determined by nano- The results of this work are assigned to the amorphous nature
mechanical tests, of alkali-activated cements and CeSeH cements. and particle size of the natural kaolin used. These characteristics

7
F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Fig. 8. SEM images of the surfaces of compositions: (a) K1, Na2O.SiO2/NaOH ¼ 2.2; and (b) K3, Na2O.SiO2/NaOH ¼ 1.0.

can be sought in other raw materials or industrial waste to produce silicate and NaOH) gives the importance of geopolymeric cements
geopolymeric cements, with the aim of reducing the environmental in an industrial society where the reduction of CO2 emissions and
impact and the energy spent on the processing of the raw materials. the mitigation of environmental impacts are fundamental for a safe
and sustainable development.
3.1. Reduction of environmental impacts by using natural kaolin in
geopolymers 4. Conclusions

The kaolin used in this work is a regular raw material used by In this work, a geopolymeric cement was produced using a
the ceramic industry to produce ceramic tiles, without any prior natural amorphous kaolin. The kaolin was not calcined nor milled,
calcination. Therefore, the geopolymers produced in this work and the derived geopolymeric cement can be considered a green
show less energy expenditure, lower cost and reduction in CO2 cement. The geopolymeric cement showed high compressive
emissions when compared to geopolymeric cements produced strength, 65 MPa, due to an efficient polymerization process. The
with metakaolin and mainly compared to Portland cement due to results of the micro-nanomechanical characterization showed a
the use of a natural, non-calcined, kaolin. In addition to the modulus of elasticity of 10.2 GPa and a hardness of 0.39 GPa for the
reduction of CO2 emissions, energy expenditure and cost, there is composition Na2O.SiO2/NaOH ¼ 1.6 (K2), results very close to the
also the exclusion of the calcination step to obtain kaolin to be used ones of the compositions K1 (Na2O.SiO2/NaOH ¼ 2.2) and K3
as precursor for geopolymeric cements. (Na2O.SiO2/NaOH ¼ 1.0).
Also, as the geopolymers synthetized in this work were The study shows that the degree of amorphism of the natural
composed of approximately 50% natural kaolin and 50% sodium kaolin was determinant for the geopolymerization process and, in
silicate and sodium hydroxide, the only environmental impacts are addition with the chemical composition, is the most important
the CO2 emissions and energy costs associated with the production factor for the mechanical performance and the efficiency of the
of the alkaline precursors. However, some studies show that those geopolymeric cements. These properties are important for the
costs and emissions are smaller than that of Portland cement (Van technological development of alternative cements and helps its
Deventer et al., 2012), therefore emphasizing the environmental application in the building industry.
advantage of using natural kaolin, even when comparing with the Regarding the environmental impact and sustainability of geo-
use of metakaolin as raw material for geopolymers. polymeric cements produced from natural kaolin, the use of a non-
Another reason for the synthesis and use of geopolymeric ce- calcined kaolin helps the reduction of costs and environmental
ments is their compressive strength after curing, which, in this impacts in the production of geopolymers, resulting in a green
work using natural kaolin, was approximately 65 MPa at 7 days of cement.
age. Several studies on geopolymeric cements show low strength The synthesis of an alternative cement using natural, non-
after curing (<20 MPa), preventing their use for building and con- processed raw materials is of upmost importance to produce effi-
struction works. In this work, the compressive strength (65 MPa) is cient cements to be used in the building industry, therefore
higher than that of Portland cement (ranging from 32 to 50 MPa at reducing the environmental impacts, especially in countries with
28 days). The compressive strength of geopolymers based on less resources. As the building industry is the largest economic
metakaolin, developed by Pelisser et al. (2013), was very similar to activity in the world, considering resources and raw material con-
this work due to the mineralogical characteristics of the kaolin sumption, the benefit of using an environmentally friendly (green)
used. Mortars (Pelisser et al., 2013) and concrete (Pelisser et al., cement is evident.
2018) prepared using geopolymeric cements based on metakaolin Considering future work, the aim is to use the geopolymeric
showed compressive strength of 55 MPa, for a standard cement to composition into concrete (adding aggregates) and measuring
aggregates ratio (1 : 5 ¼ cement: aggregates, by mass). These ad- complementary properties as durability in aggressive environ-
mixtures result in a sustainable and competitive consumption of ments (acids and sulfates), comparing the proposed geopolymeric
cement (binder intensity) of approximately 7 kg m3$MPa1. cement to Portland cement. Also, using it in structural elements,
Considering the above, the environmental and economic po- evaluating the steel/concrete adhesion in improving the mechani-
tential of using a cement composed with natural clay (plus sodium cal performance of concrete beams.

8
F. Pelisser Prof., A.M. Bernardin Prof., M.D. Michel Prof. et al. Journal of Cleaner Production 280 (2021) 124293

Funding Khairul-Nizar, I., Ruzaidi, C.M., Liew, Y.M., 2012. Study on solids-to-liquid and
alkaline activator ratios on kaolin-based geopolymers. Construct. Build. Mater.
35, 912e922.
This work was funded by the Coordination for the Improvement Longhi, M.A., Rodríguez, E.D., Bernal, S.A., Provis, J.L., Kirchheim, A.P., 2016. Valor-
of Higher Education Personnel of Brazil, National Council of Tech- isation of a kaolin mining waste for the production of geopolymers. J. Clean.
nological and Scientific Development of Brazil and the Foundation Prod. 115, 265e272.
Ma, C.-K., Awang, A.Z., Omar, W., 2018. Structural and material performance of
for Research Support and Innovation of the state of Santa Catarina, geopolymer concrete: a review. Construct. Build. Mater. 186, 90e102. https://
Brazil. doi.org/10.1016/j.conbuildmat.2018.07.111.
Medri, V., Papa, E., Lizion, J., Landi, E., 2020. Metakaolin-based geopolymer beads:
production methods and characterization. J. Clean. Prod. 244, 118844. https://
Data availability doi.org/10.1016/j.jclepro.2019.118844.
Nemecek, J., Smilauer, V., Kopecky, L., 2011. Nanoindentation characteristics of
Data will be available on request. alkali-activated aluminosilicate materials. Cement Concr. Compos. 33, 163e170.
Ng, C., Alengaram, U.J., Wong, L.S., Moa, K.H., Jumaat, M.Z., Ramesh, S., 2018.
A review on microstructural study and compressive strength of geopolymer
CRediT authorship contribution statement mortar, paste and concrete. Construct. Build. Mater. 186, 550e576. https://
doi.org/10.1016/j.conbuildmat.2018.07.075.
Oliver, W.C., Pharr, G.M., 1992. An improved technique for determining hardness
Fernando Pelisser: Conceptualization, Methodology, Writing - and elastic modulus using load and displacement sensing indentation experi-
review & editing. Adriano Michael Bernardin: Writing - original ments. J. Mater. Res. 7, 1564e1583. https://doi.org/10.1557/JMR.1992.1564.
draft. Milton Domingos Michel: Methodology, Investigation. Oliver, W.C., Pharr, G.M., 2004. Measurement of hardness and elastic modulus by
instrumented indentation: advances in understanding and refinements to
Caroline Angulski da Luz: Methodology, Investigation.
methodology. J. Mater. Res. 19, 3e20. https://doi.org/10.1557/jmr.2004.19.1.3.
Ozel, M., 2012. Cost analysis for optimum thicknesses and environmental impacts of
Declaration of competing interest different insulation materials. Energy Build. 49, 552e559.
Palomo, A., Fernandez-Jimenez, A., Kovalchuk, G., Ordonez, L.M., Naranjo, M.C.,
2007. OPC fly ash cementitious systems: study of gel binders produced during
The authors declare that they have no known competing alkaline hydration. J. Mater. Sci. 42, 2958e2966.
financial interests or personal relationships that could have Pelisser, F., Gleize, P.J.P., Michel, M.D., 2011. Nanomechanical properties of cement
appeared to influence the work reported in this paper. paste. Rev. IBRACON Estrut. Mater. 4, 561e574.
Pelisser, F., Gleize, P.J.P., Mikowski, A., 2012. Effect of the Ca/Si molar ratio on the
micro-nanomechanical properties of synthetic C-S-H measured by nano-
Acknowledgements indentation. J. Phys. Chem. C 116, 17219e17227.
Pelisser, F., Guerrino, E.L., Menger, M., Michel, M.D., Labrincha, J.A., 2013. Micro-
mechanical characterization of metakaolin-based geopolymers. Construct.
The authors acknowledge the support of the Central Laboratory Build. Mater. 49, 547e553.
of Electronic Microscopy (LCME/UFSC, Brazil). Pelisser, F., Silva, B.V., Menger, M.H., Frasson, B.J., Keller, T.A., Torii, A.J., Lopez, R.H.,
2018. Structural analysis of composite metakaolin-based geopolymer concrete.
Rev. IBRACON Estrut. Mater. 11 (3), 535e543.
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