materials
Article
Synthesis of High Crystallinity 1.13 nm Tobermorite and
Xonotlite from Natural Rocks, Their Properties and
Application for Heat-Resistant Products
R. Siauciunas *, G. Smalakys, A. Eisinas and E. Prichockiene
Citation: Siauciunas, R.; Smalakys,
G.; Eisinas, A.; Prichockiene, E.
Synthesis of High Crystallinity
1.13 nm Tobermorite and Xonotlite
from Natural Rocks, Their Properties
and Application for Heat-Resistant
Products. Materials 2022, 15, 3474.
https://doi.org/10.3390/
ma15103474
Academic Editors: Valentin
Antonovič and Jurgita Malaiškienė
Received: 30 March 2022
Accepted: 10 May 2022
Published: 12 May 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2022, 15, 3474. https://doi.org/10.3390/ma15103474
Department of Silicate Technology, Kaunas University of Technology, Radvilenu pl. 19, 50270 Kaunas, Lithuania;
giedrius.smalakys@gmail.com (G.S.); anatolijus.eisinas@ktu.lt (A.E.); edita.rupsyte@ktu.lt (E.P.)
* Correspondence: raimundas.siauciunas@ktu.lt
Abstract: The main measure to reduce energy losses is the usage of insulating materials. When the
temperature exceeds 500 ◦ C, silicate and ceramic products are most commonly used. In this work,
high-crystallinity 1.13 nm tobermorite and xonotlite were hydrothermally synthesized from lime
and Ca–Si sedimentary rock, opoka. By XRD, DSC, TG and dilatometry methods, it has been shown
that 1.13 nm tobermorite becomes the predominant compound in stirred suspensions at 200 ◦ C after
4 h of synthesis in the mixture with a molar ratio CaO/SiO2 = 0.83. It is suitable for the production
of insulating products with good physical–mechanical properties (average density < 200 kg·m−1 ,
compressive strength ~0.9 MPa) but has a limited operating temperature (up to 700 ◦ C). Sufficiently
pure xonotlite should be used to obtain materials with a higher operating temperature. Even small
amounts of semi-amorphous C–S–H(I) significantly increase its linear shrinkage during firing. It
has also been observed that an increase in the strength values of the samples correlated well with
the increase in the size of xonotlite crystallites. The optimal technological parameters are as follows:
molar ratio of mixture CaO/SiO2 = 1.2; water/solid ratio W/S = 20.0; duration of hydrothermal
synthesis at 220 ◦ C—8 h, duration of autoclaving at 220 ◦ C—4 h. The average density of the samples
was ~180 kg·m−1 , the operating temperature was at least 1000 ◦ C, and the compressive strengths
exceeded 1.5 MPa.
Keywords: high-crystallinity 1.13 nm tobermorite and xonotlite; heat-resistant insulating materials;
hydrothermal curing
1. Introduction
The 1.13 nm tobermorite Ca5 Si6 O16 (OH)2 ·4H2 O, calcium silicate hydrate of poten-
tially highest practical importance, is formed in autoclaved aerated concrete, sand-lime
bricks, fiber cement roofing and facade products, heat-insulating materials, etc. Another
important application stems from its high sorption capacity for heavy and radioactive
metal ions [1–3]. The extensive application of 1.13 nm tobermorite is due to the differences
in the physical behavior of the crystal, such as the solid state, the fibers and nanoparticles
of this compound [4]. Tobermorite of 1.13 nm is most easily synthesized in mixtures with a
molar ratio of CaO/SiO2 = 0.66–0.83 [5].
Xonotlite Ca6 Si6 O17 (OH)2 is denoted by unique physical and chemical properties [6].
This mineral is formed in aqueous suspensions of CaO and SiO2 via hydrothermal synthesis
at 200–350 ◦ C [7]. Xonotlite fibers form needle-shaped crystals [8]. The main area of
application is effective heat-resistant (up to 1000 ◦ C) thermal insulating materials due to
their high porosity, good fire resistance and strength [9]. Moreover, these xonotlite fibers
are nanoscale in size, and, due to their developed specific surface, they can be used as
catalysts in the production of hydrogen [10].
The formation of calcium silicate hydrates is inherently complex, and compounds are
closely related to each other in their chemical composition and structure. The formation ki-
https://www.mdpi.com/journal/materials
Materials 2022, 15, 3474 2 of 18

netics studies are further complicated by the co-formation of a semi-amorphous compound

C–S–H(I) or metastable crystalline phases (Z-phase). For this reason, it is hard to obtain
single-phase, pure and high-crystallinity degree materials [11].
The temperature of hydrothermal synthesis, its duration, the amount of solids in the
suspension and its stirring speed determine the rate of 1.13 nm tobermorite formation, its
degree of crystallinity and purity, the amount of intermediates and their stable existence.
Temperature plays a crucial role. This compound takes hundreds of days to form at room
temperature, yet in a high-temperature (175–200 ◦ C) saturated water vapor environment, it
forms in less than 24 h. Most of the work focuses on the 90–210 ◦ C temperature range [12].
At about 200 ◦ C (the exact value largely depends on the nature and amount of impurities),
1.13 nm tobermorite becomes metastable [13] and recrystallizes to xonotlite [14]. As a rule,
the crystallinity of 1.13 nm tobermorite and the intensity of its diffraction peaks in X-ray
curves increase with the increasing temperature. Moreover, the literature data indicates
that the most favorable temperature for the formation of this compound is usually about
180 ◦ C [14,15]. In it, sufficiently large crystallites of 1.13 nm tobermorite are formed at a
competitive rate.
Lime, quartz sand and varieties of amorphous SiO2 are most widely used. The degree
of 1.13 nm tobermorite crystallinity is also significantly influenced by the chemical compo-
sition, fineness and purity of the materials in use. This is especially important, however,
when using natural raw materials or technogenic industrial products, as the impurities
they contain can significantly adjust the synthesis process [16,17]. Moreover, 1.13 nm tober-
morite is synthesized from many different CaO and SiO2 -containing sources; lime, quartz
sand and different varieties of amorphous SiO2 are the most widely used [18,19]. However,
new sources of SiO2 are not limited to this; they tend to include silica fume Elkem (Elkem
Silicon Products, Oslo, Norway), and Grace Davison (Grace Davison Columbia, Columbia, MD,
USA), silica sand Dorsilit (KRAFT Baustoffe GmbH, Munich, Germany), and marble [20].
Research started looking for new raw materials which would contain a large amount of not
only reactive SiO2 but also impurities that promote the formation of 1.13 nm tobermorite.
Some non-traditional materials, such as kaolinite and metakoaline [21], K-feldspar [22],
rocks trachyte [23], fuka [24], and opoka [25] are already being successfully used. The data
provided in the literature shows that 1.13 nm tobermorite can be successfully synthesized
from a variety of industrial technogenic products and even waste: coal and high alumina
fly ash [12,26], biomass ash [27], blast furnace and steel slag [28,29], etc.
The formation of xonotlite largely depends on the composition of the initial mixture.
Although some researchers [30] suggest that xonotlite can be synthesized from mixtures of
very different basicity (molar ratio CaO/SiO2 = 0.41–1.66), most agree that hydrothermal
reactions are most likely to occur when CaO/SiO2 = 1.0 [31]. The formation of xonotlite
from lime–silica mixtures proceeds through the following intermediates: C–S–H(I), α-C2 SH,
and 1.13 nm tobermorite [32]. At the beginning of hydrothermal reactions, Ca-rich C–S–H
gels were formed, while quartz did not completely react; then, 1.13 nm tobermorite began
to form from these gels. The latter compound is not stable if there are free calcium ions in
the reaction medium. The stoichiometric molar ratio is disturbed, and 1.13 nm tobermorite
starts to recrystallize into xonotlite [33]. This conversion is topotactic, which means that the
new compounds are formed without altering the morphology of the particles. As a result,
xonotlite often slightly lacks Ca2+ ions, and its stability is achieved by Si–OH groups [34].
The main way to reduce the heat loss of buildings is through the use of suitable
and high-quality insulating materials. By designing inorganic nanoporous products, their
thermal resistance must be significantly increased [35]. One of the best materials of this
type is silica aerogel [36], however, it is prohibitively expensive. Therefore, alternatives are
needed, especially those that could use locally mined or otherwise sourced raw materials.
For this reason, it is worthwhile to further investigate insulating heat-resistant materi-
als based on calcium silicate hydrates [37]. The properties of the products made from them
are regulated by the Standard EN 16977:2020 [38]. The classification of calcium silicate insu-
lations is based on the compounds which form an insulation matrix. The crystalline phases
Materials 2022, 15, 3474 3 of 18

can vary among 1.13 nm tobermorite, xonotlite and others, depending on the reaction
conditions involved. The low resistance against temperature compared to other materials
characterizes the heat-insulating products based on tobermorite. The most important
performance aspects of xonotlite are as follows: low density and thermal conductivity; high
mechanical strength; good heat resistance; low shrinkage up to 1050 ◦ C; durability and
resistance to chemical corrosion [9]. However, these properties can only be achieved by syn-
thesizing compounds of high purity [39], i.e., with a minimum amount of semi-crystalline
compounds that increase the shrinkage of the products.
The world produces a large number of good quality insulation materials, their range
is wide, and all of them have their own areas of rational use and application. However,
their nomenclature decreases when the operating temperature exceeds 500 ◦ C, and silicate
or ceramic materials are usually chosen here. In order to reduce the cost of products, it
is best to use locally sourced raw materials. Unfortunately, they are often lacking and
unsatisfactory in quality or price. For these reasons, it is often necessary to look for
new, unconventional raw materials. However, for their successful use in the synthesis of
calcium silicate hydrates, systematic studies of their properties and hydrothermal treatment
parameters are required. Upon assessing this, the goal of this work is to synthesize 1.13 nm
tobermorite and xonotlite from lime and opoka with a controlled structure and properties,
and to evaluate the suitability of the obtained products for the production of heat-resistant
thermal insulation materials.

2. Materials and Methods

2.1. Characterization of the Raw Materials
In this work, the following materials were used:
Lime (EN 459-1:2010) was sourced from Lhoist Bukowa sp., Poland. It was re-calcined
for 1 h at 950 ◦ C (the heating rate was equal to 8 ◦ C/min; cooled naturally in an oven
to 100 ◦ C for 5 h, then transferred to a desiccator and cooled to room temperature) and
ground in a ball mill for 30 min (the specific surface area by laser particle size analyser
Sa = 650 m2 ·kg−1 ; CaOfree = 99.12 mass%).
Opoka: (Stoniskiu–Zemaitkiemio quarry, Lithuania; SiO2 = 54.60 mass%;
CaO = 22.10 mass%; Al2 O3 = 2.53 mass%; Fe2 O3 = 1.66 mass%; MgO = 0.55 mass%;
K2 O = 0.83 mass%). Opoka is mainly composed of opal silica and calcite, which makes
it a highly suitable raw material and a source of both silica and CaO; more details can be
found in Ref. [40]. Opoka was calcined at 775 ◦ C for 1 h (the heating rate was equal to
8 ◦ C/min; cooled in the same way as lime, only in 4 h) and milled in the ball mill for 30 min
(Sa = 950 m2 ·kg−1 ).

2.2. Experimental Methods

2.2.1. Preparation of Samples
The materials were mixed in a homogenizer Turbula Type T2F (Muttenz, Switzerland)
for 1 h at 49 rpm.
Hydrothermal syntheses were carried out and stirred at 50 rpm (unless otherwise
specified), 400 mL of suspension (W/S = 20.0) was placed in a Parr Instruments, model 4751,
(Moline, IL, USA), with a volume of 600 mL for autoclaving. The temperature of the
saturated steam was 200 and 220 ◦ C (when the heating rate was equal to 2 ◦ C/min; cooling
time to 100 ◦ C for 2 h and 2 h 30 min, respectively), with the duration of isothermal curing
of 4–72 h (Table 1). The synthesis products were filtered, rinsed with acetone to reduce
carbonization, dried at a temperature of 100 ± 1 ◦ C for 24 h, and passed through a sieve
with an 80-µm mesh.
Materials 2022, 15, 3474 4 of 18

Table 1. Main properties of hydrothermal synthesis.

Mixture with Molar The Temperature of the Duration of The Suspension

System No.
Ratio CaO/SiO2 Isothermal Curing, ◦ C Isothermal Curing, h Stirred Rate, rpm
1 0.83 200 4; 8; 12; 24; 72 50
2 1 200 4; 8; 12; 24; 72 50
120; 180; 200; 220;
3 15, x FOR PEER REVIEW 1
Materials 2022, 200 12
250;300 5 of 19
4 1.0 220 4; 8; 12; 16; 24; 72 300
5 1.2 200 4; 12; 72 300
6 1.2 220 4; 8; 12; 16; 24; 72 300
6 1.2 220 4; 8; 12; 16; 24; 72 300

The samples (20 mm × 20 mm × 60 mm) were formed in a prefabricated stainless steel

mold The samples
(60 mm (20 mm
× 70 mm × 20 with
× 60 mm) × 6020mm)
mm two mmwere
high formed
internal in a prefabricated
partitions stainless
(Figure 1). Many
steel mold (60 mm × 70 mm × 60 mm) with two 20 mm high internal partitions (Figure 1).
holes, 1 mm in diameter, were drilled at the bottom of the mold at a distance of 5 mm from
Many holes, 1 mm in diameter, were drilled at the bottom of the mold at a distance of 5 mm
each other. A water collection tank with a nozzle for connecting a vacuum pump was
from each other. A water collection tank with a nozzle for connecting a vacuum pump was
welded under it. The filter paper was placed on the bottom of the mold, the suspension
welded under it. The filter paper was placed on the bottom of the mold, the suspension was
was poured
poured in, vacuuming
in, and and vacuuming was initiated.
was initiated. As theAs the began
mass mass began
to dry, to dry,slowly
it was it waspressed
slowly
pressed by thepunch,
by the upper upper also
punch, also
with with
holes holes
1 mm in1diameter.
mm in diameter. It was until
It was pressed pressed
the until the
pressure
pressure reached 1.6 MPa and was maintained for 30 s without interrupting
reached 1.6 MPa and was maintained for 30 s without interrupting the vacuuming. The the
vacuuming. The mold was
mold was dismantled, and dismantled, and was
the excess mass the excess
cut off mass
with awas cut off wire
tightened with at
a tightened
the top of
wire at the top ofThree
the specimens. the specimens. Three
samples were samples
formed were formed simultaneously.
simultaneously.

(a) (b) (c)

Figure
Figure 1.
1. Mold
Mold of
of sample
sample formation
formation (a),
(a), formation
formation process (b) and
process (b) and samples
samples obtained
obtained (c).
(c).

The
Thehydrothermal
hydrothermalcuring
curingofofsamples
samples was
was carried
carried out
out in
in a Parr Instruments pressure
reactor,model
reactor, 4555(Moline,
model4555 (Moline,IL,
IL, USA),
USA), with
with aa maximum
maximum pressure
pressure of
of 131
131 bar,
bar, the volume
◦ C. The temperature
was18.75
was 18.75 L,
L, and
and the
the temperature range was from from − 10 to
−10 to +350
+350 °C. The temperature of the
saturatedsteam
steam was
was 200 and
200 and 220 ◦ C (when the heating rate was equal to 1 ◦ C/min; cooling
220 °C
saturated (when the heating rate was equal to 1 °C/min; cooling
time to 100 ◦ C—5 h), and the duration ofisothermal
isothermalcuring
curingwas
was4–12
4–12h.h.
time to 100 °C—5 h), and the duration of
2.2.2. Instrumental Analysis
2.2.2. Instrumental Analysis
The specific surface area of the raw materials was determined by a laser particle size
The specific surface area of the raw materials was determined by a laser particle size
analyser CILAS 1090 LD (Cilas, Orléans, France) with a measurement range of 0.04–500 µm.
analyser CILAS 1090 LD (Cilas, Orléans, France) with a measurement range of 0.04–500
The measurement principle is based on the diffraction of a light source by the sample. The
μm. The measurement principle is based on the diffraction of a light source by the sample.
results were processed by a PC running the Windows operating system. The dry method
The results were processed by a PC running the Windows operating system. The dry
was used with an air supply of 6 bar.
method was used with an air supply of 6 bar.
The chemical composition analysis of the samples was performed by X-ray fluores-
The chemical composition analysis of the samples was performed by X-ray
cence spectroscopy (XRF) on a Bruker X-ray S8 Tiger WD (Bruker AXS GmbH, Karlsruhe,
fluorescence spectroscopy
Germany) spectrometer (Rh(XRF)
tube; on a Bruker
60 keV). X-raysamples
Powder S8 Tigercompressed
WD (Brukerat AXS
4 MPaGmbH,
were
Karlsruhe, Germany) spectrometer (Rh tube; 60 keV). Powder samples compressed at 4
MPa were measured in helium atmosphere (software: SPECTRA Plus QUANT EXPRESS,
Poulsbo, WA, USA).
The amount of free CaO was determined by following the Standard ASTM C114–11b.
The X-ray diffraction analysis (XRD) was performed on a D8 Advance diffractometer
(Bruker AXS GmbH, Karlsruhe, Germany) operating at 40 kV; 40 mA; filtered with a Ni
Materials 2022, 15, 3474 5 of 18

measured in helium atmosphere (software: SPECTRA Plus QUANT EXPRESS, Poulsbo,

WA, USA).
The amount of free CaO was determined by following the Standard ASTM C114–11b.
The X-ray diffraction analysis (XRD) was performed on a D8 Advance diffractometer
(Bruker AXS GmbH, Karlsruhe, Germany) operating at 40 kV; 40 mA; filtered with a Ni
0.02 mm filter to select the CuKα wavelength; scanned over the range 2θ = 3–70◦ ; scanning
speed 6◦ /min. The software Diffrac.Eva v3.0 (Bruker AXS GmbH, Karlsruhe, Germany) was
used for the identification of compounds and for the calculation of the size of crystallites.
The size of crystallites of 1.13 nm tobermorite from the crystalline plane h k l (d–spacing
1.133 nm) and xonotlite (h k l; d–spacing 0.702 nm) was determined by following the
Scherrer equation:
k hkl · λ
Dhkl = (1)
β hkl · cos θ
where λ is the wavelength of CuKα radiation, θ is the Bragg’s diffraction angle, βhkl is the
full width at half maximum intensity, and k is a shape factor (the value used in this study
was 0.94).
By employing the Diffrac.Eva software (Bruker AXS GmbH, Karlsruhe, Germany), we
used the strategy of the entry points, the left angle and the right angle were used to measure
the interval between two points and thus, obtain the intensity of the peaks. However, the
highest value in the interval may be non-representative because of noise fluctuations. We
determined the peak maximum by fitting a parabola through the points around the highest
value and represented its value in scan units (by referring to it as plus d in Ä, because of
applying the 2θ scan).
Simultaneous thermal analysis (STA; with a Linseis PT1000 instrument; Linseis Mass-
geraete GmbH, Selb, Germany) was also employed for measuring the thermal stability
and phase transformation: under N2 atmosphere at a heating rate of 10 ◦ C·min−1 ; the
temperature range was 30–1000 ◦ C and crucibles of Pt were used.
Determination of the compressive strength was performed on a universal testing ma-
chine FORM+TEST MEGA 10-400-50 (FORM+TEST Seider&Co GmbH, Riedlingen, Germany)
at a loading rate of 0.5 kN/s.
Raw materials and samples were burned in a laboratory kiln Nabertherm LV 15/11/P330
(Nabertherm GmbH, Bremen, Germany).

3. Results and Discussion

3.1. Hydrothermal Synthesis of 1.13 nm Tobermorite and Xonotlite
Our previous work [25] showed that products with a predominance of xonotlite in
lime-calcined opoka mixtures cannot be obtained at a hydrothermal synthesis temperature
of 180 ◦ C. It is well known, however, that by increasing the temperature of the reacting
medium and stirring it, the formation of crystalline calcium silicate hydrates is greatly
accelerated [41]. For this reason, the temperature of the isothermal curing was 200 ◦ C, and
the suspension was stirred at 50 rpm. Therefore, it was determined that in the mixture with
a molar ratio of CaO/SiO2 = 0.83, 1.13 nm tobermorite (PDF No. 04-011-0271; d = 1.133;
0.548; 0.308; 0.298; 0.282 nm) was dominating in the synthesis product as early as after 4 h
of hydrothermal synthesis (Figure 2a, pattern 1). However, together with this compound,
we identified the peaks of quartz (PDF No. 00-046-1045, d = 0.3343 nm) and calcite (PDF No.
04-023-8700, d = 0.3037 nm) as well. All the other minerals which are present in calcined
opoka, such as cristobalite, tridymite and muscovite, react under these conditions.
 Materials 2022, 15, x FOR PEER REVIEW 7 of 19
Materials 2022, 15, 3474 6 of 18

(a) (b)

FigureFigure
2. XRD 2. XRD patterns (a) and intensity of the 1.13 nm tobermorite (d = 1.13 nm) peak (b) of the
patterns (a) and intensity of the 1.13 nm tobermorite (d = 1.13 nm) peak (b) of the
hydrothermal synthesis products from lime–opoka mixture with CaO/SiO2 = 0.83 at 200 °C◦under
hydrothermal synthesis
50 rpm stirring. products
Index: T—1.13from lime–opoka
nm tobermorite, mixture with
Q—quartz, CaO/SiO2 = 0.83 at 200 C under
C—calcite.
50 rpm stirring. Index: T—1.13 nm tobermorite, Q—quartz, C—calcite.
The XRD results show that when prolonging the duration of hydrothermal synthesis,
The
the XRD results
intensity of theshow
mainthat 1.13 when prolonging
nm tobermorite peak the duration of hydrothermal
(d-spacing—1.13 synthesis,
nm) increases slightly
the intensity
(Figure of
2b).the main 1.13
However, thenm tobermorite
peaks peak (d-spacing—1.13
of quartz continued to decrease (Figure nm)2a),
increases
and, afterslightly
72
(Figureh 2b). However,
of isothermal the peaks
curing, of quartz
only traces continued
of the compoundtowere decrease
left. (Figure 2a), and, after 72 h
of isothermalThecuring,
results of
onlysimultaneous
traces of the thermal analysiswere
compound (STA) of the product obtained after 4
left.
andresults
The 72 h of ofhydrothermal
simultaneous synthesis
thermalare analysis
presented(STA)
in Figure 3. The
of the DSC data
product withinafter
obtained the 4
and 72100–240 °C temperaturesynthesis
h of hydrothermal range showed a very broad
are presented in and
Figurevaguely expressed
3. The DSC data dehydration
within the
100–240effect, which is related
◦ C temperature range to showed
the water removal
a very broad from
and1.13 nm tobermorite
vaguely and semi-
expressed dehydration
amorphous calcium silicate hydrate of the C–S–H(I) type, without a clearly expressed
effect, which is related to the water removal from 1.13 nm tobermorite and semi-amorphous
crystal lattice (Figure 3, curves 3 and 4). As mentioned in the introduction, this compound
calcium silicate hydrate of the C–S–H(I) type, without a clearly expressed crystal lattice
remains stable when the synthesis duration is insufficient, or when the molar ratio of the
(Figure 3, curves 3 and 4). As mentioned in the introduction, this compound remains
mixture is disturbed. Thermogravimetric analysis (TG) showed a slight difference in
stable weight
when thelosssynthesis
in the range duration is insufficient,
of 100–240 °C—for the or whensynthesized
product the molar ratio of itthe
for 4 h, wasmixture
equal is
disturbed. Thermogravimetric analysis (TG) showed a slight difference
to 6.32 mass%, and for the 72 h synthesized product, 6.23 mass%, and similarly, with in weight loss
a in
the range of 100–240 ◦ C—for the product synthesized for 4 h, it was equal to 6.32 mass%,
total weight loss of 12.1 mass% and 11.3 mass%, respectively (Figure 3, curves 1 and 2). In
and for the 72 hthe
addition, synthesized
heat flow valuesproduct,
of the6.23 mass%, and
exothermic effectsimilarly, with a total
at a temperature weight
of ~840 loss of
°C (C–S–
12.1 mass% and 11.3 mass%,
H(I) recrystallization respectivelyare
into wollastonite) (Figure 3, curves
also close: 1 and −12).ofIn
12.5 mW·mg theaddition,
synthesized thefor
heat
4 h product (Figure 3, curve 3); 10.4 mW·mg ◦
−1 of the synthesized for
flow values of the exothermic effect at a temperature of ~840 C (C–S–H(I) recrystallization 72 h product (Figure
3, curve 4). When
into wollastonite) are alsosummarizing
close: 12.5 mW these·mg −1 of
data, it can be stated thatfor
the synthesized sufficiently
4 h product pure 1.13 3,
(Figure
tobermorite from the
− 1 lime–calcined opoka mixture at a temperature
curve 3); 10.4 mW·mg of the synthesized for 72 h product (Figure 3, curve 4). When of 200 °C is already
available these
summarizing in 4 h.data,
Increasingit canthebeduration
stated of thesufficiently
that isothermal curing does tobermorite
pure 1.13 not significantly from
affect the mineral composition of the product (either qualitatively ◦ or quantitatively). The
the lime–calcined opoka mixture at a temperature of 200 C is already available in 4 h.
Increasing the duration of the isothermal curing does not significantly affect the mineral
composition of the product (either qualitatively or quantitatively). The small amount
of quartz remaining in the product is likely to react during the treatment of the thermal
insulation samples.
Materials 2022, 15, x FOR PEER REVIEW 8 of 19

Materials 2022, 15, 3474 7 ofof

small amount of quartz remaining in the product is likely to react during the treatment 18
the thermal insulation samples.

Figure 3. TG (1, 2) and DSC (3, 4) curves of the synthesis products from lime–opoka mixture with
CaO/SiO2 = 0.83 at 200 °C under 50 rpm stirring after 4 h (1, 3) and 72 h (2, 4).

A negligible endothermal effect at 375 °C shows that the hydrogarnets (3CaO·Al2O3·

(3−x)SiO2·2H2O, where x may vary from 0 to 3; PDF No. 04014-9841, d = 0.2722; 0.1975;
0.1688 nm) form at the beginning of the synthesis (Figure 3). This phenomenon is logical
because opoka contains 2.53 mass% Al2O3. As the synthesis duration is prolonged,
hydrogarnets decompose, and the released Al3+ ions intervene in the crystal lattice
structure of 1.13 nm tobermorite. This sequence of reactions has been known for a long
time
Figure
Figure[14,21].
3.
3. TG
TG(1,The
(1, 2) thermal
2) and
and DSCDSCeffect
(3,
(3, 4) in theof
4) curves
curves DSC
of the curve
the synthesis
synthesis at aproducts
temperature
products from of 664 °C is
from lime–opoka
lime–opoka related
mixture
mixture to
with
with
the decomposition
CaO/SiO = 0.83 at 200of °C calcite,
◦ under 50and
rpm this endothermic
stirring after 4 h
CaO/SiO2 = 0.83 at 200 C under 50 rpm stirring after 4 h (1, 3) and 72 h (2, 4).
2 effect
(1, 3) and is72very
h (2,weak—the
4). data of TG
analyses showed less than 0.5 mass% mass loss (Figure 3, curve 1).
◦ C shows h and·Al
AAnegligible
negligibleanalysis
Dilatometric endothermal
endothermal effect
of theeffect
powder at 375 sample,
°C that the hydrogarnets
synthesized at 200 °C for 4(3CaO
(3CaO·Al 2 O33··
dried
to (3 − x)SiO
(3−x)SiO 2·2H
a constant · 2HO, O,
2 where
2 2weight where x
x may
at 100 may
± 1vary vary from
from 0 to
°C, showed 0 to
that 3; PDF
3; the
PDFlinear No. 04014-9841,
No. 04014-9841,
shrinkage ind the d = 0.2722;
= 0.2722; 0.1975;
0.1975;
temperature
0.1688
0.1688
range nm)25
nm)
from form
form
to 700 at the
at the beginning
°C beginning
is negligible ofand
of the does
the synthesis
synthesis (Figure
(Figure
not exceed 3).mass%
3).
1.5 This phenomenon
This phenomenon
(Figure 4). isislogical
logical
because
because opoka
opoka contains
Unfortunately, from2.53
contains 2.53
720 mass%
°Cmass% Al2 O
upwards, Al32.OAs
the3. the
As
samplesynthesis
the begins duration
synthesis is prolonged,
duration
to shrink very hydrog-
is intensively,
prolonged,
arnets 3+ ions intervene
and the decompose,
hydrogarnets
linear shrinkage and in
decompose, thethereleased
and 715–815 Al°C
the released range in the
3+ ions intervene
Alexceeds 11 crystal
mass%. in lattice
Wethe structure
crystal
assume lattice
that thisof
1.13 nm
isstructure tobermorite. This
of 1.13 nm tobermorite.
due to aluminum-containing sequence of reactions
This sequence
impurities. has
As early been known
of reactions
as at for a long
has been known
the beginning time [14,21]. The
for a long
of the synthesis,
thermal effect in the DSC effect
curve in at the
a temperature of 664 ◦ C is related to the decomposition
time [14,21]. The thermal DSC curve
some quantity of Al ions intervene in the C–S–H(I) structure and stabilize
3+ at a temperature of 664 °C is related to
it, i.e.,
of calcite,
the and this endothermic
decomposition of calcite, and effect
this isendothermic
very weak—the effect data
is of TG
very analyses showed
weak—the data of less
TG
complicated recrystallization to the 1.13 nm tobermorite is observed. This phenomenon
than 0.5 mass%
analyses showed mass loss (Figure
less than 0.5 mass% 3, curve
mass 1).
loss (Figure 3,hydrates
curve 1). of the same chemical
has long been studied
Dilatometricanalysis and
analysisof proven
of the
the powder for calcium
powder sample, silicate
synthesized atat200 ◦ for 4 h and dried to
Dilatometric
composition, only with a higher degree sample,
of synthesized
crystallinity, i.e., 200 C
1.13 °C fortobermorite
4 h and dried
nmtemperature →
a constant weight at 100 ± 1 ◦ C, showed that the linear shrinkage in the range
to a constant
xonotlite [33]. weight
◦
at 100 ± 1 °C, showed that the linear shrinkage in the temperature
from 25 to 700 C is negligible and does not exceed 1.5 mass% (Figure 4).
range from 25 to 700 °C is negligible and does not exceed 1.5 mass% (Figure 4).
Unfortunately, from 720 °C upwards, the sample begins to shrink very intensively,
and the linear shrinkage in the 715–815 °C range exceeds 11 mass%. We assume that this
is due to aluminum-containing impurities. As early as at the beginning of the synthesis,
some quantity of Al3+ ions intervene in the C–S–H(I) structure and stabilize it, i.e.,
complicated recrystallization to the 1.13 nm tobermorite is observed. This phenomenon
has long been studied and proven for calcium silicate hydrates of the same chemical
composition, only with a higher degree of crystallinity, i.e., 1.13 nm tobermorite →
xonotlite [33].

Figure 4. Dilatometric curve of the product from lime–opoka mixture with CaO/SiO2 = 0.83 at 200 ◦ C
under 50 rpm stirring after 4 h.

Unfortunately, from 720 ◦ C upwards, the sample begins to shrink very intensively,
and the linear shrinkage in the 715–815 ◦ C range exceeds 11 mass%. We assume that this is
due to aluminum-containing impurities. As early as at the beginning of the synthesis, some
quantity of Al3+ ions intervene in the C–S–H(I) structure and stabilize it, i.e., complicated
recrystallization to the 1.13 nm tobermorite is observed. This phenomenon has long been
studied and proven for calcium silicate hydrates of the same chemical composition, only
with a higher degree of crystallinity, i.e., 1.13 nm tobermorite → xonotlite [33].
Thus, from the technological and economic point of view, the optimal synthesis
conditions for 1.13 nm tobermorite precursor from which heat-resistant (up to 700 ◦ C)
thermal insulation materials can be produced are the following: molar ratio of lime–calcined
 Figure 4. Dilatometric curve of the product from lime–opoka mixture with CaO/SiO2 = 0.83 at 200
°C under 50 rpm stirring after 4 h.

Thus, from the technological and economic point of view, the optimal synthesis
Materials 2022, 15, 3474 conditions for 1.13 nm tobermorite precursor from which heat-resistant (up to8700 of 18°C)
thermal insulation materials can be produced are the following: molar ratio of lime–
calcined opoka mixture CaO/SiO2 = 0.83, water–solids ratio W/S = 20, synthesis
temperature—200 °C, duration—4 h, stirring intensity—50 rpm.
opoka mixture CaO/SiO2 = 0.83, water–solids ratio W/S = 20, synthesis temperature—
In order to produce heat-resistant (up to 1000 °C) thermal insulation products from
200 ◦ C, duration—4 h, stirring intensity—50 rpm.
the local raw material, opoka, it is necessary to study the parameters of xonotlite synthesis
In order to produce heat-resistant (up to 1000 ◦ C) thermal insulation products from
in detail.
the local raw material, opoka, it is necessary to study the parameters of xonotlite synthesis
in detail.The stoichiometry of xonotlite Ca6Si6O17(OH)2 corresponds to the molar ratio
CaO/SiO 2 = 1.0; therefore, the mixtures of this composition were studied. A temperature
The stoichiometry of xonotlite Ca6 Si6 O17 (OH)2 corresponds to the molar ratio
CaO/SiO2 = 1.0; therefore,since
of 200 °C was chosen this compound
the mixtures at 200 °C, although
of this composition with difficulty,
were studied. A temper-was
nevertheless
ature of 200 ◦ C was formed in unstirred
chosen since thislime–calcined
compound atopoka 200 ◦ C,suspensions
although with[42].difficulty, was
nevertheless formed in unstirred lime–calcined opoka suspensions [42]. synthesis, only 1.13
It was found, however, that in the product of 4 h hydrothermal
nm tobermorite
It was formed from
found, however, that incrystalline
the product calcium silicate hydrates,
of 4 h hydrothermal however,
synthesis, onlythe intensity
1.13 nm
of its diffraction peaks (Figure 5a, pattern 1) was much lower
tobermorite formed from crystalline calcium silicate hydrates, however, the intensity of than in the product with
CaO/SiO
its diffraction peaks (Figure 5a, pattern 1) was much lower than in the product with of
2 = 0.83. A small amount of xonotlite, together with a high crystallinity degree
1.13 nm
CaO/SiO tobermorite, was found after 8 h of isothermal curing (Figure 5a, pattern 2). The
2 = 0.83. A small amount of xonotlite, together with a high crystallinity degree of
intensity of the xonotlite
1.13 nm tobermorite, was foundmainafter
peak 8 h(d-spacing—0.702
of isothermal curing nm) (Figure
increased
5a, from 86 2).
pattern to 174
Thecps
intensity of the xonotlite main peak (d-spacing—0.702 nm) increased from 86 to 174 cpsnm
when the synthesis duration extended to 12 h (Figure 5b). The intensity of the 1.13
whentobermorite
the synthesis peakduration
(d = 1.13 nm) reached
extended to its
12 maximum
h (Figure 5b).afterThe
12 hintensity
of synthesis (1843
of the cps)
1.13 nmand
then began
tobermorite to (d
peak decrease fairly
= 1.13 nm) rapidly
reached itstomaximum
1535 cps after
(24 h)12and
h ofeven plummeted
synthesis to 981
(1843 cps) andcps
then(72began
h). Although
to decreasethe intensity of thetoxonotlite
fairly rapidly 1535 cpspeak was
(24 h) andconsistently increasing,
even plummeted to 981evencpsafter
(72 72
h).h, we still had
Although the aintensity
mixtureofoftheit and 1.13 nm
xonotlite tobermorite
peak in the synthesis
was consistently increasing,product (Figure
even after
5).we still had a mixture of it and 1.13 nm tobermorite in the synthesis product (Figure 5).
72 h,

(a) (b)

Figure 5. XRD patterns (a) and intensity of the 1.13 nm tobermorite (d = 1.13 nm) and xonotlite
(d = 0.702 nm) peaks (b) of the hydrothermal synthesis products from lime–opoka mixture with
CaO/SiO2 = 1.0 at 200 ◦ C under 50 rpm stirring. Index: T—1.13 nm tobermorite, X—xonotlite,
Q—quartz, C—calcite.
 The STA data of the products obtained after 12 and 72 h of synthesis at 200 °C
stirring at 50 rpm is presented in Figure 6. The endothermic effect at 204 °C indicat
1.13 nm tobermorite is formed. The main exothermic effects were detected at 840
Materials 2022, 15, 3474
844 °C (Figure 6, curves 3 and 4). Moreover, at this thermal effect (related 9 of 18
to C–
recrystallization into wollastonite), the heat flow from 20.63 mW/mg (Figure 6, c
decreased to 14.62 mW/mg (Figure 6, curve 4). When summarizing these results, it
stated that
The STAthe amount
data of semi-crystalline
of the products obtained after 12C–S–H(I)
and 72 h ofwas loweratafter
synthesis 200 ◦ Ca under
longer dura
stirring at 50This
rpm result
is presented ◦
synthesis. is in in Figure
good 6. The endothermic
agreement with theeffect
XRDat data,
204 Cwhere
indicatesthe that
intensive
1.13 nm tobermorite is formed. The main exothermic effects were detected at 840 ◦ C and
of xonotlite after 72 h of synthesis were identified (Figure 5a, curve 5).
844 ◦ C (Figure 6, curves 3 and 4). Moreover, at this thermal effect (related to C–S–H(I)
Unfortunately, it has to be acknowledged that a product in which the do
recrystallization into wollastonite), the heat flow from 20.63 mW/mg (Figure 6, curve 3)
compound would
decreased to 14.62 be xonotlite
mW/mg (Figure 6,could not
curve 4). be synthesized
When in this
summarizing these case,
results, either.
it can be It is
formed with
stated that 1.13 nm
the amount tobermorite and
of semi-crystalline C–S–H
C–S–H(I) (I), and
was lower afterthese calcium
a longer durationsilicate
of hy
synthesis. Thislower
significantly result isthe
in good agreement
application with the XRDof
temperature data, where the intensive
heat-resistant products.peaks
of xonotlite after 72 h of synthesis were identified (Figure 5a, curve 5).

Figure 6.6. TG
Figure TG(1,(1,2) 2)
andandDSCDSC
(3, 4)(3,
curves of synthesis
4) curves products from
of synthesis lime–opoka
products from mixture with mixtu
lime–opoka
CaO/SiO = 1.0 at 200 ◦ C under stirring at 50 rpm after 12 h (1, 3) and 72 h (2, 4).
CaO/SiO22 = 1.0 at 200 °C under stirring at 50 rpm after 12 h (1, 3) and 72 h (2, 4).
Unfortunately, it has to be acknowledged that a product in which the dominant
Some would
compound authors suggestcould
be xonotlite thatnotthe
be formation
synthesized in ofthis
xonotlite andIt other
case, either. is alwayscalcium
hydrates is accelerated by intensively stirring the suspensions [43,44]. Howev
formed with 1.13 nm tobermorite and C–S–H (I), and these calcium silicate hydrates
significantly
literature lower
data onthethe
application
positivetemperature
influence of ofheat-resistant
the mixingproducts.
intensity on xonotlite synth
Some authors suggest that the formation of xonotlite and other calcium silicate hy-
difficult to compare among alternative sources because of the different raw ma
drates is accelerated by intensively stirring the suspensions [43,44]. However, the literature
equipment, and hydrothermal
data on the positive influence of thecuring
mixing parameters being used.
intensity on xonotlite Foristhese
synthesis reasons,
difficult to it is
investigating
compare amongin detail the
alternative influence
sources becauseofofthe
the stirring intensity
different raw onequipment,
materials, the formation and proce
the target compounds. Therefore, hydrothermal synthesis at 200 °C for 12inh by stir
hydrothermal curing parameters being used. For these reasons, it is worth investigating
detail the influence of the stirring intensity on the formation processes of the target com-
120–300 rpm when CaO/SiO2 = 1.0 was examined. Furthermore, it was determin
pounds. Therefore, hydrothermal synthesis at 200 ◦ C for 12 h by stirring at 120–300 rpm
under stirring2 =at1.0120
when CaO/SiO wasrpm, in the
examined. synthesisitproducts,
Furthermore, 1.13 that
was determined nmunder
tobermorite
stirring at of the h
crystallinity
120 rpm, in thedegree
synthesis(according
products, 1.13tonmTaylor),
tobermoritetogether with xonotlite,
of the highest crystallinityisdegree
formed (Fi
(according
pattern 1) to[45].
Taylor), togetherincrease
A further with xonotlite,
in theis formed
stirring(Figure 7, pattern
intensity had1)no [45]. A further
effect on the min
increase in the stirring intensity had
ical composition of the product (Figure 7). no effect on the mineralogical composition of the
product (Figure 7).
Materials 2022, 15, x FOR PEER REVIEW 11 of 19
Materials 2022, 15, 3474 10 of 18

Figure 7.
Figure XRDpatterns
7.XRD patternsof of hydrothermal
hydrothermal synthesis
synthesis products
products afterafter
12 h 12 h under
under different
different stirring
stirring rates
from
rates lime–opoka mixture
from lime–opoka with with
mixture CaO/SiO 2 = 1.02 at
CaO/SiO 200at°C.
= 1.0 ◦ C. Index:
200Index: T—1.13 nm tobermorite,
T—1.13 nm tobermorite,X—
xonotlite, C—calcite.
X—xonotlite, C—calcite.

However, we noticed that the stirring intensity during

However, during hydrothermal
hydrothermal synthesis
synthesis hashas aa
significant impact
significant impact on onthetheconsistency
consistency of the
of suspension.
the suspension. Calcium silicate
Calcium hydrates
silicate physi-
hydrates
cally bind abind
physically large amount
a large of water
amount and form
of water and something
form somethinglike gels
likethat
gelsarrange in the layers
that arrange in the
(sediments-water)
layers very slowly.
(sediments-water) It hasItbeen
very slowly. observed
has been that that
observed the thicker the the
the thicker suspension
suspension ob-
tained during hydrothermal synthesis, the lower the density of the
obtained during hydrothermal synthesis, the lower the density of the samples formed samples formed during
simultaneous
during vacuuming
simultaneous and pressing.
vacuuming This parameter
and pressing. was named
This parameter the relative
was named volume
the relative
and was
volume anddetermined by sedimentation.
was determined The synthesis
by sedimentation. products
The synthesis were cooled
products were to cooled 1 ◦22
22 ± to C,
±poured into a measuring
1 °C, poured cylinder,
into a measuring and kept
cylinder, and at restatfor
kept rest24for
h.24The relative
h. The volume
relative volumeof the
of
synthesis
the product
synthesis is the
product is ratio of the
the ratio ofvolume of theofsediments
the volume the sedimentsin a cylinder and their
in a cylinder and mass.
their
This relative volume increases steadily with the increasing stirring
mass. This relative volume increases steadily with the increasing stirring rate (Table rate (Table 2). We have
2).
found that when the value of this parameter is less than 10, samples
We have found that when the value of this parameter is less than 10, samples with an with an average density
−3
of less than
average 200 kg
density of·mlesscannot be obtained
than 200 or their be
kg·m−3 cannot strength is unsatisfactory.
obtained or their strength For this
is
reason, the precursor for the formation of thermal insulation specimens
unsatisfactory. For this reason, the precursor for the formation of thermal insulation was synthesized in
stirred suspensions
specimens at 300 rpm.
was synthesized in stirred suspensions at 300 rpm.

Table 2.
Table Ratio of
2. Ratio of the
the volume
volume of
of sediments
sediments and
and their
their mass
mass after
after 24
24 h
h of
of sedimentation.
sedimentation.

Stirring rate, rpm 50 Stirring120

rate, rpm 180 50 120
200 180 220 200 220
250 250 300
300
Relative volume, cm3 /g 6 Relative volume,
7 cm3/g 7.5 6 107 7.5 11 10 11
13.5 13.5 1515

By summarizing this part of the work, it can be stated, however, that at 200 °C, ◦in the
By summarizing this part of the work, it can be stated, however, that at 200 C, in
lime–calcined opoka mixture, we could not obtain products in which the predominant
the lime–calcined opoka mixture, we could not obtain products in which the predominant
compound would be
compound would be xonotlite.
xonotlite. ItIt isisknown,
known,however,
however,that
thatbybyincreasing
increasing the
the temperature
temperature of
Materials 15, 3474
2022,2022,
Materials 15, x FOR PEER REVIEW 11 of1218of 19

hydrothermal synthesis,
of hydrothermal the rate
synthesis, theofrate
xonotlite formation
of xonotlite increases
formation significantly
increases [33]. [33].
significantly DueDue
to this reason, we performed hydrothermal synthesis at a temperature of 220 ◦ C under
to this reason, we performed hydrothermal synthesis at a temperature of 220 °C under
stirring at 300
stirring atrpm. It wasItfound
300 rpm. that xonotlite
was found was detected
that xonotlite in the product
was detected as early as
in the product as after
early as
4 h of isothermal
after 4 h of curing (Figure
isothermal 8a,
curing pattern
(Figure 1)
8a, and its
pattern peak
1) andd = 0.702
its peak nm
d =intensity
0.702 nmis higher is
intensity
than at 200 ◦ C (Figure 8b). However, even after 72 h of curing, this compound coexists with
higher than at 200 °C (Figure 8b). However, even after 72 h of curing, this compound
1.13 nm tobermorite (Figure 8a, curve 3).
coexists with 1.13 nm tobermorite (Figure 8a, curve 3).

(a) (b)
Figure
Figure 8. XRD
8. XRD patterns
patterns (a) and
(a) and intensity
intensity ofxonotlite
of the the xonotlite
(d = (d = 0.702
0.702 nm) nm)
peakpeak
(b) of(b) of hydrothermal
hydrothermal
synthesis products from lime–opoka mixture with CaO/SiO2 = 1.0 at 220 C under 300 rpmrpm
synthesis products from lime–opoka mixture with CaO/SiO 2 = 1.0 at ◦
220 °C under 300 stirring.
stirring.
Index: T—1.13 nm tobermorite, X—xonotlite, Q—quartz, C—calcite.
Index: T—1.13 nm tobermorite, X—xonotlite, Q—quartz, C—calcite.

Many Many researchers

researchers suggest suggest that in
that in order order xonotlite
to obtain to obtainviaxonotlite
hydrothermal via hydrothermal
synthesis,
synthesis, mixtures with a molar ratio of CaO/SiO
mixtures with a molar ratio of CaO/SiO2 = 1.0 have to be used [31]. However, 2 = 1.0 have to be used [31]. However,
in the in
the lime–calcined
lime–calcined opoka suspension,
opoka suspension, in all the
in all the cases, thetarget
cases,compound
the target was compound was formed
formed together
withtogether with other
other low-base low-base
calcium silicatecalcium
hydrates.silicate
Thishydrates.
leads to the This leads to thethat
assumption assumption
the molarthat
ratiothe molar
is too lowratio is tooxonotlite
for pure low for pure xonotlite
formation. Oneformation. One ofmay
of the reasons the reasons
be that notmayall beCaO
that not
was involved in the formation of calcium silicate hydrates: part of it reacted with thewith
all CaO was involved in the formation of calcium silicate hydrates: part of it reacted
the impurities
impurities in opoka, inandopoka,
2.95andmass%2.95of mass%
CaO was of CaOin thewas in the composition
composition of CaCO3of, whichCaCO3was , which
was calcination
left after left after calcination
of opoka atof775 ◦
opoka at 775 °C.the
C. Increasing Increasing
calcination thetemperature
calcination istemperature
definitely is
definitelyhowever,
problematic, problematic, becausehowever,
during because during theofdecomposition
the decomposition carbonates, the of carbonates,
obtained CaO the
obtained
is highly CaO is
reactive, highly
and, reactive,
together withand, together
silica, with silica,
wollastonite wollastonite
is formed. Due to is this
formed.reason,Due to
this reason,
the molar ratio of the molar ratio
CaO/SiO 2 in of
the CaO/SiO
reactive in
media
2 thecanreactive
be lowermediathan can
1.0.be lower
Moreover, than as 1.0.
mentioned in the introduction, 1.13 nm tobermorite is closely related to xonotlite by its to
Moreover, as mentioned in the introduction, 1.13 nm tobermorite is closely related
xonotlite
structure and by its structure
synthesis and synthesis
mechanism. Therefore, mechanism.
the lower molar Therefore,
ratio is the lower
more molar ratio
favorable for is
1.13 more
nm tobermorite
favorable for formation
1.13 nmthan it is for xonotlite.
tobermorite formation than it is for xonotlite.
DueDue to thisto reason, it wasitdecided
this reason, to increase
was decided the molar
to increase theratio
molar upratio
to CaO/SiO 2 = 1.2 and
up to CaO/SiO 2 = 1.2

investigate the formation

and investigate of xonotlite
the formation ofinxonotlite
this particular
in thiscase. It was determined,
particular case. It was however,determined,
that however,
under thethat same synthesis
under the same conditions,
synthesis theconditions,
reaction sequence
the reaction in the products
sequence in with this
the products
molar ratio changes significantly.
with this molar ratio changes significantly.
In summary,
In summary, in the
in themixtures
mixtures withwithCaO/SiO
CaO/SiO22 = 1.2, 1.2,thetheformation
formationofof xonotlite
xonotlite at °C
at 200
200 ◦isCslow
is slow enough
enough because,
because, afterafter 4 hsynthesis,
4 h of of synthesis, onlyonly
tracestraces
werewere identified
identified (Figure
(Figure 9,
9, pattern
pattern 1). However,
1). However, an important
an important difference
difference waswas observed
observed in in
thatthat 1.13
1.13 nm nmtobermorite
tobermoriteis no
is nolonger
longerformed
formedininthis thismixture
mixture(Figure
(Figure10, 10,patterns
patterns22and and3).3). In
Inorder
order to to improve
improve the the for-
formation of xonotlite, it was decided to increase the
mation of xonotlite, it was decided to increase the synthesis temperature.synthesis temperature.
Materials
Materials 2022,
2022, 15,
15, x3474
FOR PEER REVIEW 1312ofof19
18

Figure 9. XRD patterns of hydrothermal synthesis products from lime–opoka mixture with
CaO/SiO2 = 1.2 at 200 °C under 300 rpm stirring. Index: X—xonotlite, C—calcite.

The results of the XRD analysis of hydrothermal synthesis products from the mixture
with CaO/SiO2 = 1.2 at 220 °C under 300 rpm stirring are presented in Figure 10. It was
determined that the formation of xonotlite is extremely rapid, and as early as after 4 h of
hydrothermal curing, it was identified as the main compound (Figure 10a, pattern 1). It
should be noted, however, that in the synthesis product, we could not identify even traces
of quartz. Furthermore, and most importantly, no other crystalline calcium silicate
hydrates were found. The intensity of the xonotlite peak d = 0.702 nm was high—we did
not obtain such values in the earlier stages of the work (Figure 10b). When prolonging the
synthesis duration, no phase transformations were found to occur, and xonotlite remained
Figure
Figure 9.for
stable9. XRD
XRD
up to patterns
patterns ofof hydrothermal
72 h (Figure hydrothermal synthesis
synthesis
10a). The only products
products
ongoing from
from
process lime–opoka
lime–opoka
was mixture with
mixture
a steady increase with
in the
CaO/SiO
CaO/SiO = = 1.2
1.2 atat 200
200 °C◦C under
under 300
300 rpm
rpm stirring.
stirring. Index:
Index: X—xonotlite,
X—xonotlite, C—calcite.
C—calcite.
intensity of the diffractive peaks of this compound (Figure 10b).
22

The results of the XRD analysis of hydrothermal synthesis products from the mixture
with CaO/SiO2 = 1.2 at 220 °C under 300 rpm stirring are presented in Figure 10. It was
determined that the formation of xonotlite is extremely rapid, and as early as after 4 h of
hydrothermal curing, it was identified as the main compound (Figure 10a, pattern 1). It
should be noted, however, that in the synthesis product, we could not identify even traces
of quartz. Furthermore, and most importantly, no other crystalline calcium silicate
hydrates were found. The intensity of the xonotlite peak d = 0.702 nm was high—we did
not obtain such values in the earlier stages of the work (Figure 10b). When prolonging the
synthesis duration, no phase transformations were found to occur, and xonotlite remained
stable for up to 72 h (Figure 10a). The only ongoing process was a steady increase in the
intensity of the diffractive peaks of this compound (Figure 10b).

(a) (b)

Figure 10. XRD patterns (a) and intensity of the xonotlite (d = 0.702 nm) peak (b) of hydrothermal
synthesis products from lime–opoka mixture with CaO/SiO2 = 1.2 at 220 ◦ C under 300 rpm stirring.
Index: X—xonotlite, C—calcite.

The results of the XRD analysis of hydrothermal synthesis products from the mixture
with CaO/SiO2 = 1.2 at 220 ◦ C under 300 rpm stirring are presented in Figure 10. It was
determined that the formation of xonotlite is extremely rapid, and as early as after 4 h of
hydrothermal curing, it was identified as the main compound (Figure 10a, pattern 1). It
should be noted, however, that in the synthesis product, we could not identify even traces
of quartz. Furthermore, and most importantly, no other crystalline calcium silicate hydrates
were found. The intensity of the xonotlite peak d = 0.702 nm was high—we did not obtain
(a) (b)
Materials 2022, 15, x FOR PEER REVIEW 14 of 19

Materials 2022, 15, 3474 13 of 18

Figure 10. XRD patterns (a) and intensity of the xonotlite (d = 0.702 nm) peak (b) of hydrothermal
synthesis products from lime–opoka mixture with CaO/SiO2 = 1.2 at 220 °C under 300 rpm stirring.
such values in the earlier stages of the work (Figure 10b). When prolonging the synthesis
Index: X—xonotlite, C—calcite.
duration, no phase transformations were found to occur, and xonotlite remained stable for
up to 72 h (Figure 10a). The only ongoing process was a steady increase in the intensity of
The exothermic effect at 842 °C in the DSC curve suggests, however, that in the 4 h
the diffractive peaks of this compound (Figure 10b).
synthesis product, there is quite◦ a large quantity of C–S–H(I) (Figure 11, curve 3).
The exothermic effect at 842 C in the DSC curve suggests, however, that in the 4 h
However, the area of this effect in the 12 h synthesis sample decreased significantly, and
synthesis product, there is quite a large quantity of C–S–H(I) (Figure 11, curve 3). However,
only a blurred signal was captured (Figure 11, curve 4). Comparing the values of the heat
the area of this effect in the 12 h synthesis sample decreased significantly, and only a blurred
flow, we see that they differ almost threefold, i.e., a decrease from 3.0 mW (4 h) to 1.03
signal was captured (Figure 11, curve 4). Comparing the values of the heat flow, we see
mW
that (12
theyh).
differ almost threefold, i.e., a decrease from 3.0 mW (4 h) to 1.03 mW (12 h).

Figure 11.
Figure TG (1,
11. TG (1, 2)
2) and
and DSC
DSC (3,
(3, 4)
4) curves
curves of of the
the synthesis
synthesis products
products from from lime–opoka
lime–opoka mixture
mixture with
with
CaO/SiO2 2= =1.2
CaO/SiO 220°C◦ Cunder
1.2atat220 understirring
stirringatat300
300rpm
rpmafter
after4 4h h(1,(1,3)3)and
and1212h h(2,(2,4).4).

Such results
Such results indicate
indicate that
that very
very small
small amounts
amounts of of semi-amorphous
semi-amorphous compounds
compounds are are
formed under
formed under these
these conditions. According
According to to literature
literature data,
data, the
the recrystallization
recrystallization of of
xonotlite to
xonotlite to wollastonite
wollastonite is is not
not associated
associated with
with heat
heat release
release or or consumption
consumption [46]. [46]. Hence,
Hence,
this exothermic
this exothermic effect
effect occurs
occurs only
onlywhen
whensemi-amorphous
semi-amorphousC–S–H(I)C–S–H(I)recrystallizes.
recrystallizes. This
Thisis is
in
good agreement with the XRD data, as only intensive peaks of xonotlite
in good agreement with the XRD data, as only intensive peaks of xonotlite were identified were identified
(Figure 10).
10). In
In the
the DSC
DSC curve,
curve, we we identified
identified an
an exothermic
exothermic effect
effect at
at 845 ◦ C, which suggests
845 °C,
(Figure which suggests
that xonotlite
that xonotlite already
already dominates
dominatesininthe theproducts
products obtained
obtained after 12 h
after 12ofhhydrothermal
of hydrothermal syn-
thesis. In addition,
synthesis. In addition, in the
in DSC
the DSCcurve, we identified
curve, an endothermic
we identified an endothermic at 723at◦ C
effecteffect (after
723 °C
4 h), which is related to the decomposition of calcite. Moreover, the same
(after 4 h), which is related to the decomposition of calcite. Moreover, the same effect is effect is identified
after 12 h of
identified hydrothermal
after synthesis. synthesis.
12 h of hydrothermal
We would also like tomention
We would also like to mention that when
that whenthe the
material under
material studystudy
under contains an amor-
contains an
phous part, the XRD pattern of this material shows a visible blunt
amorphous part, the XRD pattern of this material shows a visible blunt similar to a slopingsimilar to a sloping
hill. We
hill. We did
did not
not notice
notice this
this in
in the
thesynthesis
synthesisproduct
productpattern,
pattern,therefore,
therefore,we wecan
cansaysaythat
thatit it
is
composed entirely of a compound with a high degree of crystallinity,
is composed entirely of a compound with a high degree of crystallinity, xonotlite, and a xonotlite, and a few
percent impurities of semi-crystalline C–S–H (I) and calcite.
few percent impurities of semi-crystalline C–S–H (I) and calcite.
To summarize, the following technical parameters should be selected for the produc-
To summarize, the following technical parameters should be selected for the
tion of heat-resistant thermal insulating products with predominant xonotlite: the molar
production of heat-resistant thermal insulating products with predominant xonotlite: the
ratio of lime–calcined opoka mixture CaO/SiO2 = 1.2; water/solid ratio W/S = 20.0; the
molar ratio of lime–calcined opoka mixture CaO/SiO 2 = 1.2; water/solid ratio W/S = 20.0;
duration of hydrothermal synthesis to be set at 220 ◦ C from 4 h to 12 h while stirring the
the duration of hydrothermal synthesis to be set at 220 °C from 4 h to 12 h while stirring
suspension at 300 rpm.
the suspension at 300 rpm.
3.2. Evaluation of Suitability of Opoka for the Production of Heat-Resistant Thermal Insulating
Materials from Calcium Silicate Hydrates
As it can be seen from the data presented in Section 3.1, 1.13 nm tobermorite can be
synthesized in a lime–calcined opoka suspension at a lower temperature and in a shorter
time than xonotlite. However, its samples begin to shrink intensively from 720 ◦ C (Figure 4);
Materials 2022, 15, 3474 14 of 18

therefore, thermal insulation materials made of 1.13 nm tobermorite can only serve up to the
above-mentioned temperature. On the other hand, there is a lot of heating equipment and
pipelines in the industry with lower operating temperatures. Tobermorite-based products
may be well suited for their insulation.
Precursors of thermal insulating materials were prepared from the suspension
(CaO/SiO2 = 0.83, W/S = 20) which was obtained via hydrothermal synthesis at 200 ◦ C for
4 h. The samples (20 mm × 20 mm × 60 mm) were formed in a vacuum-press form by using
simultaneous water suction and pressing at 1.6 MPa. Afterward, they were reprocessed in
an autoclave (200 ◦ C, 4–12 h) and dried at 100 ± 1 ◦ C until constant weight. The obtained
results are presented in Table 3. It shows the mean values of the three samples; the scatter
of the data did not exceed 10 mass%.

Table 3. The main properties from 1.13 nm tobermorite-based samples.

Duration of Hydrothermal Curing Duration at 200 ◦ C, h

Properties
Synthesis at 200 ◦ C—4 h 4 6 8 12
Size of crystallites, nm 35.0 38.1 39.9 43.1 50.3
Average density, kg/m3 – 193.3 188.5 191.8 190.1
Compressive strength, MPa – 0.77 0.87 0.92 0.93
Bending strength, MPa – 0.46 0.56 0.53 0.59

Medium quality products are obtained (average density ≤ 200 kg/m3 , compressive
strength ~0.9 MPa) that have their own areas of rational use. No changes in the qualitative
mineralogical composition were observed in the XRD curves. We would like to point out,
however, that a minor but steady increase in the strength values correlates well with the
increase in the size of 1.13 nm tobermorite crystallites as the hydrothermal curing duration
is prolonged. However, xonotlite should be used as a precursor to obtaining higher working
temperature materials.
One of the essential requirements for heat-resistant thermal insulating products is
their minimal shrinkage at high temperatures. Since semi-amorphous C–S–H(I) type
calcium silicate hydrate does not have a clear crystalline structure, its shrinkage during
recrystallization into wollastonite is very high. Meanwhile, the structure of the crystal
lattice of xonotlite and wollastonite is very similar; therefore, the shrinkage during this
recrystallization process is negligible. It means that the mineralogical composition of the
products determines their working temperature. The change in the linear dimensions of the
material and its ability to withstand the effects of a high temperature can be pre-determined
by dilatometry analysis. When using this method, three samples of synthesized powder
were investigated in order to select the optimal conditions for the production of precursors
for thermal insulating products.
The linear shrinkage of the sample, which was synthesized at 200 ◦ C for 72 h, is too
high at 2.48 mass% (Figure 12, curve 1). Although we can see in the XRD curve that a high
degree of crystallinity xonotlite has formed (Figure 9, curve 3), due to some amount of
C–S–H(I) remaining in the product, items made from it can be used only up to 750–800 ◦ C.
By increasing the synthesis temperature to 220 ◦ C, the shrinkage of the samples in the range
of 30–1000 ◦ C decreases significantly: after 4 h of isothermal curing, it is 1.68 mass%, and
after 12 h, it is only 0.86 mass% (Figure 12, curves 2 and 3). This is in good agreement with
the DSC data, which shows that the latter product is virtually free of C–S–H(I) type calcium
silicate hydrate (Figure 11, curve 4).
Materials2022,
Materials 15,x3474
2022,15, FOR PEER REVIEW 1615ofof19
18

Figure12. Dilatometryanalysis
12.Dilatometry analysiscurves
curvesofofthe
thesynthesis
synthesisproducts
productsat
at200 ◦ C for 72 h (3) and at 220 ◦ C
200°C
Figure for 72 h (3) and at 220 °C
for44hh(1)
for (1)and
and12
12hh(2),
(2),when
whenCaO/SiO
CaO/SiO 2 = = 1.2.
2 1.2.

Precursors of
Precursors of thermal
thermalinsulating
insulatingmaterials
materialswere
were prepared
preparedfromfrom
the suspensions which
the suspensions
were obtained via hydrothermal synthesis at 220 ◦ C for 4, 8, and 12 h. It should be noted
which were obtained via hydrothermal synthesis at 220 °C for 4, 8, and 12 h. It should be
that the
noted thatformed xonotlite
the formed physically
xonotlite binds binds
physically a largea amount of water,
large amount which which
of water, results results
in very
inthick
verysuspensions with a relative
thick suspensions with a volume
relative of about 20.
volume The formed
of about 20. Thesamples
formedwere autoclaved
samples were
at 220 ◦ C for 12 h and dried. As with the samples based on 1.13 nm tobermorite, no changes
autoclaved at 220 °C for 12 h and dried. As with the samples based on 1.13 nm tobermorite,
in the qualitative mineral composition were observed in the XRD curves. However, the
no changes in the qualitative mineral composition were observed in the XRD curves.
size of the crystallites increases gradually, and, at the same time, the strength values of
However, the size of the crystallites increases gradually, and, at the same time, the
the samples increase (Table 4, columns 1–3). It is assumed that the xonotlite suspension
strength values of the samples◦ increase (Table 4, columns 1–3). It is assumed that the
should be synthesized at 200 C for 8 h, as the average density of the obtained samples
xonotlite suspension should be synthesized at 200 °C for 8 h, as the average density of the
is ~180 kg/m−1 , and the compressive and bending strengths exceed 1.5 and 0.8 MPa,
obtained samples is ~180 kg/m−1, and the compressive and bending strengths exceed 1.5
respectively. By extending the synthesis duration to 12 h, the properties of the samples
and 0.8 MPa, respectively. By extending the synthesis duration to 12 h, the properties of
improve only slightly (Table 4, column 3).
the samples improve only slightly (Table 4, column 3).
Table 4. Main properties from xonotlite-based samples.
Table 4. Main properties from xonotlite-based samples.
Duration ◦ C,
Duration◦
ofof Synthesis
Synthesis at at
220 °C, Curing
Curing Duration
Duration atat 220
220 °C,
Properties 220 C, When Curing When Duration of Synthesis
Properties When Curing Duration at When Duration of Synthesis
Duration at 220 ◦ C—12 h at 220 ◦ C—8 h
220 °C—12 h at 220 °C—8 h
Columns
Columnsnumber
number 11 22 33 44 55 66
Hydrothermaltreatment,
Hydrothermal treatment,hh 44 88 1212 44 66 88
Sizeof
Size ofcrystallites,
crystallites,nm
nm 30.4
30.4 31.7
31.7 34.0
34.0 27.3
27.3 27.9
27.9 30.7
30.7
Average density, kg/m33 214.2 184.0 178,1 178.6 181.3 183.1
Average density, kg/m 214.2 184.0 178,1 178.6 181.3 183.1
Compressive strength, MPa 1.40 1.54 1.84 1.40 1.34 1.44
Compressive strength,MPa
Bending strength, MPa 1.40
0.78 1.54
0.83 1.84
0.86 1.40
0.61 1.34
0.68 1.44
0.85
Bending strength, MPa 0.78 0.83 0.86 0.61 0.68 0.85
By varying the duration of hydrothermal treatment at 220 °C from 4 to 8 h for the
samples formed from
By varying the 8 h of
the duration synthesized
hydrothermal suspension,
treatmentboth ◦ C physical-mechanical
their
at 220 from 4 to 8 h for the
properties and the from
samples formed size ofthethe8crystallites
h synthesizedchange only slightly
suspension, (Table
both their4, physical-mechanical
columns 4–6). Thus,
in the production
properties and theof heat-resistant
size thermal
of the crystallites insulation
change products
only slightly based
(Table on xonotlite
4, columns 4–6). from
Thus,
the lime–calcined opoka mixture, the optimal technological parameters
in the production of heat-resistant thermal insulation products based on xonotlite from are as follows:
molar ratio of the initial
the lime–calcined opokamixture CaO/SiO
mixture, 2 = 1.2;technological
the optimal the water/solid ratio of the
parameters aresuspension
as follows:
W/S
molar= 20.0;
ratioduration of hydrothermal
of the initial mixture CaO/SiO synthesis at 220
2 = 1.2; the °C—8 h, duration
water/solid ratio of autoclaving
the suspensionat
220
W/S °C—4 h. duration of hydrothermal synthesis at 220 ◦ C—8 h, duration of autoclaving at
= 20.0;
◦ C—4 h.
220 Linear shrinkage is only one of the indicators limiting the temperature of the use of
Linear
products. Evenshrinkage
more sois atonly
up toone
800of°C,the
allindicators limiting
calcium silicate the temperature
hydrates of the use of
are finally dehydrated
products. Even more so at up to 800 ◦ C, all calcium silicate hydrates are finally dehydrated
and transformed to anhydrous forms, and in this case, mainly to wollastonite CaO‧SiO2.
and transformed
During to anhydrous
recrystallization, internalforms,
stresses andmayin this
occurcase, mainly
in the productto wollastonite CaO·may
and its strength SiO2 .
Materials 2022, 15, 3474 16 of 18

During recrystallization, internal stresses may occur in the product and its strength may
decrease. No less important is the decrease in strength during burning. To evaluate this
property, the samples prepared under the above-outlined conditions were fired at 650, 800,
and 1000 ◦ C for 2 h. They did not show any cracks or other damage. After cooling to room
temperature, the compressive strength of the samples was determined. The results are
shown in Table 5. It can be stated, however, that even at a temperature of 1000 ◦ C, despite
losing crystalline water, the samples retain high strength for a sufficiently long time.

Table 5. Compressive strength of burned xonotlite-based samples.

Burning Temperature, ◦ C, With Duration of 2 h

Properties
650 800 1000
Compressive strength, MPa 1.39 1.22 0.97
Variation, % of initial value 96.5 84.7 67.3

The thermal conductivity of the samples calculated according to the Japanese Standard
JISA1413 was relatively low at around 0.040 W/m·K. This is due to the fact that the xonotlite
density is 2700 kg/m3 , while the average density of the samples is ~180 kg/m3 . This means
that the solid material occupies only 4.8 mass% of the sample volume, while the remaining
95.2 mass% is air entrapped in very small pores.
In addition, the obtained compressive strength for xonotlite-based thermal insulation
materials is sufficient for product transportation and installation on site.

4. Conclusions
1. The 1.13 nm tobermorite, with a high degree of crystallinity in the lime–calcined
opoka mixture with a molar ratio of CaO/SiO2 = 0.83 at 200 ◦ C, is formed rapidly at
4 h. However, even if the duration of the hydrothermal curing is extended to 72 h,
a relatively high amount of semi-amorphous C–S–H (I) remains in the product. For
this reason, tobermorite-based insulation products with good physical-mechanical
properties (average density < 200 kg/m3 , compressive strength ~0.9 MPa) but limited
operating temperature (up to 700 ◦ C) can be produced.
2. The synthesis of xonotlite from industrial raw materials requires a very careful assess-
ment of the amounts of impurities and their influence on the course of hydrothermal
reactions. Impurities can react with CaO and alter the basicity of the reacting medium.
In this case, the composition of the initial mixture needs to be adjusted.
3. Sufficiently pure xonotlite must be synthesized from calcined opoka to produce
heat-resistant materials. Even a small amount of C–S–H(I) remaining in the product
increases the linear shrinkage of the samples when burned to 1000 ◦ C from 0.86 to
2% or more. Xonotlite precursors physically bind a large amount of water, resulting
in very thick suspensions with a relative volume of about 20. It has been observed,
however, that the thicker the suspension obtained during hydrothermal synthesis, the
lower the density of the formed samples.
4. High-quality heat-resistant (up to at least 1000 ◦ C) xonotlite-based products can be
made from lime–calcined opoka mixtures. Our recommended parameters are as
follows: a molar ratio of the initial mixture of CaO/SiO2 = 1.2; a water/solid ratio of
suspension W/S = 20.0; the duration of hydrothermal synthesis to be set at 220 ◦ C for
8 h and the duration of autoclaving to be set at 220 ◦ C for 4 h. The relative volume
of the suspension is ~20, the average density of the obtained samples is ~180 kg/m3 ,
and the compressive strengths exceed 1.5 MPa.
Materials 2022, 15, 3474 17 of 18

Author Contributions: Conceptualization, R.S.; methodology, A.E. and G.S.; analysis of the literature
sources, G.S., E.P. and A.E.; hydrothermal synthesis of calcium silicate hydrates and autoclaving of
products, G.S., E.P. and A.E.; data curation, R.S.; XRD analysis, A.E.; studies of STA and dilatometry,
R.S.; writing—original draft preparation, G.S., E.P. and A.E.; writing—review and editing, R.S.;
visualization, G.S.; supervision, R.S.; funding acquisition, R.S. All authors have read and agreed to
the published version of the manuscript.
Funding: This research was funded by a grant (No. S-MIP-21-4) from the Research Council of Lithuania
and the Doctoral Fund of Kaunas University of Technology No. A-410, approved 26 June 2019.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data supporting the findings of this study are available from the
corresponding author, R.S., upon reasonable request.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Coleman, N.J.; Brassington, D.S.; Raza, A.; Mendham, A.P. Sorption of Co2+ and Sr2+ by waste-derived 11 Å tobermorite. Waste
Manag. 2006, 26, 260–267. [CrossRef] [PubMed]
2. Komarneni, S.; Roy, D.M. Tobermorites: A New Family of Cation Exchangers. Science 1983, 221, 647–648. [CrossRef] [PubMed]
3. Komarneni, S.; Roy, D.M. New tobermorite cation exchangers. J. Mater. Sci. 1985, 20, 2930–2936. [CrossRef]
4. Paradiso, P.; Santos, R.L.; Horta, R.B.; Lopes, J.N.C.; Ferreira, P.J.; Colaço, R. Formation of nanocrystalline tobermorite in calcium
silicate binders with low C/S ratio. Acta Mater. 2018, 152, 7–15. [CrossRef]
5. Grangeon, S.; Claret, F.; Roosz, C.; Sato, T.; Gaboreau, S.; Linard, Y. Structure of nanocrystalline calcium silicate hydrates: Insights
from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance. J. Appl. Cryst. 2016, 49, 771–783. [CrossRef]
6. Frost, R.L.; Mahendran, M.; Poologanathan, K.; Xi, Y. Raman spectroscopic study of the mineral xonotlite Ca6 Si6 O17 (OH)2 —A
component of plaster boards. Mater. Res. Bull. 2012, 47, 3644–3649. [CrossRef]
7. Luke, K.; Taylor, H.F.W.; Kalousek, G.L. Some factors affecting formation of truscottite and xonotlite at 300–350 ◦ C. Cem. Concr.
Res. 1981, 11, 197–203. [CrossRef]
8. Liu, F.; Cao, J.X.; Zhu, B. Effect of anion impurity on preparing xonotlite whiskers via hydrothermal synthesis. Adv. Mat. Res.
2011, 148–149, 1755–1758. [CrossRef]
9. Pugovkina, Y.; Kutugin, V.; Ostroumova, A.; Rymanova, I. High temperature and heat insulated calcium silicate materials. Key
Eng. Mater. 2016, 683, 209–214. [CrossRef]
10. Akbayrak, S.; Özkar, S. Inverse relation between the catalytic activity and catalyst concentration for the ruthenium(0) nanoparticles
supported on xonotlite nanowire in hydrogen generation from the hydrolysis of sodium borohydride. J. Mol. Catal. A Chem. 2016,
424, 254–260. [CrossRef]
11. Black, L.; Garbev, K.; Stemmermann, P.; Hallam, K.R.; Allen, G.C. Characterisation of crystalline C-S-H phases by X-ray
photoelectron spectroscopy. Cem. Concr. Res. 2003, 33, 899–911. [CrossRef]
12. Ding, J.; Tang, Z.; Ma, S.; Wang, Y.; Zheng, S.; Zhang, Y.; Shen, S.; Xie, Z. A novel process for synthesis of tobermorite fiber from
high-alumina fly ash. Cem. Concr. Compos. 2016, 65, 11–18. [CrossRef]
13. Zou, J.; Guo, C.; Jiang, Y.; Wei, C.; Li, F. Structure, morphology and mechanism research on synthesizing xonotlite fiber from
acid-extracting residues of coal fly ash and carbide slag. Mater. Chem. Phys. 2016, 172, 121–128. [CrossRef]
14. Guo, X.; Meng, F.; Shi, H. Microstructure and characterization of hydrothermal synthesis of Al-substituted tobermorite. Constr.
Build. Mater. 2017, 133, 253–260. [CrossRef]
15. Grangeon, S.; Claret, F.; Lerouge, C.; Warmont, F.; Sato, T.; Anraku, S.; Numako, C.; Linard, Y.; Lanson, B. On the nature of
structural disorder in calcium silicate hydrates with a calcium/silicon ratio similar to tobermorite. Cem. Concr. Res. 2013,
52, 31–37. [CrossRef]
16. Hartmann, A.; Khakhutov, M.; Buhl, J.-C. Hydrothermal synthesis of CSH-phases (tobermorite) under influence of Ca-formate.
Mater. Res. Bull. 2014, 51, 389–396. [CrossRef]
17. Kikuma, J.; Tsunashima, M.; Ishikawa, T.; Matsuno, S.-Y.; Ogawa, A.; Matsui, K.; Sato, M. In situ Time-Resolved X-ray diffraction
of tobermorite formation process under autoclave condition. J. Am. Ceram. Soc. 2010, 93, 2667–2674. [CrossRef]
18. E`-Hemaly, S.; Mitsuda, T.; Taylor, H. Synthesis of normal and anomalous tobermorites. Cem. Concr. Res. 1977, 7, 429–438.
[CrossRef]
19. Chan, C.; Mitsuda, T. Formation of 11 Å tobermorite from mixtures of lime and colloidal silica with quartz. Cem. Concr. Res. 1978,
8, 135–138. [CrossRef]
20. Galvánková, L.; Másilko, J.; Solný, T.; Štěpánková, E. Tobermorite synthesis under hydrothermal conditions. Procedia Eng. 2016,
151, 100–107. [CrossRef]
Materials 2022, 15, 3474 18 of 18

21. Ríos, C.A.; Williams, C.D.; Fullen, M.A. Hydrothermal synthesis of hydrogarnet and tobermorite at 175 ◦ C from kaolinite and
metakaolinite in the CaO–Al2 O3 –SiO2 –H2 O system: A comparative study. Appl. Clay Sci. 2009, 43, 228–237. [CrossRef]
22. Liu, S.K.; Han, C.; Liu, J.M.; Li, H. Hydrothermal decomposition of potassium feldspar under alkaline conditions. RSC Adv. 2015,
5, 93301–93309. [CrossRef]
23. Youssef, H.; Ibrahim, D.; Komarneni, S.; Mackenzie, K.J.D. Synthesis of 11 Å Al-substituted tobermorite from trachyte rock by
hydrothermal treatment. Ceram. Int. 2010, 36, 203–209. [CrossRef]
24. Maeshima, T.; Noma, H.; Sakiyama, M.; Mitsuda, T. Natural 1.1 and 1.4 nm tobermorites from Fuka, Okayama, Japan: Chemical
analysis, cell dimensions, 29Si NMR and thermal behavior. Cem. Concr. Res. 2003, 33, 1515–1523. [CrossRef]
25. Smalakys, G.; Siauciunas, R. The synthesis of 1.13 nm tobermorite from carbonated opoka. J. Therm. Anal. Calorim. 2018, 134,
493–502. [CrossRef]
26. Panda, S.; Biswal, A.; Mishra, S.; Panda, P.K.; Pradhan, N.; Mohapatra, U.; Sukla, L.B.; Mishra, B.K.; Akcil, A. Reductive
dissolution by waste newspaper for enhanced meso-acidophilic bioleaching of copper from low grade chalcopyrite: A new
concept of biohydrometallurgy. Hydrometallurgy 2015, 153, 98–105. [CrossRef]
27. Jiménez, I.; Pérez, G.; Guerrero, A.; Ruiz, B. Mineral phases synthesized by hydrothermal treatment from biomass ashes. Int. J.
Miner. Process. 2017, 158, 8–12. [CrossRef]
28. Tsutsumi, T.; Nishimoto, S.; Kameshima, Y.; Miyake, M. Hydrothermal preparation of tobermorite from blast furnace slag for Cs+
and Sr2+ sorption. J. Hazard. Mater. 2014, 266, 174–181. [CrossRef]
29. Wang, S.; Peng, X.; Tang, L.; Zeng, L.; Lan, C. Influence of inorganic admixtures on the 11 Å-tobermorite formation prepared from
steel slags: XRD and FTIR analysis. Constr. Build. Mater. 2014, 60, 42–47. [CrossRef]
30. Hartmann, A.; Schulenberg, D.; Buhl, J.-C. Synthesis and structural characterization of CSH-phases in the range of C/S= 0.41–1.66
at temperatures of the tobermorite xonotlite crossover. J. Mater. Sci. Chem. Eng. 2015, 3, 39–55. [CrossRef]
31. Liu, F.; Chen, S.; Lin, Q.; Wang, X.D.; Cao, J.X. Study on hydrothermal synthesis dynamics of nanoscale xonotlite fibers. IOP Conf.
Ser. Mater. Sci. Eng. 2018, 292, 012050. [CrossRef]
32. Garbev, K.; Black, L.; Beuchle, G.; Stemmermann, P. Inorganic polymers in cement based materials. Wasser-Und Geotechnol. 2002,
1, 19–30.
33. Shaw, S.; Clark, S.M.; Henderson, C.M.B. Hydrothermal formation of the calcium silicate hydrates, tobermorite (Ca5 Si6 O16 (OH)2 ·
4H2 O) and xonotlite (Ca6 Si6 O17 (OH)2 ): An in situ synchrotron study. Chem. Geol. 2000, 167, 129–140. [CrossRef]
34. Kalousek, G.L.; Mitsuda, T.; Taylor, H.F.W. Xonotlite: Cell parameters, thermogravimetry and analytical electron microscopy.
Cem. Concr. Res. 1977, 7, 305–312. [CrossRef]
35. Liu, F.; Chen, S.; Lin, Q.; Wang, X.-D.; Cao, J.-X. Effect of anions from calcium sources on the synthesis of nano-sized xonotlite
fibers. Optoelectron. Lett. 2017, 13, 81–83. [CrossRef]
36. Lin, J.; Li, G.; Liu, W.; Qiu, R.; Wei, H.; Zong, K.; Cai, X. A review of recent progress on the silica aerogel monoliths: Synthesis,
reinforcement, and applications. J Mater. Sci. 2021, 56, 10812–10833. [CrossRef]
37. Liu, F.; Zeng, L.; Cao, J.; Li, J. Preparation of ultra-light xonotlite thermal insulation material using carbide slag. J. Wuhan Univ.
Technol. 2010, 25, 295–297. [CrossRef]
38. Standard EN 16977; Thermal Insulation Products for Buildings—Factory Made Calcium Silicate (CS) Products—Specification.
Technical Committee CEN/TC 88 “Thermal INSULATING Materials and Products”: Brussels, Belgium, 2020; pp. 1–34.
39. Biagoni, C.; Bonaccorsi, E.; Lezzerini, M.; Merlino, S. Thermal behaviour of Al-rich tobermorite. Eur. J. Miner. 2016, 28, 23–32.
[CrossRef]
40. Siauciunas, R.; Mikaliunaite, J.; Urbonas, L.; Baltakys, K. Tribochemical and thermal activation of α-C2 S hydrate as precursor for
cementitious binders. J. Therm. Anal. Calorim. 2014, 118, 817–823. [CrossRef]
41. Baltakys, K.; Siauciunas, R. The influence of γ-Al2 O3 and Na2 O on the formation of gyrolite in the stirring suspension. J. Mater.
Sci. 2006, 41, 4799–4805. [CrossRef]
42. Smalakys, G.; Siauciunas, R. Peculiarities of xonotlite synthesis from the raw materials with different SiO2 activities. J. Therm.
Anal. Calorim. 2020, 142, 1671–1679. [CrossRef]
43. Cao, J.; Liu, F.; Lin, Q.; Zhang, Y. Hydrothermal synthesis of xonotlite from carbide slag. Prog. Nat. Sci. 2008, 18, 1147–1153.
[CrossRef]
44. Cao, J.X.; Zhang, Y.; Zeng, L.K. Preparation of nanoporous super thermal insulation material compounded with xonotlite-SiO2 -
aerogel and characterization of the pore structure. Key Eng. Mater. 2007, 336–338, 1505–1508. [CrossRef]
45. Taylor, H.F.W. Tobermorite, jennite, and cement gel. Z. Krist. -Cryst. Mater. 1992, 202, 41–50. [CrossRef]
46. Shaw, S.; Henderson, C.M.B.; Komanschek, B.U. Dehydration/recrystallization mechanisms, energetics, and kinetics of hydrated
calcium silicate minerals: An in situ TGA/DSC and synchrotron radiation SAXS/WAXS study. Chem. Geol. 2000, 167, 141–159.
[CrossRef]