Ceramics International 45 (2019) 11233–11240

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

LaMgAl11O19 synthesis using non-hydrolytic sol-gel methods T

a a,∗ a a b
Václav Doležal , Ladislav Nádherný , Kateřina Rubešová , Vít Jakeš , Alena Michalcová ,
Ondřej Jankovskýa, Morgane Pouponc
a
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
b
Department of Metals and Corrosion Engineering, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
c
Institute of Physics of the Academy of Sciences of the Czech Republic, Cukrovarnická 10, 162 00 Prague 6, Czech Republic

ARTICLE INFO ABSTRACT

Keywords: Polycrystalline LaMgAl11O19 (LMA) was prepared by four different non-hydrolytic sol-gel methods. From stable
Lanthanum-magnesium aluminate solutions, four powder precursors containing an amorphous and nanocrystalline phase with specific reactivity
Hexagonal aluminate were obtained. The particle size, morphology, thermal behaviour, and phase composition of the powder pre-
Microstructure cursors were studied using DLS, TEM, DSC/TG and XRD. Bulk ceramic samples containing LMA were prepared at
Phase equilibria
1200 °C for 16 h and examined in terms of phase purity and microstructure using XRD, SEM, and TEM. Raman
Optical materials
spectroscopy of pure LMA was used to study the structure in detail. A mechanism of LMA formation and a
Nanograined ceramics
relation between powder precursor properties and final phase composition is proposed. These findings may be
useful for designing modern technologies for fabrication of LMA for optical or protective coating applications.

1. Introduction surface and other material properties are of interest [3].

Due to their isotropic properties, radiation resistance, and excep-
tional chemical and thermal stability aluminates are widely used for
coating or optical applications and are suitable for detection of high-
energy sources. Additionally, the greatest advantages of the lanthanum-
magnesium hexagonal aluminate are low thermal conductivity [1,2],
high melting point, low oxygen diffusion [3], and the possibility to be
doped with a high concentration of various transition metals or rare-
earth elements without concentration quenching [4,5]. LaMgAl11O19
aluminate (LMA) is a relatively new material [6]; the very first article
was published only in 1973. More notable focus on this hexaaluminate
was in the 1990's [7–9], and for the past decade LMA has been widely
studied for its attractive use as luminescence matrix, laser material
[10–12], white LED [13,14], solar-cell panels, thermal-barrier coatings
[15,16], catalysts [17] and non-contact thermometers [18]. LMA is a
high-temperature material that entails technological demands when
prepared by a solid-state method at relatively high temperatures
(1600–1700 °C) [1,4,5,13,14,19–24]. However, it does not always give
a secondary-phases free material [19,21–23]. Therefore, alternative
preparation methodologies have been proposed, such as combustion
synthesis [25,26], co-precipitation [27], reverse micro emulsion [17],
or sol-gel methods (a citrate method [16,18,23,28,29]). For thin films,
Pechini polyesterification [30] is frequently used. The effects of a pre-
paration method on LMA structure, crystallite size, density, specific
Hydrolytic sol-gel methods are disadvantaged for the different re-
activity of different metal precursor when the precursors are hydrolysed
and condensed in water. In the case of a mixed-oxide system, this can
result in a non-homogeneous material. Furthermore, water has high
surface tension, which creates a porous material when dried [31].
An advantage of non-hydrolytic sol-gel methods is the control of
homogeneity at an atomic level. This feature results in a homogeneous
and well-defined material [32]. Using non-hydrolytic sol-gel methods,
it is possible not only to achieve perfect homogeneity of the material,
but also to positively affect the reaction kinetics thus reducing the re-
action time and lowering the sintering temperature by hundreds of
degrees. In this study, phase-pure LMA was prepared at 1200 °C using
two different sol-gel polyesterification approaches described herein.
2. Experimental
Four series of bulk polycrystalline LaMgAl11O19 were prepared
using four non-hydrolytic sol-gel methods, using La3+, Mg2+ and Al3+
cations in the form of La(CH3COO)3.xH2O (99.9% REO, Strem
Chemicals), MgO (99.95%, Strem Chemicals) and AlCl3.6H2O (p. a.,
Sigma Aldrich). The lanthanum acetate polyhydrate was (before
weighing) dehydrated at 140 °C for 12 h. The first sol-gel approach was
based on active polymerisation; the first method being polyesterifica-
tion of ethylenediaminetetraacetic acid (EDTA, 99%, Penta) and

∗
Corresponding author.
E-mail address: Ladislav.Nadherny@vscht.cz (L. Nádherný).

https://doi.org/10.1016/j.ceramint.2019.02.162
Received 4 September 2018; Received in revised form 23 February 2019; Accepted 23 February 2019
Available online 25 February 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
V. Doležal, et al. Ceramics International 45 (2019) 11233–11240

Fig. 3. XRD of the LMA powder precursors prepared by the ‘PAA’ (a), ‘PVP’ (b),
‘Pechini’ (c), and ‘EDTA/TEA’ (d) sol-gel method (* – the unidentified phase).

Table 1
Phase analysis and particle size values of the powder precursors.
Precursor name/ Formula of Crystallite size Particle size
sol-gel method nanocrystalline phase from XRD (nm) from DLS (nm)

EDTA/TEA MgAl2O4 –a 22
Pechini MgAl2O4 3.2 3.8
Fig. 1. Calculated ternary phase diagram of an La2O3eAl2O3eMgO system at PVP MgAl2O4 –a 29
1500 K (1227 °C) with p(O2)/patm = 0.21. PAA LaOCl 13 19

triethanolamine (TEA, p. a., Penta), and the second Pechini poly-
esterification of citric acid and polyethylene glycol. In the second ap-
proach, two methods based on water-soluble polymers were used.
Polyvinylpyrrolidone (PVP, Mr = 29 000 g mol−1, Sigma Aldrich) and
polyacrylic acid (PAA, Mr = 100 000 g mol−1, Sigma Aldrich) were
introduced. The Al3+ cations were added in the form of an AlCl3 water
solution (12 g/L).
All three cations were mixed in a stoichiometric ratio with diluted
a
Not listed due to lack of diffraction reflexions, the value was skewed by a
high analytical uncertainty.
acetic acid (1:1). Afterwards, chelating and polymerizing agents were
added. In the EDTA/TEA method, ammonia was added to adjust the
alcality to pH ≈ 9.5. The mixture was stirred and heated at 85 °C
(consequently at 130 °C in the case of the polyesterification methods)
until a dense gel was obtained. After drying the gel and firing the metal-
organic precursor, brown and white fine powder was obtained,

Fig. 2. Thermal behaviour of La3+–Mg2+–Al3+ solutions prepared by the ‘EDTA/TEA’ (a), ‘Pechini’ (b), ‘PVP’ (c), and ‘PAA’ (d) sol-gel method measured by STA.

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V. Doležal, et al.
Fig. 4. Particle size distribution of the LMA powder precursors prepared by the
‘EDTA/TEA’ (a), ‘Pechini’ (b), ‘PVP’ (c), and ‘PAA’ (d) sol-gel method measured
by DLS.
Fig. 5. TEM images of the ‘EDTA/TEA’ (a, b) and Pechini (c, d) precursors.
respectively. This powder was uniaxially pressed at 400 MPa into bars
(with dimensions of 4 × 4 × 12 mm), which were annealed in air for
various dwell times (5 min–48 h) and varying temperatures
(1000–1500 °C). The heating and cooling rates were set to 10 and 2 °C
min−1, respectively.
Thermal behaviour was studied by means of STA. The DTA and TG
data were collected simultaneously on a Linseis STA PT1600 apparatus
at a heating rate of 10 °C min−1 from room temperature in an airflow of
50 mL min−1.
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Ceramics International 45 (2019) 11233–11240
Fig. 6. TEM images of the ‘PVP’ (a, b) and ‘PAA’ (c, d) precursors.
Fig. 7. SAED patterns of ‘Pechini’ precursor nanoparticles with continuous
diffraction rings (a) and amorphous ‘PVP’ precursor nanoparticles with crys-
talline grains proved by point diffraction maxima (b).
The phase composition of the powder precursors and final samples
were determined by XRD in a powder diffractometer Bruker D2 Phaser
in a range of 10–100° 2θ with a step size of 0.02° 2θ. For diffraction,
cobalt X-ray emission (K-α1 = 1.78901 Å, and K-α2 = 1.7929 Å) was
used. Multiple scans were merged and evaluated in the DIFFRAC.EVA
programme (ver. 4). For the phase analysis, the scans were matched
with the Bruker COD-2016.01.04 reference database [33], and refined
in the TOPAS programme ver. 5 [34] using a fundamental approach.
The profile was fitted using the Pawley and double-Voigt methods. The
phase quantification was determined by a Rietveld refinement. The
crystallite size was determined from the XRD full-profiles. With in-
strument corrections, the crystallite size was evaluated from the
broadening reflections as the integral breath calculation using Lor-
entzian and Gaussian type component convolutions.
For a detailed structural study, Raman spectroscopy was utilized.
The Raman spectra were acquired in a Stokes spectral range of
0–1200 cm−1 with a Renishaw (Yobin–Ivon) confocal Raman micro-
scope equipped with an Nd-YAG (532 nm) laser. The laser was adjusted
to minimum power in order to prevent heating of the samples.
V. Doležal, et al.
Fig. 8. STA analysis of the powder precursors prepared by the ‘EDTA/TEA’ (a), ‘Pechini’ (b), ‘PVP’ (c), ‘PAA’ (d) sol-gel methods.
Fig. 9. XRD scans of the quenched ‘EDTA/TEA’ (a), ‘PVP’ (b), and ‘PAA’ (c)
precursors; LMA ( × ), MgAl2O4 spinel (s), LaAlO3 perovskite (p).
Fig. 10. Macro photography of the prepared LMA bulk ceramics with dimen-
sions of 4 × 4 × 12 mm.
The particle-size distribution was evaluated from the dynamic-light
scattering (DLS) data measured by Zetasizer Nano ZS (Malvern,
England) in disposable silica cuvettes. Prior to the measurement, the
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Ceramics International 45 (2019) 11233–11240
powder precursor was ultrasonically dispersed in filtered demineralized
water and centrifuged at 6000 rpm for 30 min in order to separate large
conglomerates.
The microstructure of the powder precursors and final annealed
materials was studied using a EFTEM Jeol 2200 FS transmission elec-
tron microscope in a bright field with an acceleration voltage of 200 kV
(ZrO/W) and magnification up to 106×.
The surface morphology was investigated using scanning electron
microscopy (SEM) with an FEG electron source (Tescan Lyra dual-beam
microscope). To conduct the measurements, the samples were placed
on a carbon conductive tape. The SEM images were acquired with a
10 kV electron beam.
A thermodynamic model used for the calculation of the phase
equilibria of an La2O3eAl2O3eMgO system is briefly described in Refs.
[1,35]. A ternary phase diagram of the respective stoichiometric end-
members (Fig. 1) was calculated in the FactSage 6.4 programme. The
standard H°, S°, and temperature dependence of cp were adopted from
the FactSage Compound database ver. 6.4 [36]. The Gibbs energy of all
solution phases is expressed in a standard way, similarly to the previous
publications [37,38]. The presented ternary diagram was calculated for
1500 K (1227 °C) and oxygen partial pressure p(O2)/patm = 0.21.
3. Results and discussion
3.1. Precursors of LaMgAl11O19
Using four different chelating systems, La3+, Mg2+ and Al3+ ca-
tions were quantitatively dissolved forming a stable yellowish solution.
After gelation of the solution, subsequent two-step heat treatments –
drying the gel and firing the organic component – were designed ac-
cording to the thermal behaviour of the prepared solutions (Fig. 2). In
the first step, to remove free and bound water, the gels were dried at
V. Doležal, et al.
Fig. 11. XRD refined patterns of the LMA ceramics prepared by the ‘EDTA/TEA’
method (a; indexed with LMA hkl indexes), ‘Pechini’ (b), ‘PVP’ (c), and ‘PAA’ (d)
method; observed (black) and calculated (red) pattern, difference plot (green),
and background (blue). (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
250 °C for 2.5 h. After drying, a solid, deep brown shapeless matter was
obtained, which was ground and fired in air at 800–900 °C for 2.5 h.
The specific firing temperature of the dried (and partly decomposed)
gels was set according to the DSC analysis. The ‘PVP’, ‘PAA’, and
‘EDTA/TEA’ precursors were fired at 800 °C, and the Pechini precursor
was fired at 900 °C. An exothermic peak, observed at this temperature
region (at 810 °C), suggests nanoparticles formation in the powder
precursor (described in the next paragraphs). Such an exothermic peak
in this temperature region was clearly detected only in the ‘Pechini’
solution (Fig. 2-b). In the other solutions, this exothermic peak was
negligibly small due to a high ratio of the organic to inorganic com-
ponent.
Due to specific bonding and non-bonding metal-ligand interactions,
each solution underwent noticeably different decomposition stages.
While ‘EDTA/TEA’ and ‘Pechini’ solutions decomposed in a narrow
temperature interval with a maximum exothermic effect at 470 °C and
455 °C, respectively (Fig. 2-a, b), the second two – ‘PVP’ and ‘PAA’
solutions continually decomposed between ≈350 °C and 500 °C (Fig. 2-
c, d). These thermic distinctions likely affected nucleation of nano-
particles, phase composition, and amorphous content in the powder
precursors. While the gradual decomposition led to larger particles
having more time for growing, the abrupt decomposition favoured
short nucleation and formation of small particles as commented below.
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Ceramics International 45 (2019) 11233–11240
After firing the solid brown matter and decomposing the organic
component, white amorphous powder was obtained. All four powder
precursors contained a fraction of nanocrystalline and amorphous
phase. The XRD maxima matched the MgAl2O4 phase with the Fd-3m
space group and a unit-cell parameter of a = 7.958 Å (Fig. 3-b, c, d).
The highest amount of spinel nanoparticles was in the ‘Pechini’ pre-
cursor (Fig. 3-b) from which the spinel unit-cell parameter was calcu-
lated. The spinel phase is considered an intermediate phase [3]. This
precursor also contained a sharp reflection at 31.05° 2θ (Fig. 3-b,
marked with an asterisk), which did not match any considered phase
containing at least one cation used. Despite the same starting stoi-
chiometric ratio of the metal ions used, only ‘PAA’ precursor contained
a crystalline fraction identified as the tetragonal LaOCl phase with the
P4/nmm space group and unit-cell parameters of a = 4.1221 Å, and
c = 6.8964 Å (Fig. 3-a). This phase was recently synthesised using a sol-
gel method to prepare luminescent nanoparticles [39].
The crystallite size values of the major phase in the powder pre-
cursors produced by each method are listed in Table 1. The average
particle size of the powder precursors (evaluated from the DLS method)
fell into a range of 3–30 nm (Fig. 4). The smallest particles (≈3.8 nm)
were prepared by Pechini polyesterification. The particles produced by
the other three methods (‘EDTA/TEA, PVP, and PAA’) were comparable
in size – approximately 20–30 nm. Small particles are patently one of
the presumptions of high precursor reactivity that is favourable for
preparing a single-phase material. As shown later in this work, it is also
the precursor particle morphology that apparently plays an important
role in the reactivity and final phase composition.
The morphology and crystallinity of the precursor particles ob-
served by TEM were other interesting features contributing to the ex-
planation of the precursors' different reactivity. While the precursors
prepared by the ‘EDTA/TEA’ and ‘Pechini’ method contained only one
type of cobble-shaped nanoparticles (Fig. 5), the precursors prepared
using water-soluble polymers contained cobble-shaped and needle-
shaped particles (Fig. 6). The nanocrystalline structure of the precursor
particles was confirmed by the selected-area electron diffraction
(SAED) patterns (Fig. 7). The ‘Pechini’ precursor nanoparticles showed
continuous diffraction rings, in comparison to the ‘PVP’ precursor
(containing amorphous and crystalline grains) showing one broad dif-
fraction ring and spot reflections. Despite the comparable particle size
of ‘EDTA/TEA’ precursor with the ‘PVP’ and ‘PAA’ precursors, the
morphology of the particles should also be considered a kinetics af-
fecting parameter.
Thermal behaviour of the powder precursors is shown in Fig. 8. An
exothermic effect at ≈1100 °C is related to the crystallization of LMA
[29]. This thermic effect was remarkably stronger in the ‘EDTA/TEA’
and ‘Pechini’ precursors (compared to the other two), which could be
ascribed to high precursor reactivity. Another exothermic effect at
785 °C (the ‘PVP’ and ‘PAA’ precursors) and 850 °C (the ‘EDTA/TEA’
precursor) is related to the formation of an intermediate crystalline
phase [3]. In the case of the ‘PVP’ and ‘PAA’ precursors, the MgAl2O4
and LaAlO3 phases were detected, similar to when LMA was prepared at
1100 °C by a citric-acid sol-gel method [29]. The intermediate phase in
the ‘EDTA/TEA’ precursor was MgAl2O4. This precursor also contained
LMA. These phases were confirmed by XRD analysis (Fig. 9) of the
samples quenched at a temperature 100 °C higher than the respective
first exothermic peak of each powder precursor. Since such an exo-
thermic effect was not observed in the ‘Pechini’ precursor, we can an-
ticipate direct crystallization of the LMA phase without formation of
any other intermediate phase (apart from the spinel nanoparticles
contained in the precursor). This mechanism again suggests high re-
activity of the ‘EDTA/TEA’ and especially ‘Pechini’ precursors, in which
the LMA phase is formed more directly in contrast to the polymer
precursors. Based on the STA analysis, the final annealing temperature
was set to 1200 °C.
V. Doležal, et al. Ceramics International 45 (2019) 11233–11240

or 24 h [21,22]. In one thermal aging study of plasma sprayed LMA,

Fig. 12. Crystal structure of hexagonal LaMgAl11O19 (La – purple, Mg – orange,
Al – blue, O – red) adopted from ICSD (collection code 48171 [25]). (For in-
terpretation of the references to colour in this figure legend, the reader is re-
ferred to the Web version of this article.)
3.2. Bulk LaMgAl11O19 hexaaluminate ceramics
The bulk ceramics in the form of small firm white blocks (Fig. 10)
were prepared at 1200 °C for 16 h. The phase composition of these
ceramic samples is shown in the refined XRD patterns for which a re-
presentative sample of each sol-gel method was selected (Fig. 11). All
prepared samples contained lanthanum-magnesium aluminate (LaM-
gAl11O19, LMA) crystalizing in a hexagonal structure (Fig. 12) with the
P63/mmc space group [1,19,28]. The XRD profiles were fitted to the
LMA structure model with the unit-cell parameters of a = 5.592 Å,
c = 21.965 Å (ICSD collection code 48171). Only the samples prepared
from the ‘EDTA/TEA’ and ‘Pechini’ precursors were single-phase. The
samples prepared from the ‘PVP’ and ‘PAA’ precursors contained a small
amount of an LaAlO3 and corundum phase. These phases were antici-
pated in our calculated ternary phase diagram (Fig. 1). A small amount
of an LaAlO3 secondary phase was also detected in LMA prepared by a
solid-state method when sintered at 1600 °C for 8–12 h [19], 12 h [22],
both secondary phases LaAlO3 and corundum were present [1]. In our
case, the formation of these secondary phases is likely ascribed to a
thermodynamically enhanced effect towards the formation of more
stable phases. In contrast, the phase-pure LMA ceramics were likely
formed due to favourable reaction kinetics, and high reactivity of the
precursor nanoparticles outweighing the thermodynamic effect.
The refined unit-cell parameters of the LMA prepared by a re-
spective sol-gel method are compared in Table 2. The ‘EDTA/TEA’
samples had slightly larger unit-cell volume (comparing to the ICSD
model) and the lowest crystallite density, which could be due to a
higher concentration of micro defects or subtle non-stoichiometry in the
structure [40]. The lattice parameters of LMA described here are,
however, similar to those of LaMgAl11O19 prepared in the previous
research in which this structure was prepared by SPS [41] or a solid-
state method [5]. The particle size of the prepared single-phase LMA
ceramics (refined from the XRD patterns) was in a range of 26–36 nm
(Table 2).
The Raman spectrum of the ‘EDTA/TEA’ sample (Fig. 13) measured
from −10 to 1200 cm−1 contained 16 active modes (Table 3) of 42
total modes expected based on the group theory analysis [41]. No signal
of secondary phases (as crystallized in the ‘PVP’ and ‘PAA’ samples) was
detected. Two marginal modes (at 67 and 135 cm−1) could be assigned
to the E1g mode, which is related to the vibration of the LMA spinel
block [3]. The signals at 768, 805 and 860 cm−1 are probably related to
the A1g mode of the AlO6 octahedral, AlO5 bipyramidal, and AlO4 tet-
rahedral symmetry, respectively; by analogy to barium hexaferrite with
the same symmetry group [42]. Interestingly, only one Raman mode
(ascribed to an AlO6 octahedral asymmetric stretching mode at
≈1405 cm−1) was detected when LMA had been prepared by a sol-gel
method as a precursor for SPS [41].
Using SEM, the surface of the polycrystalline bulk samples were
analysed (Fig. 14). The prepared bulk ceramics were sintered into very
fine grains and compact bulk with minimum cracks or other defects. A
more defined crystalline structure was confirmed in the TEM micro-
graphs, in which the crystal clusters with needle-shaped nano-crystal-
lites were observed (Fig. 15, left). These nano-crystallites had a width
(≈35 nm) similar to the calculated width (as L-Volume IB) from the
XRD full profiles. At higher magnification, fringes were observed with
very regular crystal periodicity (Fig. 15, right) which demonstrates a
high material quality and thus a convenient preparation method.
4. Conclusion
The nanoparticle precursors prepared by the non-hydrolytic sol-gel
methods favourably enhance the formation kinetics of the LaMgAl11O19
aluminate. Consequently, the synthesis temperature was approximately
400 °C lower compared to any solid-state method. The mechanism of
LMA crystallization led through the intermediate MgAl2O4 and/or
LaAlO3 phases. The intermediate phase composition depends on the
precursor and sol-gel method used. The microstructure and particle

Table 2
Unit-cell parameters of LaMgAl11O19 prepared with different sol-gel methods
Sol-gel method Unit-cell parameter a Unit-cell parameter c Unit-cell volume V Crystallite density L-Volume IBa Secondary phase(s), wt. Agreement indices
(Å) (Å) (nm3) ρ(g cm−3) (nm) %
R Rwp GOF

EDTA/TEA 5.6181 21.9988 601.329 7.27 36 ± 2 0 4.08 5.35 1.59

Pechini 5.5934 21.9038 593.488 7.37 26 ± 1 0 3.91 5.03 1.29
PVP 5.5893 21.9392 593.570 7.37 34 ± 2 LaAlO3, 7.6 5.37 7.07 1.72
Al2O3, 20.5
PAA 5.5951 21.9724 595.714 7.34 35 ± 2 LaAlO3, 7.5 4.61 5.97 1.45
Al2O3, 3.8

a
L-Volume IB is the volume weighted apparent crystallite size.

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V. Doležal, et al. Ceramics International 45 (2019) 11233–11240

Fig. 13. Raman spectrum of the LMA ceramics prepared by the ‘EDTA/TEA’
method.

Table 3
Raman modes in polycrystalline LMA prepared by the ‘EDTA/TEA’ method.
No. Raman shift (cm−1) Relative intensity (%)

1 67 55
2 135 40
3 224 62
4 288 59
5 391 73
6 442 97
7 472 100
8 518 72 Fig. 15. TEM images of the LMA polycrystalline fine ceramics prepared by the
9 539 75 ‘EDTA/TEA’ (a, b), ‘Pechini’ (c, d) method.
10 607 47
11 650 63
12 680 58 reactivity. The powder precursors containing one type of particle (such
13 768 50 as cobbles in ‘EDTA/TEA’ and Pechini precursor) resulted in phase-pure
14 805 95
nanograined compact LMA ceramics with a high degree of crystallinity.
15 860 50
16 967 26 These findings imply that not only particle size, but also particle
morphology plays an important role in reactivity, thus, final structure
of the prepared material. These results will be useful for designing new
methods for producing doped lanthanum aluminates with low techno-
logical and energetic demands. In the case of LMA, doping with other
elements used for its functionalization can lead to highly homogenous
ceramics prepared by the sol-gel methods published herein.

Acknowledgement

This work was supported by the Czech Science Foundation, grant N°

17-13161S, and by The Ministry of Education of the Czech Republic
grant N° 21-SVV/2019 for specific university research. Many thanks
belong to Emilly Schroering, BSc. for her help with the improvement of
the English language in this article.

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mechanism of nucleation that produced nanoparticles with different
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