ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2023, Vol. 68, No. 12, pp. 1744–1751.

© Pleiades Publishing, Ltd., 2023.

Russian Text © The Author(s), 2023, published in Zhurnal Neorganicheskoi Khimii, 2023, Vol. 68, No. 12, pp. 1722–1730.

SYNTHESIS AND PROPERTIES

OF INORGANIC COMPOUNDS

Low-Temperature Synthesis
of Highly Dispersed Strontium Aluminate
L. O. Kozlovaa, *, Yu. V. Ionia, b, A. G. Sona, G. A. Buzanova, G. P. Murav’evac, and I. V. Kozerozhetsa
a Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
b Moscow Aviation Institute (National Research University), Moscow, 125993 Russia
c
Moscow State University, Moscow, 119991 Russia
*e-mail: [email protected]
Received June 16, 2023; revised August 11, 2023; accepted August 18, 2023

Abstract―A new method for producing highly dispersed strontium aluminate with specified properties (low
bulk density, particle size and shape) is described. The essence of the method is the sequential multi-stage
heat treatment of a concentrated water-carbohydrate solution of Al(NO3)3, Sr(NO3)2, and D-glucose. The
final product has a molar ratio of SrO : Al2O3 = 1 : 1. The main stages of the synthesis have been characterized
by X-ray powder diffraction, SEM, and TEM methods. The initial stages of crystallization of SrAl2O4 upon
heating at 1400°C have been revealed.

Keywords: strontium aluminate, sol-gel method, heat treatment, specified properties, hydrothermal treatment
DOI: 10.1134/S0036023623602374

INTRODUCTION earth elements as an effective emitter in various solid-

Currently, the problem of the synthesis of highly state matrices is well known [20].
dispersed strontium aluminates is becoming increas- In industry, strontium aluminate is produced by
ingly relevant due to their widespread use in various various modifications of high-temperature solid-
fields of industry: in the construction industry (pro- phase synthesis [21]. Currently, due to the increase in
duction of various structural materials, including the CO2 emissions into the atmosphere during high-tem-
production of cement for refractory concrete) [1]; perature combustion, “soft chemistry” methods [22,
electrical industry (as a phosphor in fluorescent 23] are becoming a priority [24]. These methods include
lamps) [2]; textile industry (coloring fabric with fluo- the sol-gel method [25], extraction-pyrolytic method
rescent dyes) [3], in medicine (a new type of marker [26], and hydrothermal treatment method [27–29].
for biomedical use) [4], as well as in the manufacture The SrO–Al2O3 system may contain many differ-
of radiation barriers [5]. According to studies [6–14], ent modifications of strontium aluminate, among
phosphors based on strontium aluminates have which SrAl12O19, SrAl4O7, Sr3Al2O6, SrAl2O4, and
intense emission depending on the percentage of Sr4Al2O7 are thermodynamically stable [30]. Sr4Al2O7
alloying element input. They are used in the manufac- has two modifications: high-temperature α-Sr4Al2O7,
ture of luminous paints for marking roads, runways, stable in the temperature range 1320–1690°С, and
ceramic products, warning signs and escape routes, low-temperature β-Sr4Al2O7, stable in the temperature
watch dials, emergency lighting for rooms, mines,
stairs, as well as projection screens, etc. [15, 16]. The range 1125–1320°С. It is known that the low-tem-
use of strontium aluminate for artificial lighting perature modification of β-Sr4Al2O7 forms solid solu-
reduces energy consumption, which provides environ- tions with alumina (Sr3Al2O6) [31].
mental benefits against light pollution [17]. Monoclinic α-SrAl2O4 is unique among other stron-
Strontium-based aluminate phosphors have a long tium aluminates because it can exhibit luminescence
afterglow time, high quantum efficiency, chemical upon elastic deformation [32]. This is due to the lowest
stability, and excellent luminescent properties, which symmetry in the monoclinic structure, which is required
makes them suitable candidates to replace the well- to improve optical-mechanical devices [30]. This discov-
known phosphors based on rare earth elements [18]. ery was used as a guide for the development of durable
Strontium aluminates have become the objects of in- luminescent materials with elastic deformation.
depth research due to their excellent luminescent The purpose of this study is to develop a new low-
properties and long-term phosphorescence retention temperature approach to the synthesis of highly dis-
at low temperatures [19]. In addition, the role of rare persed strontium aluminate with reproducible and

1744
 LOW-TEMPERATURE SYNTHESIS 1745

Al(NO3)3·9H2O + Sr(NO3)2
Heat treatment
T = 500–1400qС
D-C6H12O6
Nano-sized
strontium
aluminate
95qС powder
Evaporation

Gel

Fig. 1. Scheme for the synthesis of highly dispersed strontium aluminates.

specified properties, such as low bulk density, particle samples were placed on a holder, which was placed
size, and shape. inside a chamber with a vacuum of 10–6 mbar. The
accelerating voltage when obtaining images in second-
EXPERIMENTAL ary scattered electrons was 1–10 kV, and the aperture
was 30 μm. Transmission electron microscopy (TEM)
Preparation of strontium aluminate by low-tempera- was performed on a JEOL Jem-1011 instrument at an
ture synthesis. The developed approach is based on the accelerating voltage of 80 kV. The samples were
method of burning a concentrated water-carbohydrate applied to copper grids coated with carbon film by
solution proposed [21, 22, 28, 29, 33]. The general ultrasonic atomization of an aqueous suspension
scheme for the synthesis of strontium aluminates is and then placed inside a chamber with a vacuum of
shown in Fig. 1. 6–10 mbar. IR absorption spectra of the samples were
To obtain a water-carbohydrate solution, alumi- recorded on a Bruker Alpha IR Fourier spectrometer
num nitrate Al(NO3)3∙9Н2О (20.79 g) and strontium with a Platinum ATR attachment in the range of 400–
nitrate Sr(NO3)2 (4.02 g) were dissolved in distilled 4000 cm–1, scanning step 4 cm–1. The analysis of the
water (200 mL). After adding D-glucose (m(C6H12O6) = obtained IR spectra was carried out on the basis of lit-
16 g), the resulting solution was evaporated at 95°C for erature and reference data.
4 h to obtain a gel. When using these samples in the
final product, the molar ratio of SrO : Al2O3 was 1 : 1. Fluorescence spectroscopy was carried out on a
The introduction of D-glucose into the reaction Perkin Elmer LS 55 single-beam spectrometer. Oper-
solution prevents the agglomeration of strontium alu- ating parameters: excitation source, 150 W xenon lamp
minate particles by foaming and creating a carbon operating in pulsating mode with a frequency of 50 Hz,
matrix around the particles. Multi-stage heat treat- Monk–Jillison type monochromator, wavelength
ment in air at temperatures up to 1400°C for 6 h leads range 200–700 nm with spectral slits width 4 nm
to burn out excess carbon. (excitation), 4 nm (emission), and a scanning speed of
Study of samples. The determination of the phase 300 nm/min. The excitation wavelength was chosen
composition of the obtained samples was carried out based on data from the electronic absorption spectrum
on a Bruker D8 Advance instrument in reflection of the sample.
mode with CuKα radiation (40 kV, 40 mA, λ = Samples were analyzed for C, H, and N content on
1.54056 Å) with a scanning step of 4°/min. The mor- an EA1108 CarloEbra Instruments analyzer (Italy).
phology of the particles was studied using a Carl Zeiss Combustion of samples obtained at different firing
Supra 40 scanning electron microscope (SEM). The
temperatures was ensured by adding Co2O3 to the cap-
sule. A sample weighing <1 mg was burned automati-
Table 1. Properties of strontium aluminate synthesized cally in the reaction tube of the analyzer at 980°C with
after heat treatment of carbon-containing gel with Sr2+ and a pulsed supply of oxygen. A complete analysis of
Al3+ at 1400°C combustion products was carried out using a thermal
Parameter Value conductivity detector with computer processing of the
obtained chromatographic data.
Bulk density, g/cm3 0.0015
Particle size, nm 30–70 Thermal conductivity was measured using an
ITP-MG4 Zond device manufactured by SKB Stroi-
Thermal conductivity coefficient, W/(m2 K) 0.03 pribor.

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

1746 KOZLOVA et al.

PDF 00-010-0061 SrAl2O4

I
PDF 00-010-0066 SrAl12O19

PDF 00-028-1203 Sr3Al2O6

PDF 00-001-0886 J-Al2O3

PDF 01-071-2393 Sr(CO3)

2
1
20 40 60
2T, deg

Fig. 2. X-ray diffraction patterns of samples obtained after thermal treatment of a carbon-containing gel with Sr2+ and Al3+ at (1)
500, (2) 900, (3) 1000, (4) 1100, (5) 1200, and (6) 1400°C.

RESULTS AND DISCUSSION spherical nanosized particles with an average size of

30–70 nm.
Figure 2 shows diffraction patterns of samples A generalized scheme of transformations of stron-
obtained by burning an aqueous-carbohydrate solu- tium aluminates during heat treatment up to 1400°C is
tion with Sr2+ and Al3+ salts at 500 (1), 900 (2), 1000 (3), presented in Fig. 5. Heating a water-carbohydrate
1100 (4), 1200 (5), and 1400°C (6). According to the solution with Sr2+ and Al3+ salts at 1100°C leads to the
diffraction pattern (Fig. 2, curve 1), sample 1 is X-ray appearance of SrAl4O7 inclusions in the dominant
amorphous with trace inclusions of SrCO3 (PDF-01- phase of SrAl2O4. During subsequent heating, the
071-2393), which is formed when the element-con- Sr3Al2O6 phase transforms into the SrAl12O19 phase,
taining Sr2+ matrix is heated in air under conditions of which is remained as an inclusion up to 1400°C.
access to CO2 and an excess of carbon-containing Thus, according to the X-ray powder diffraction
compounds during combustion of D-glucose. The data, with increasing heating temperature, phases with
SEM image (Fig. 3a) of sample 1 shows enlarged an increased content of aluminum relative to stron-
blocks of an element-containing organic matrix with tium begin to form in the sample.
an average size of 100 μm, while the TEM image The X-ray powder diffraction results correlate with
shows that the blocks consist of smaller accumulations the IR spectroscopy data (Fig. 6). The IR spectrum of
of particles with an average size of 1 μm. the sample obtained by heat treatment at 1000 and
Upon subsequent heating at 900°C, according to 1100°C contains bands at 672 and 731 cm–1, which
X-ray diffraction (Fig. 2, curve 2), the sample is a mix- apparently correspond to vibrations of SrAl4O7, the
ture of SrAl2O4 (PDF 00-010-0061) and Sr3Al2O6 phase of which disappears when heated to 1400°C.
(PDF 00-028-1203), and trace inclusions are also SEM and TEM images (Fig. 7) of a sample
remained in SrCO3. According to SEM data (Fig. 4a), obtained by heating an aqueous-carbohydrate solution
synthesized sample 2 also represents enlarged agglom- with Sr2+ and Al3+ salts at 1400°C make it possible to
erates, which, according to TEM (Fig. 3b), consist of record the initial stages of melting of SrAl2O4 with

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

 LOW-TEMPERATURE SYNTHESIS 1747

(а) (b)

30 Pm 100 nm

Fig. 3. (a) SEM and (b) TEM image of a sample obtained after heat treatment of a carbon-containing gel with Sr2+ and Al3+ at
a temperature of 500°C.

(а) (b)

30 Pm 100 nm

Fig. 4. (a) SEM (b) and TEM of a sample obtained after heat treatment of a carbon-containing gel with Sr2+ and Al3+ at a tem-
perature of 900°C.

crystallization on the surface of needle-shaped crystals Table 1 shows the properties of strontium alumi-
of SrAl12O19. TEM images (Fig. 7c) show that crystal- nate synthesized by heating a concentrated water-car-
lization nuclei at the initial stages are in the nanoscale bohydrate solution of Sr2+ and Al3+ salts at 1400°C.
range. According to data [24], the melting point of Table 2 shows the analysis of the content of C, H,
SrAl2O4 is ~1800°C; thus, obtaining the initial compo- N in wt % depending on the processing temperature of
nents in the nanoscale range makes it possible to a concentrated water-carbohydrate solution of
reduce the melting point of SrAl2O4. Al(NO3)3 and Sr(NO3)2.

Table 2. Content of C, H, N (in wt %) depending on the temperature of processing of carbon-containing gel with Sr2+ and Al3+
T, °С
Element
150 250 350 450 550 650 750 850 950
С 22.91 37.62 34.51 8.93 5.72 1.16 0.35 – –
Н 5.03 2.56 2.54 2.42 2.39 0.26 0.24 0.11 –
N 5.71 2.25 2.19 0.72 – – – – –
Dash corresponds to “not defined.”

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

1748 KOZLOVA et al.

Sr(NO3)2 500qС X-ray amorphous 900qС

Al(NO3)3 intermediate SrAl2O4
D-C6H12O6 form Sr3Al2O6
H2 O

1000qС

SrAl2O4 1200qС SrAl2O4 1100qС

SrAl4O7 Sr3Al2O6 SrAl2O4
SrAl12O19 SrAl4O7 Sr3Al2O6

1400qС

SrAl2O4
with inclusions
of SrAl12O19

Fig. 5. Generalized scheme of transformations of strontium aluminates during heat treatment up to 1400°C.

I 3

527 893
553
801 2
464
592 838
613
445 640 771
412
1

731
672

400 500 600 700 800 900 1000 1100

Q, cm–1

Fig. 6. IR spectra of strontium aluminates obtained after heat treatment of carbon-containing gel Sr2+ and Al3+ at temperatures
of 1000 (1), 1100 (2), 1400°C (3).

Figures 8 and 9 present the results of a study of the length of 253 nm, the spectrum contains bands at 447 nm,
fluorescent properties of strontium aluminate powders corresponding to violet, at 459 nm (blue), at 484 nm
synthesized at temperatures up to 1400°C. As can be (blue), at 529 and 542 nm (green). When excited in the
seen from the graph (Fig. 9), at an excitation wave- visible region of the spectrum at 400 nm (Fig. 8), the

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

 LOW-TEMPERATURE SYNTHESIS 1749

(а)

3 Pm

(b)

1 Pm

(c)

100 nm

Fig. 7. (a, b) SEM and (c) TEM image of a sample obtained after heat treatment of a carbon-containing gel with Sr2+ and Al3+
at a temperature of 1400°C.

same bands are retained. However, the band at 447 nm CONCLUSIONS

is split into two with maxima at 440 and 446 nm. As
shown in the graphs (Figs. 8, 9), the most intense flu- A new low-temperature approach to the synthesis
orescence appears in a sample of strontium aluminate of highly dispersed strontium aluminate powders is
obtained by burning an element-containing polymer presented, which consists of sequential multi-stage
matrix at 1100°C. heat treatment of a concentrated aqueous-carbohy-
Structural materials based on synthesized stron- drate solution of Al(NO3)3, Sr(NO3)2, and D-glucose
tium aluminate have high refractory properties and up to 1400°C. The intermediate stages of the synthesis
can serve as the basis for producing phosphors with a are characterized. The role of D-glucose in the syn-
long afterglow time at low temperatures [8–13]. thesis of powders with low bulk density has been estab-

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

1750 KOZLOVA et al.

Fluorescence spectra, Oexc = 400 nm

400 1000qС
446
440 1100qС
1200qС
459 1300qС
1400qС
900qС
IFLUO 484 700qС
542 800qС
200
529 500qС

0
400 450 500 550 600 650
O, nm

Fig. 8. Fluorescence spectra of strontium aluminate samples at λexc = 400 nm.

Fluorescence spectra, Oexc = 253 nm

1000
1000qС
484
1100qС
800 1200qС
459 1300qС
447 1400qС
600 900qС
484 700qС
IFLUO

800qС
400 529 500qС
542

200

400 450 500 550 600 650

O, nm
Fig. 9. Fluorescence spectra of strontium aluminate samples at λexc = 253 nm.

lished. The initial stages of crystallization of SrAl2O4 at ACKNOWLEDGMENTS

a heating temperature of 1400°C were revealed. Based
on the fluorescence spectra, nanosized particles of X-ray diffraction studies were carried out using the
strontium aluminate showed a good response in a wide equipment of the Center for Collective Use of the Physical
wavelength range, which suggests the manifestation of Research Methods at the Kurnakov Institute of General and
stable luminescent properties at room temperature Inorganic Chemistry, Russian Academy of Sciences. For
when doped with rare earth elements. SEM studies, we used the equipment of the Educational

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 68 No. 12 2023

 LOW-TEMPERATURE SYNTHESIS 1751

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