Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route
A new process was developed to synthesize niobium diboride (NbB₂) nanosheets with the dimension of about 500 nm and thickness of about 10 nm by using metal niobium, iodine and sodium borohydride as starting materials in an stainless steel autoclave at 700 °C. Iodine was used to facilitate the exothe...
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Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України
2018
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| Cite this: | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route / Wang Liangbiao, Shen Qianli, Qin Hengfei, Zhao Dejian, Liu Weiqiao, Sun Jianhua, Zhu Binglong, Zhou Quanfa // Надтверді матеріали. — 2018. — № 6 (236). — С. 36-40. — Бібліогр.: 15 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859586110854791168 |
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| author | Wang Liangbiao Shen Qianli Qin Hengfei Zhao Dejian Liu Weiqiao Sun Jianhua Zhu Binglong Zhou Quanfa |
| author_facet | Wang Liangbiao Shen Qianli Qin Hengfei Zhao Dejian Liu Weiqiao Sun Jianhua Zhu Binglong Zhou Quanfa |
| citation_txt | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route / Wang Liangbiao, Shen Qianli, Qin Hengfei, Zhao Dejian, Liu Weiqiao, Sun Jianhua, Zhu Binglong, Zhou Quanfa // Надтверді матеріали. — 2018. — № 6 (236). — С. 36-40. — Бібліогр.: 15 назв. — англ. |
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| description | A new process was developed to synthesize niobium diboride (NbB₂) nanosheets with the dimension of about 500 nm and thickness of about 10 nm by using metal niobium, iodine and sodium borohydride as starting materials in an stainless steel autoclave at 700 °C. Iodine was used to facilitate the exothermic reaction between metal niobium and sodium borohydride and the formation of NbB₂. X-ray powder diffraction pattern indicated that the obtained product is hexagonal phase NbB₂ with the calculated lattice constants a = 110 Å and c = 3.2929 Å. The obtained product was also studied by thermogravimetric analysis. It had good oxidation resistance below 400 °C in air.
Розроблено новий процес синтезу наношарів дибориду ніобію (NbB₂) розмірами ~ 500 нм і товщиною ~ 10 нм з використанням металічного ніобію, йоду і боргідриду натрію як вихідних матеріалів у автоклаві з нержавіючої сталі при 700 °С. Йод використовували для полегшення екзотермічної реакції між металічним ніобієм і боргідридом натрію для утворення наношарів NbB₂. Рентгенограма порошку показала, що отриманий продукт є гексагональною фазою NbB₂ з розрахованими константами решітки a = 110 Å і c = 3,2929 Å. Отриманий продукт також вивчали термогравіметричним аналізом. Він мав гарну стійкість до окиснення в повітрі за температури нижче 400 °C .
Разработан новый процесс синтеза нанослоев диборида ниобия (NbB₂2) размерами ~ 500 нм и толщиной ~ 10 нм с использованием металлического ниобия, йода и боргидрида натрия в качестве исходных материалов в автоклаве из нержавеющей стали при 700 °C. Йод использовали для облегчения экзотермической реакции между боргидридом натрия и ниобием для получения нанослоев NbB₂. Рентгенограмма порошка показала, что полученный продукт представляет собой гексагональную фазу NbB₂ с рассчитанными постоянными решетки a = 110 Å и c = 3,2929 Å. Полученный продукт также изучали с помощью термогравиметрического анализа. Он имел хорошую стойкость к окислению на воздухе при температуре ниже 400 °C .
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| first_indexed | 2025-11-27T10:39:52Z |
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http://stmj.org.ua 36
UDC 66.091:661.888.2
Liangbiao Wang*, Qianli Shen, Hengfei Qin, Dejian Zhao,
Weiqiao Liu, Jianhua Sun, Binglong Zhu, Quanfa Zhou*
*Jiangsu Key Laboratory of Precious Metals Chemistry
and Engineering, School of Chemistry and Environment Engineering,
Jiangsu University of Technology, Changzhou, P. R. China
*lbwang@jsut.edu.cn
**labzqf@jsut.edu.cn
Chemical synthesis of niobium diboride
nanosheets by a solid-state reaction route
A new process was developed to synthesize niobium diboride (NbB2)
nanosheets with the dimension of about 500 nm and thickness of about 10 nm by using
metal niobium, iodine and sodium borohydride as starting materials in an stainless
steel autoclave at 700 °C. Iodine was used to facilitate the exothermic reaction between
metal niobium and sodium borohydride and the formation of NbB2. X-ray powder diffrac-
tion pattern indicated that the obtained product is hexagonal phase NbB2 with the cal-
culated lattice constants a = 110 Å and c = 3.2929 Å. The obtained product was also
studied by thermogravimetric analysis. It had good oxidation resistance below 400 °C
in air.
Keywords: solid state route, X-ray diffraction, niobium diboride,
nanosheets, chemical synthesis.
INTRODUCTION
Niobium boride (NbB2) is an important ceramic material and has
been used in many fields for their excellent mechanical properties, such as high
melting point, high chemical stability, good electrical and thermal conductivity,
and high hardness [1–4]. In addition, Nb1–xB2 (x = 0–0.48) was a superconductor
with the maximum superconducting transition temperature at 9.2 K [5].
Up to now, several synthetic methods had been developed to synthesize NbB2
materials, such as, the carbothermal reduction of niobium pentoxide, boron and
cornstarch at 1700 °C [6], borothermal reduction of niobium pentoxide and boron
at 1600–1650 °C [7], borothermal reduction of niobium chloride, boron and acetic
acid at 1300 °C [8], self-propagating high temperature synthesis (SHS) [9], mecha-
nochemically assisted preparation [10], solid-state reaction of noibium and boron
[11]. NbB2 nanorods were prepared by a solid-state reaction of niobium chloride
and sodium borohydride at 550–650 °C [12]. Ran et al. have prepared NbB2
nanocrystallines by borothermal reduction of niobium pentoxide and boron in mol-
ten salt at 800–1000 °C [13]. A general rout towards metal boride nanocrytals had
been developed by ionothermal process at a relatively mild temperature (500–
900 °C) [14]. Torabi et al. developed a mechanical-thermal approach to synthesize
NbB2 powder from Mg/B2O3/Nb powder mixture [15]. Herein, NbB2 nanosheets
were prepared from metal niobium and sodium borohydride via an iodine-assisted
synthesis process at low temperature of 700 °C in a stainless steel autoclave.
©LIANGBIAO WANG, QIANLI SHEN, HENGFEI QIN, DEJIAN ZHAO, WEIQIAO LIU, JIANHUA SUN, BINGLONG
ZHU, QUANFA ZHOU, 2018
ISSN 0203-3119. Надтверді матеріали, 2018, № 6 37
Experimental procedure
All the reagents used in the experiments were purchased from Shanghai
Chemical Reagents Company. All manipulations in our experimental were carried
out in a glove box purged with flowing argon gas. In a typical procedure, metal
niobium (0.23 g), iodine (0.60 g) and sodium borohydride (1.00 g) were mixed and
load into a stainless steel autoclave with a capacity of about 20 mL. The autoclave
was sealed and heated in an electric stove with a heating ramp rate of 10 °C/min
from room temperature to 700 °C. The autoclave was kept at 700 °C for 10 h, and
then followed by cooling to room temperature in the furnace naturally. The product
collected from the autoclave was washed by absolute ethyl alcohol, distilled water
and dilute HCl aqueous solution for several times to remove the impurities. Finally
the final product was dried under vacuum at 60 °C for 10 h for further
characterization.
X-ray diffraction (XRD) pattern of the obtained product was performed with a
Philips X′Pert X-ray powder diffractometer using CuKα radiation (λ = 1.54178 Å).
The microstructure of the obtained product was investigated with a field-emitting
scanning electron microscope (FE-SEM, JEOL-JSM-6700F), a transmission elec-
tron microscope (TEM, H7650), and a high-resolution transmission electron mi-
croscope (HRTEM, JEOL-2010) with an accelerating voltage of 200 kV. Thermo-
gravimetric analysis (TGA) profile was performed on a Shimadzu-50 thermoana-
lyzer apparatus under flowing air below 700 °C at a rate of 10 °C/min.
RESULTS AND DISCUSSION
XRD was used to check the crystal structure and the phase purity of the
obtained product. A typical XRD pattern of the obtained product was shown in
Fig. 1. All the peaks in Fig. 1 of the (001), (100), (101), (002), (110), (102), (111),
(200), and (201) reflections can be indexed to pure hexagonal NbB2 with lattice
constants of a = 3.1170 Å and c = 3.2929 Å, which were consistent with the
reported values of hexagonal NbB2 (Joint Committee on Powder Diffraction
Standards (JCPDS) cards, No. 35-0724, a = 3.1113 Å and c = 3.2742 Å). No
impurity peaks were detected in Fig. 1, suggesting the NbB2 product with the high
purity. All peaks with strong diffraction intensity indicated the obtained NbB2 with
excellent crystallinity.
10 20 30 40 50 60 70
(2
01
)
(2
00
)
(1
11
)
(1
10
)
(0
02
)
(1
01
)
(1
00
)
(0
01
)
In
te
n
si
ty
, a
rb
. u
ni
ts
2θ, deg
Fig. 1. XRD pattern of the obtained NbB2.
FE-SEM, TEM and HRTEM were used to investigate the microstructure of the
obtained NbB2 product. The FE-SEM image of the obtained NbB2 nanosheets was
http://stmj.org.ua 38
shown in Fig. 2, a. The FE-SEM image revealed that the obtained NbB2 product
was composed of nanosheets with a dimension of about 500 nm. The TEM image
(see Fig. 2, b) of the NbB2 product showed the average thickness of NbB2
nanosheets was about 10 nm. The HRTEM image of the obtained NbB2 was shown
in Fig. 2, c. Well-resolved lattice fringes of the NbB2 nanosheets were observed in
Fig. 2, c with an average distance of 0.33 nm, which corresponded to the (001)
planes of hexagonal phase NbB2.
200 nm
500 nm 2 nm
0.33 nm
a b c
Fig. 2. SEM image of NbB2 nanosheets (a), TEM image of NbB2 nanosheets (b), HRTEM image
of NbB2 nanosheets (c).
The oxidation resistances of materials determine their application conditions.
To investigate the oxidation resistance of the obtained NbB2 product, the
thermogravimetric analysis (TGA) was carried out from room temperature to
700 °C with a heating ramp rate of 10 °C/min under flowing air. The TGA curve of
the NbB2 was shown in Fig. 3. The TGA curve showed that the weight of the
product had not changed below 400 °C. The onset of the oxidation of the NbB2
product is found to begin at about 400 °C. The oxidation rate is very slow within
400–550 °C, which may be due to the produced oxide (niobium oxide and diboron
trioxide) layer coating on the surface of the product. When the temperature is over
550 °C, the weight gain increases significantly. This may be due to the formed
protective oxide layer is destroyed and the oxidation rate increases rapidly. The
result of the TGA demonstrates that the obtained NbB2 has a good oxidation
resistance below 400 °C.
0 100 200 300 400 500 600
–5
0
5
10
15
20
25
30
35
40
W
ei
gh
t
ga
in
,
%
T, °C
Fig. 3. TGA profile of the NbB2 product under flowing air.
ISSN 0203-3119. Надтверді матеріали, 2018, № 6 39
CONCLUSIONS
In summary, we have developed an iodine-assisted approach to prepare NbB2
nanosheets with the dimensions of about 500 nm and thickness of about 20 nm in
an autoclave through the reaction of metal niobium, sodium borohydride and io-
dine as reactants. The exothermic reaction between sodium borohydride and iodine
was favorable for the final formation of NbB2 nanosheets. The NbB2 nanosheets
obtained by our designed route have anti-oxidation under 400 °C.
ACKNOWLEDGEMENTS
This work was financially supported by the Natural Science Foundation of
Jiangsu Province (No. BK20160292) and Natural Science Foundation of the
Higher Educations Institutions of Jiangsu Province (No. 16KJB150013).
Розроблено новий процес синтезу наношарів дибориду ніобію (NbB2) роз-
мірами ∼ 500 нм і товщиною ∼ 10 нм з використанням металічного ніобію, йоду і боргідриду
натрію як вихідних матеріалів у автоклаві з нержавіючої сталі при 700 °С. Йод використо-
вували для полегшення екзотермічної реакції між металічним ніобієм і боргідридом натрію
для утворення наношарів NbB2. Рентгенограма порошку показала, що отриманий продукт є
гексагональною фазою NbB2 з розрахованими константами решітки a = 110 Å і c =
3,2929 Å. Отриманий продукт також вивчали термогравіметричним аналізом. Він мав
гарну стійкість до окиснення в повітрі за температури нижче 400 °C .
Ключові слова: твердотільний шлях, рентгенівська дифракція, диборид
ніобію, наношари, хімічний синтез.
Разработан новый процесс синтеза нанослоев диборида ниобия (NbB2)
размерами ∼ 500 нм и толщиной ∼ 10 нм с использованием металлического ниобия, йода и
боргидрида натрия в качестве исходных материалов в автоклаве из нержавеющей стали
при 700 °C. Йод использовали для облегчения экзотермической реакции между боргидри-
дом натрия и ниобием для получения нанослоев NbB2. Рентгенограмма порошка показала,
что полученный продукт представляет собой гексагональную фазу NbB2 с рассчитанны-
ми постоянными решетки a = 110 Å и c = 3,2929 Å. Полученный продукт также изучали с
помощью термогравиметрического анализа. Он имел хорошую стойкость к окислению на
воздухе при температуре ниже 400 °C .
Ключевые слова: твердотельный путь, дифракция рентгеновских лу-
чей, диборид ниобия, нанослои, химический синтез.
1. Ucisik A. H., Bindal C. Fracture toughness of boride formed on low-alloy steels // Surf. Coat.
Technol. – 1997. – 94–95. – P. 561–565.
2. Otani S., Korsukova M. M., Mitsuhashi T. Floating zone growth and high-temperature hard-
ness of NbB2 and TaB2 single crystals // J. Cryst. Growth. – 1998. – 3–4. – P. 430–433.
3. Adams R. M. Boron, metallo-boron compounds and boranes. – New York: Interscience, 1964.
4. Samsonov G. V., Vinitskii I. M. Handbook of refractory compounds. – New York: Plenum
Press, 1980.
5. Yamamoto A., Takao C., Masui T., Izumi M., Tajima S. High-pressure synthesis of supercon-
ducting Nb1–xB2 (x = 0–0.48) with the maximum Tc = 9.2 K // Physica C. – 2002. – 383. –
P. 197–206.
6. Maeda H., Yoshikawa T., Kusakabe K., Morooka S. Synthesis of ultrafine NbB2 powder by
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process for the synthesis of nanocrystalline oxides and borides of niobium // Dalton Trans. –
2011. – 40. – P. 7879–7888.
9. Jin S., Shen P., Li Y., Zhou D., Jiang Q. Synthesis of spherical NbB2–x particles by controlling
the stoichiometry // Cryst. Eng. Comm. – 2012. – 14. – P. 1925–1928.
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10. Iizumi K., Sekiya C., Okada S., Kudou K., Shishido T. Mechanochemically assisted prepara-
tion of NbB2 powder // J. Eur. Ceram. Soc. – 2006. – 26. – P. 635–638.
11. Matsudaira T., Itoh H., Naka S., Hamamoto H. synthesis of niobium boride powder by solid
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P. 3550–3552.
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Received 10.04.17
Revised 08.11.17
Accepted 08.11.17
|
| id | nasplib_isofts_kiev_ua-123456789-167271 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 0203-3119 |
| language | English |
| last_indexed | 2025-11-27T10:39:52Z |
| publishDate | 2018 |
| publisher | Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України |
| record_format | dspace |
| spelling | Wang Liangbiao Shen Qianli Qin Hengfei Zhao Dejian Liu Weiqiao Sun Jianhua Zhu Binglong Zhou Quanfa 2020-03-22T17:25:15Z 2020-03-22T17:25:15Z 2018 Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route / Wang Liangbiao, Shen Qianli, Qin Hengfei, Zhao Dejian, Liu Weiqiao, Sun Jianhua, Zhu Binglong, Zhou Quanfa // Надтверді матеріали. — 2018. — № 6 (236). — С. 36-40. — Бібліогр.: 15 назв. — англ. 0203-3119 https://nasplib.isofts.kiev.ua/handle/123456789/167271 66.091:661.888.2 A new process was developed to synthesize niobium diboride (NbB₂) nanosheets with the dimension of about 500 nm and thickness of about 10 nm by using metal niobium, iodine and sodium borohydride as starting materials in an stainless steel autoclave at 700 °C. Iodine was used to facilitate the exothermic reaction between metal niobium and sodium borohydride and the formation of NbB₂. X-ray powder diffraction pattern indicated that the obtained product is hexagonal phase NbB₂ with the calculated lattice constants a = 110 Å and c = 3.2929 Å. The obtained product was also studied by thermogravimetric analysis. It had good oxidation resistance below 400 °C in air. Розроблено новий процес синтезу наношарів дибориду ніобію (NbB₂) розмірами ~ 500 нм і товщиною ~ 10 нм з використанням металічного ніобію, йоду і боргідриду натрію як вихідних матеріалів у автоклаві з нержавіючої сталі при 700 °С. Йод використовували для полегшення екзотермічної реакції між металічним ніобієм і боргідридом натрію для утворення наношарів NbB₂. Рентгенограма порошку показала, що отриманий продукт є гексагональною фазою NbB₂ з розрахованими константами решітки a = 110 Å і c = 3,2929 Å. Отриманий продукт також вивчали термогравіметричним аналізом. Він мав гарну стійкість до окиснення в повітрі за температури нижче 400 °C . Разработан новый процесс синтеза нанослоев диборида ниобия (NbB₂2) размерами ~ 500 нм и толщиной ~ 10 нм с использованием металлического ниобия, йода и боргидрида натрия в качестве исходных материалов в автоклаве из нержавеющей стали при 700 °C. Йод использовали для облегчения экзотермической реакции между боргидридом натрия и ниобием для получения нанослоев NbB₂. Рентгенограмма порошка показала, что полученный продукт представляет собой гексагональную фазу NbB₂ с рассчитанными постоянными решетки a = 110 Å и c = 3,2929 Å. Полученный продукт также изучали с помощью термогравиметрического анализа. Он имел хорошую стойкость к окислению на воздухе при температуре ниже 400 °C . en Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України Сверхтвердые материалы Одержання, структура, властивості Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route Article published earlier |
| spellingShingle | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route Wang Liangbiao Shen Qianli Qin Hengfei Zhao Dejian Liu Weiqiao Sun Jianhua Zhu Binglong Zhou Quanfa Одержання, структура, властивості |
| title | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| title_full | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| title_fullStr | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| title_full_unstemmed | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| title_short | Chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| title_sort | chemical synthesis of niobium diboride nanosheets by a solid-state reaction route |
| topic | Одержання, структура, властивості |
| topic_facet | Одержання, структура, властивості |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/167271 |
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