Exploring superhard materials is of great significance in materials research. Ternary B-C-N superhard compounds exhibit a superior thermal stability to diamond, with hardness surpassing cubic boron nitride. However, synthesizing cubic B-C-N compounds is challenging, and few studies have been reported on their high-temperature oxidation resistance, impeding their potential applications. In this study, cubic B-C-N compounds (c-BCN) were synthesized using the high-pressure high-temperature synthesis method at 10 GPa and 1530 °C, half the reported pressure and one-quarter lower than the reported temperature. The thermal stability of the obtained c-BCN compound was examined. The results indicated that the air oxidation temperature of c-BCN was as high as 1200 °C, suitable for high-speed cutting of hardened steels. This study provided a production method of cubic B-C-N superhard compounds and extended their potential applications to milling/machining.

1.
P.
Németh
,
K.
McColl
,
L. A. J.
Garvie
,
C. G.
Salzmann
,
M.
Murri
, and
P. F.
McMillan
, “
Complex nanostructures in diamond
,”
Nat. Mater.
19
,
1126
1131
(
2020
).
2.
W. J.
Zhang
,
Y. M.
Chong
,
I.
Bello
, and
S. T.
Lee
, “
Nucleation, growth and characterization of cubic boron nitride (cBN) films
,”
J. Phys. D: Appl. Phys.
40
,
6159
6174
(
2007
).
3.
S. N.
Monteiro
,
A. L. D.
Skury
,
M. G.
de Azevedo
, and
G. S.
Bobrovnitchii
, “
Cubic boron nitride competing with diamond as a superhard engineering material – an overview
,”
J. Mater. Res. Technol.
2
,
68
74
(
2013
).
4.
V. L.
Solozhenko
,
D.
Andrault
,
G.
Fiquet
,
M.
Mezouar
, and
D. C.
Rubie
, “
Synthesis of superhard cubic BC2N
,”
Appl. Phys. Lett.
78
,
1385
1387
(
2001
).
5.
N.
Dubrovinskaia
,
V. L.
Solozhenko
,
N.
Miyajima
,
V.
Dmitriev
,
O. O.
Kurakevych
, and
L.
Dubrovinsky
, “
Superhard nanocomposite of dense polymorphs of boron nitride: Noncarbon material has reached diamond hardness
,”
Appl. Phys. Lett.
90
,
101912
(
2007
).
6.
X.
Wang
,
Y.
Wang
,
M.
Zhang
, and
H.
Liu
, “
Superhard BC2N in cubic diamondlike structure
,”
Phys. Rev. B
107
,
134101
(
2023
).
7.
X.
Liu
,
X.
Jia
,
Z.
Zhang
,
M.
Zhao
,
W.
Guo
,
G.
Huang
, and
H.-A.
Ma
, “
Synthesis and characterization of new “BCN” diamond under high pressure and high temperature conditions
,”
Cryst. Growth Des.
11
,
1006
1014
(
2011
).
8.
L.
Liu
,
Z.
Zhao
,
T.
Yu
,
S.
Zhang
,
J.
Lin
, and
G.
Yang
, “
Hexagonal BC2N with remarkably high hardness
,”
J. Phys. Chem. C
122
,
6801
6807
(
2018
).
9.
H. A.
Castillo
,
P. J.
Arango
,
J. M.
Velez
,
E.
Restrepo-Parra
,
G.
Soto
, and
W.
de la Cruz
, “
Synthesis and characterization of cubic BC2N grown by reactive laser ablation
,”
Surf. Coat. Technol.
204
,
4051
4056
(
2010
).
10.
Y.
Zhang
,
H.
Sun
, and
C.
Chen
, “
Superhard cubic BC2N compared to diamond
,”
Phys. Rev. Lett.
93
,
195504
(
2004
).
11.
L.
Zhu
,
M.
Ma
,
Q.
Gao
,
B.
Li
,
X.
Wei
,
M.
Xiong
,
Z.
Zhao
, and
J.
He
, “
Prediction of a series of superhard BC4N structures
,”
Diamond Relat. Mater.
127
,
109192
(
2022
).
12.
Y.
Gao
,
Y.
Wu
,
Q.
Huang
,
M.
Ma
,
Y.
Pan
,
M.
Xiong
,
Z.
Li
,
Z.
Zhao
,
J.
He
, and
D.
Yu
, “
First principles studies of superhard BC6N phases with unexpected 1D metallicity
,”
Comput. Mater. Sci.
148
,
157
164
(
2018
).
13.
X.
Luo
,
X.
Guo
,
Z.
Liu
,
J.
He
,
D.
Yu
,
Y.
Tian
, and
H.-T.
Wang
, “
Ground-state properties and hardness of high density BC6N phases originating from diamond structure
,”
J. Appl. Phys.
101
,
083505
(
2007
).
14.
Y.
Sakai
,
S.
Saito
, and
M. L.
Cohen
, “
Electronic properties of B-C-N ternary kagome lattices
,”
Phys. Rev. B
91
,
165434
(
2015
).
15.
D.
Golberg
,
Y.
Bando
,
P.
Dorozhkin
, and
Z.-C.
Dong
, “
Synthesis, analysis, and electrical property measurements of compound nanotubes in the B-C-N ceramic system
,”
MRS Bull.
29
,
38
42
(
2004
).
16.
D.
Wang
,
R.
Shi
, and
L.-H.
Gan
, “
t-C8B2N2: A potential superhard material
,”
Chem. Phys. Lett.
669
,
80
84
(
2017
).
17.
L.
Ci
,
L.
Song
,
C.
Jin
,
D.
Jariwala
,
D.
Wu
,
Y.
Li
,
A.
Srivastava
,
Z. F.
Wang
,
K.
Storr
,
L.
Balicas
,
F.
Liu
, and
P. M.
Ajayan
, “
Atomic layers of hybridized boron nitride and graphene domains
,”
Nat. Mater.
9
,
430
435
(
2010
).
18.
S.
Tang
,
H.
Wang
,
H. S.
Wang
,
Q.
Sun
,
X.
Zhang
,
C.
Cong
,
H.
Xie
,
X.
Liu
,
X.
Zhou
,
F.
Huang
,
X.
Chen
,
T.
Yu
,
F.
Ding
,
X.
Xie
, and
M.
Jiang
, “
Silane-catalysed fast growth of large single-crystalline graphene on hexagonal boron nitride
,”
Nat. Commun.
6
,
6499
(
2015
).
19.
S. D.
Nehate
,
A. K.
Saikumar
,
A.
Prakash
, and
K. B.
Sundaram
, “
A review of boron carbon nitride thin films and progress in nanomaterials
,”
Mater. Today Adv.
8
,
100106
(
2020
).
20.
R.
Attri
,
S.
Roychowdhury
,
K.
Biswas
, and
C. N. R.
Rao
, “
Low thermal conductivity of 2D borocarbonitride nanosheets
,”
J. Solid State Chem.
282
,
121105
(
2020
).
21.
A. V.
Kurdyumov
and
V. L.
Solozhenko
, “
Shock synthesis of ternary diamond-like phases in the B-C-N system
,”
Powder Metall. Met. Ceram.
39
,
467
473
(
2000
).
22.
Q.
Wu
,
Z.
Liu
,
Q.
Hu
,
H.
Li
,
J.
He
,
D.
Yu
,
D.
Li
, and
Y.
Tian
, “
The thermal expansion of a highly crystalline hexagonal BC2N compound synthesized under high temperature and pressure
,”
J. Phys. Condens. Matter
18
,
9519
9524
(
2006
).
23.
Y.
Zhao
,
D. W.
He
,
L. L.
Daemen
,
T. D.
Shen
,
R. B.
Schwarz
,
Y.
Zhu
,
D. L.
Bish
,
J.
Huang
,
J.
Zhang
,
G.
Shen
,
J.
Qian
, and
T. W.
Zerda
, “
Superhard B–C–N materials synthesized in nanostructured bulks
,”
J. Mater. Res.
17
,
3139
3145
(
2002
).
24.
P.
Wang
,
D.
He
,
L.
Wang
,
Z.
Kou
,
Y.
Li
,
L.
Xiong
,
Q.
Hu
,
C.
Xu
,
L.
Lei
,
Q.
Wang
,
J.
Liu
, and
Y.
Zhao
, “
Diamond-cBN alloy: A universal cutting material
,”
Appl. Phys. Lett.
107
,
101901
(
2015
).
25.
B.
Xu
,
H.
Du
,
B.
Yang
,
Z.
Ding
,
X.
Wang
,
Y.
Wang
,
Z.
Li
,
Y.
Li
,
B.
Yao
,
H.-A.
Ma
, and
Y.
Lan
, “
Ternary B-C-N compounds layered materials with regulated electronic properties ultrawide bandgaps
,”
Appl. Phys. Lett.
122
,
182108
(
2023
).
26.
P.-E.
Werner
,
L.
Eriksson
, and
M.
Westdahl
, “
TREOR, a semi-exhaustive trial-and-error powder indexing program for all symmetries
,”
J. Appl. Crystallogr.
18
,
367
370
(
1985
).
27.
S. K.
Sharma
,
H. K.
Mao
,
P. M.
Bell
, and
J. A.
Xu
, “
Measurement of stress in diamond anvils with micro-Raman spectroscopy
,”
J. Raman Spectrosc.
16
,
350
352
(
1985
).
28.
D.
Schiferl
,
M.
Nicol
,
J. M.
Zaug
,
S. K.
Sharma
,
T. F.
Cooney
,
S. Y.
Wang
,
T. R.
Anthony
, and
J. F.
Fleischer
, “
The diamond 13C/12C isotope Raman pressure sensor system for high-temperature/pressure diamond-anvil cells with reactive samples
,”
J. Appl. Phys.
82
,
3256
3265
(
1997
).
29.
E.
Knittle
,
R. B.
Kaner
,
R.
Jeanloz
, and
M. L.
Cohen
, “
High-pressure synthesis, characterization, and equation of state of cubic C-BN solid solutions
,”
Phys. Rev. B
51
,
12149
12155
(
1995
).
30.
H. W.
Hubble
,
I.
Kudryashov
,
V. L.
Solozhenko
,
P. V.
Zinin
,
S. K.
Sharma
, and
L. C.
Ming
, “
Raman studies of cubic BC2N, a new superhard phase
,”
J. Raman Spectrosc.
35
,
822
825
(
2004
).
31.
K. S.
Park
,
D. Y.
Lee
,
K. J.
Kim
, and
D. W.
Moon
, “
Observation of a hexagonal BN surface layer on the cubic BN film grown by dual ion beam sputter deposition
,”
Appl. Phys. Lett.
70
,
315
317
(
1997
).
32.
K.
Nose
,
H.
Oba
, and
T.
Yoshida
, “
Electric conductivity of boron nitride thin films enhanced by in situ doping of zinc
,”
Appl. Phys. Lett.
89
,
112124
(
2006
).
33.
E.
Pascual
,
E.
Martínez
,
J.
Esteve
, and
A.
Lousa
, “
Boron carbide thin films deposited by tuned-substrate RF magnetron sputtering
,”
Diamond Relat. Mater.
8
,
402
405
(
1999
).
34.
K. J.
Boyd
,
D.
Marton
,
S. S.
Todorov
,
A. H.
Al‐Bayati
,
J.
Kulik
,
R. A.
Zuhr
, and
J. W.
Rabalais
, “
Formation of C-N thin films by ion beam deposition
,”
J. Vacuum Sci. Technol. A
13
,
2110
2122
(
1995
).
35.
Y.
Kang
,
Z.
Chu
,
D.
Zhang
,
G.
Li
,
Z.
Jiang
,
H.
Cheng
, and
X.
Li
, “
Incorporate boron and nitrogen into graphene to make BCN hybrid nanosheets with enhanced microwave absorbing properties
,”
Carbon
61
,
200
208
(
2013
).
36.
S.
Cao
,
J.
Low
,
J.
Yu
, and
M.
Jaroniec
, “
Polymeric photocatalysts based on graphitic carbon nitride
,”
Adv. Mater.
27
,
2150
2176
(
2015
).
37.
C. G.
Cofer
and
J.
Economy
, “
Oxidative and hydrolytic stability of boron nitride-A new approach to improving the oxidation resistance of carbonaceous structures
,”
Carbon
33
,
389
395
(
1995
).
38.
Y.
Wang
and
M.
Trenary
, “
Surface chemistry of boron oxidation. 2. The reactions of B2O2 and B2O3 with boron films grown on Ta (110)
,”
Chem. Mater.
5
,
199
205
(
1993
).
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