Materials Science & Engineering A 590 (2014) 16–20

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Materials Science & Engineering A

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Toughening in boron nitride nanotubes/silicon nitride composites

Ya-Fei Chen a,b, Jian-Qiang Bi a,b,n, Wei-Li Wang a,b, Yan Zhao a,b, Guang-Lei You a,b,
Chong-Long Yin a,b, Yu-Jun Bai a
a
Key Laboratory for Liquid–Solid Structure Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061, China
b
Engineering Ceramics Key Laboratory of Shandong Province, Shandong University, Jinan 250061, China

art ic l e i nf o a b s t r a c t

Article history: Boron nitride nanotubes (BNNTs)/silicon nitride composites were fabricated by hot pressing. The fracture
Received 17 July 2013 toughness of the composite containing 1.5 wt% BNNTs increases about 40% than that of the monolithic.
Received in revised form The BNNTs pullout, BNNTs necking and the development of elongated grains are the main responsible
2 October 2013
factors for the toughness improvement.
Accepted 4 October 2013
Available online 11 October 2013
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Boron nitride nanotubes
Silicon nitride
Hot pressing
Composites
Toughening

1. Introduction Silicon nitride (Si3N4) is an important candidate for structural

As an analog of carbon nanotubes (CNTs), boron nanotubes
(BNNTs) have attracted tremendous attentions over the past
twenty years due to their excellent properties. They have high
tensile modulus and tensile strength like CNTs, while the differ-
ence is that the BNNTs are normally insulating, with a wide band
gap of ca. 5.5 eV [1]. They also possess excellent chemical inertness
and oxidation resistance [2–5]. The oxidation resistance tempera-
ture is up to 900 1C, as reported in [6]. Therefore it is commonly
assumed that BNNT is more promising for toughing composites.
To the best of our knowledge, only a few investigations have
been done on the mechanical properties of composites incorpo-
rated by BNNTs. Reinforced with 4 wt% of BNNTs, the strength and
fracture toughness of G18 glass composite improved as much as
90% and 35%, respectively [7]. Huang et al. reported that a small
addition of BNNTs could dramatically improve the high-
temperature superplastic deformation of engineering ceramics
[8]. The elastic modulus of the polylactide-polycaprolactone copo-
lymer (PLC) with 5 wt% BNNTs showed a 1370% increase and the
tensile strength enhanced 109% [9]. In our laboratory, we have
fabricated BNNTs/Al2O3 and BNNTs/SiO2 composites [10–15],
which have excellent mechanical properties.
ceramics owing to its combination of excellent properties such as
high strength, good corrosion and oxidation resistance and high
thermal shock resistance. Hence, Si3N4 has been researched
intensively in recent years [16–20]. However, the relatively low
fracture toughness still hindered the wide application of Si3N4.
These years, plenty of researchers have made endeavor to improve
the reliability of Si3N4 ceramic. Si3N4 composites were prepared
with CNTs using hot-pressing by Pasupuleti et al., which had a
high fracture toughness (6.6 MPa m1/2) [21]. Corral et al. found
that the addition of single walled carbon nanotubes (SWNTs) could
increase the fracture toughness of the Si3N4 from 5.27 to
8.48 MPa m1/2 when increasing the SWNTs content from 0 to
2.0 vol% and sintering by SPS [22]. Kusunose et al. reported that
the strength of the Si3N4 composites was significantly improved
with increasing h-BN content, while the fracture toughness
decreased a little [23].
In this paper, hence, for the first time, we studied the influence
of a small amount of BNNTs on the microstructure of Si3N4 and
toughening behavior in Si3N4 ceramic.
2. Experimental

n
High pure and submicron Si3N4 powder (  93% α-silicon
Corresponding author at: Key Laboratory for Liquid–Solid Structure Evolution
and Processing of Materials, Ministry of Education, Shandong University, Jinan
nitride) was selected as raw material. We used the sintering aids
250061, China. as the following powers, 4 wt% of Y2O3 and 6 wt% of Al2O3.
E-mail address: bjq1969@163.com (J.-Q. Bi). Different amount of BNNTs were added into the batches (0, 1,

0921-5093/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2013.10.011
 Y.-F. Chen et al. / Materials Science & Engineering A 590 (2014) 16–20 17

1.5 wt%) and the corresponding composites were denoted as SN0, Table 1
SN1, and SN1.5, respectively. The synthesis of BNNTs was produced Properties of SN0, SN1, and SN1.5.
as described elsewhere [24]. The mixed powers were prepared in
BNNTs Relative Bending strength Fracture toughness
ethanol by ball milling for 8 h. After drying at 80 1C, the mixtures composition (wt%) density (%) (MPa) (MPa m1/2)
were sieved in a 100-mesh sieve. Then the batches were hot
pressed at 1750 1C in a hot pressing sintering furnace (Shandong 0 98.7 839.6 7 33.9 6.9 7 0.1
University Research Center of Advanced Materials, Jinan, Shan- 1.0 96.7 814.0 7 19.5 8.2 7 1.0
1.5 95.5 785.4 7 32.3 9.8 7 0.8
dong, China) under a pressure of 30 MPa in vacuum for 1 h.
The bending strength of the bar specimens (3.0 mm 
4.0 mm  25 mm) was measured by a three-point bending test
with a span of 20 mm at a crosshead speed of 0.5 mm/min. Five
specimens were tested in each group. Besides, fracture toughness
of three specimens (2.0 mm  4.0 mm  25 mm) for each sample
was measured by the single-edge notched beam (SENB) method.
A notch of 2.0 mm in depth and 0.3 mm in width was introduced
in the middle of each specimen by a thin diamond blade. Both the
bending strength and fracture toughness tests were conducted on
a CMT5105 electromechanical universal testing machine (Shenz-
hen SANS Testing Machine Co., Ltd., Shenzhen, Guangdong, China).
The density of the sintered samples was measured by the
Archimedes method, where the theoretical densities for Si3N4,
Al2O3, Y2O3 and BNNTs were 3.44, 3.97, 5.01 and 1.38 g/cm3 [25],
respectively.
X-ray diffraction (XRD; Rigaku Dmax-rc, Tokyo, Japan) analysis
was used for the determination of the crystalline phases of the
samples. In addition, the morphology of BNNTs and the fracture
surfaces of the composites were examined via thermal field
Fig. 2. XRD patterns of SN0 (a), SN1 (b), and SN1.5(c).
emission scanning electron microscope (FESEM; Hitachi SU-70,
Tokyo, Japan). After polishing, all the samples were chemically
etched in a molten mixture of NaOH and KCl to expose grain well. Meanwhile, there are no signs of any α peaks. This indicates
boundaries for estimating the mean diameter and the aspect ratio. the BNNTs have not hindered the transformation from α phase to
High-resolution transmission electron microscope (HRTEM; JEOL
β phase. And no obvious peaks associated with the BNNTs are
JEM-2100, Tokyo, Japan) investigations were performed to study observed, as shown in Fig. 2, due to the low BNNTs contents in the
the pristine BNNTs and to investigate the microstructure between composites and the low XRD intensity of BNNTs compared with
BNNTs and Si3N4 matrix. the highly crystalline Si3N4.
The FESEM images of chemically etched monolithic Si3N4 and
BNNTs/Si3N4 samples are given in Fig. 3. Fig. 3(a) shows the
3. Results and discussion
monolithic Si3N4 is dominated by equiaxed grains, with some
elongated grains, which is well known that the additives during
Fig. 1 displays the morphology of the as-received BNNTs used in
this work, whose diameters are all less than 100 nm and lengths hot-pressing promote the development of elongated β-Si3N4
reach several micrometers. And the hollow structure of the BNNTs [26–33]. And the amount of elongated β-Si3N4 increases with
is obvious. the BNNTs content, as observed in Fig. 3(b and c). The mean grain
The bending strength and fracture toughness of the monolithic size and aspect ratio are summarized in Table 2. The aspect ratio
Si3N4 and BNNTs/Si3N4 are shown in Table 1. The bending strength increases from 2.1 to 2.7, and the grain size also increases from
decreases marginally with BNNTs additions. On the contrary, the 0.77 μm to 0.84 μm. Like CNTs in [21], the addition of BNNTs
fracture toughness is improved remarkably. The SN1.5 composites provides nucleation sites for β grains, which promotes the devel-
possess fracture toughness of 9.8 MPa m1/2, about 40% higher than
opment of elongated β-Si3N4. However, the results in our research
that of SN0 (6.9 MPa m1/2).
are not in consistent with the observation totally made by
Fig. 2 shows the XRD pattern of monolithic Si3N4 and BNNTs/
Pasupuletti et al. In Table 1, the densities decrease with BNNT
Si3N4. β-Si3N4 is always the dominant phase. The diffraction peak content, which means the BNNTs could provide more growth
is sharp and the intensity is high, which suggest the grains develop
space for the β grains. These elongated β grains will contribute to
the self-toughening of the composites.
The morphology of fracture surfaces of monolithic Si3N4 and
BNNTs/Si3N4 were observed by FESEM, as shown in Fig. 4(a–c).
As we can see, the incorporation of BNNTs increases the grain size,
just as that observed in Fig. 3. In the BNNTs/Si3N4 composites
sintered in our laboratory, expect for providing nucleation sites
and growth space, BNNTs can also tough the composites. Fig. 4(d–f)
are the high magnification of fracture surface of SN1.5 compo-
sites. As depicted in Fig. 4(d and e), BNNTs distribute around the
grain boundaries or into the grains. When crack propagates across
the grain boundaries, the BNNTs will be stretched. With the
propagation of crack, the BNNTs vertical to the crack propagation
direction or with a certain angle will exhibit the effect of crack
Fig. 1. FESEM image of the as-received BNNTs.
18 Y.-F. Chen et al. / Materials Science & Engineering A 590 (2014) 16–20

Fig. 3. FESEM images of etched surface for SN0 (a), SN1 (b), and SN1.5 (c).

Table 2
Grain size and aspect ratio of SN0, SN1, and SN1.5.

BNNTs composition (wt%) Aspect ratio Grain size (μm)

0 2.1 0.77
1.0 2.3 0.80
1.5 2.7 0.84

Fig. 4. FESEM images of the fractured surfaces of SN0 (a), SN1 (b), SN1.5 (c) and magnified images of SN1.5 (d), (e) and (f).
 Y.-F. Chen et al. / Materials Science & Engineering A 590 (2014) 16–20
Fig. 5. Schematic of fracture of BNNTs.
Fig. 6. HRTEM images of SN1.5 composite sintered at 1750 1C.
bridging. And they will fail when reaching their critical strain or
pull out when reaching the limitation of bonding strength, which
will consume lots of energy. And we can see the diameter of the
BNNTs decreasing clearly in Fig. 4(f). This does not like the sword-
in-sheath fracture mode as depicted in [34]. Fig. 5 shows the
fracture of BNNTs in composites. During the crack bridging, the
necking of BNNT appears with the increase of external strain in
Fig. 5(c). When the strain reaches the critical value, the BNNT will
be broken (Fig. 5d).
Fig. 6 shows the HRTEM images of SN1.5 composite. The lattice
fringe image of BNNTs can be seen obviously in matrix and there is
no obvious diffusion layer.
In summary, with the coupling effect of BNNTs and elongated
β-Si3N4, the toughness of the Si3N4 composite improves greatly.
4. Conclusion
BNNTs as toughening agency were added into Si3N4 to improve
its toughness. Although the bending strength decreases a little, the
fracture toughness increases remarkably. The composite with
1.5 wt% BNNTs possesses fracture toughness of 9.8 MPa m1/2,
approximately 40% higher than that of monolithic Si3N4 ceramic
(6.9 MPa m1/2). The addition of BNNTs provides nucleation sites
and growth space for β grains, which promotes the growth of
β-Si3N4. And the development of elongated β-Si3N4 is beneficial to
the self-toughness. The pullout and necking of BNNTs are also
responsible for the toughness improvement. In the near future, we
will continue this work and turn to focus on clarifying the effect of
BNNTs and β-Si3N4 on fracture toughness, separately.
Prime novelty statement
In this paper, for the first time, we studied the influence of
small amount of BNNTs on the microstructure of Si3N4 and
toughening behavior in Si3N4 ceramic. We observed the necking
fracture mode of BNNTs in Si3N4 ceramic.
19
Acknowledgments
This work is supported by the National Natural Science Foun-
dation of China (No. 51272132) and Independent Innovation
Foundation of Shandong University (2012TS213).
References
[1] X. Blase, A. Rubio, S. Louie, M. Cohen, Europhys. Lett. 28 (1994) 335–340.
[2] D. Golberg, Y. Bando, C.C. Tang, C.Y. Zhi, Adv. Mater. 19 (2007) 2413–2432.
[3] A.P. Suryavanshi, M.F. Yu, J.G. Wen, C.C. Tang, Y. Bando, Appl. Phys. Lett. 84
(2004) 2527–2529.
[4] D. Golberg, Y. Bando, Y. Huang, T. Terao, M. Mitome, C.C. Tang, C.Y. Zhi, ACS
Nano 4 (2010) 2979–2993.
[5] C.Y. Zhi, Y. Bando, C.C. Tang, D. Golberg, Mater. Sci. Eng.: R 70 (2010) 92–111.
[6] Y. Chen, J. Zou, S.J. Campbell, G. Le Caer, Appl. Phys. Lett. 84 (2004) 2430–2432.
[7] N.P. Bansal, J.B. Hurst, S.R. Choi, J. Am. Ceram. Soc. 89 (2006) 388–390.
[8] Q. Huang, Y.S. Bando, X. Xu, T. Nishimura, C.Y. Zhi, C.C. Tang, F.F. Xu, L. Gao,
D. Golberg, Nanotechnology 18 (2007).
[9] D. Lahiri, F. Rouzaud, T. Richard, A.K. Keshri, S.R. Bakshi, L. Kos, A. Agarwal, Acta
Biomater. 6 (2010) 3524–3533.
[10] W.L. Wang, J.Q. Bi, K.N. Sun, M. Du, N.N. Long, Y.J. Bai, J. Am. Ceram. Soc. 94
(2011) 3636–3640.
[11] W.L. Wang, J.Q. Bi, S.R. Wang, K.N. Sun, M. Du, N.N. Long, Y.J. Bai, J. Eur. Ceram.
Soc. 31 (2011) 2277–2284.
[12] W.L. Wang, J.Q. Bi, K.N. Sun, M. Du, N.N. Long, Y.J. Bai, S. Choi, J. Am. Ceram. Soc.
94 (2011) 2304–2307.
[13] M. Du, J.Q. Bi, W.L. Wang, X.L. Sun, N.N. Long, Y.J. Bai, Mater. Sci. Eng.: A 530
(2011) 669–674.
[14] M. Du, J.Q. Bi, W.L. Wang, X.L. Sun, N.N. Long, J. Alloys Compd. 509 (2011)
9996–10002.
[15] M. Du, J.Q. Bi, W.L. Wang, X.L. Sun, N.N. Long, Mater. Sci. Eng.: A 543 (2012)
271–276.
[16] G. Blugan, M. Hadad, J. Janczak-Rusch, J. Kuebler, T. Graule, J. Am. Ceram. Soc.
88 (2005) 926–933.
[17] J. Tatami, T. Katashima, K. Komeya, T. Meguro, T. Wakihara, J. Am. Ceram. Soc.
88 (2005) 2889–2893.
[18] P.F. Becher, G.S. Painter, N. Shibata, S.B. Waters, H.T. Lin, J. Am. Ceram. Soc. 91
(2008) 2328–2336.
[19] X. Xu, T. Nishimura, N. Hirosaki, R.J. Xie, Y.C. Zhu, Y. Yamamoto, H. Tanaka, J.
Am. Ceram. Soc. 88 (2005) 934–937.
[20] J. Dusza, J. Morgiel, A. Duszová, L. Kvetková, M. Nosko, P. Kun, C. Balázsi, J. Eur.
Ceram. Soc. 32 (2012) 3389–3397.
[21] S. Pasupuleti, R. Peddetti, S. Santhanam, K.P. Jen, Z.N. Wing, M. Hecht, J.
P. Halloran, Mater. Sci. Eng.: A 491 (2008) 224–229.
20 Y.-F. Chen et al. / Materials Science & Engineering A 590 (2014) 16–20

[22] E.L. Corral, J. Cesarano, A. Shyam, E. Lara-Curzio, N. Bell, J. Stuecker, N. Perry, [27] S. Baik, R. Raj, J. Am. Ceram. Soc. 68 (1985) C124–C126.
M. Di Prima, Z. Munir, J. Garay, E.V. Barrera, J. Am. Ceram. Soc. 91 (2008) [28] R. Raj, M.J. Hoffmann, J. Am. Ceram. Soc. 80 (1997) 3250–3252.
3129–3137. [29] M. Zenotchkine, R. Shuba, I.W. Chen, J. Am. Ceram. Soc. 87 (2004) 1040–1046.
[23] T. Kusunose, T. Sekino, Y.H. Choa, K. Niihara, J. Am. Ceram. Soc. 85 (2002) [30] X. Wu, I.W. Chen, J. Am. Ceram. Soc. 75 (1992) 2733–2741.
2678–2688. [31] L.L. Wang, T.Y. Tien, I.W. Chen, J. Am. Ceram. Soc. 81 (1998) 2677–2686.
[24] J.Q. Bi, W.L. Wang, Y.X. Qi, Y.J. Bai, L.L. Pang, H.L. Zhu, Y. Zhao, Y. Wang, Mater. [32] S.L. Hwang, I.W. Chen, J. Am. Ceram. Soc. 77 (1994) 1719–1728.
Lett. 63 (2009) 1299–1302. [33] Z. Shen, Z. Zhao, H. Peng, M. Nygren, Nature 417 (2002) 266–269.
[25] C. Zhi, Y. Bando, C. Tang, D. Golberg, Solid State Commun. 151 (2011) 183–186. [34] G. Yamamoto, K. Shirasu, T. Hashida, T. Takagi, J.W. Suk, J. An, R.D. Piner, R.
[26] S. Baik, R. Raj, J. Am. Ceram. Soc. 70 (1987) C105–C107. S. Ruoff, Carbon 49 (2011) 3709–3716.