Materials Letters 159 (2015) 257260

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Absorption properties of twinned SiC nanowires reinforced Si3N4

composites fabricated by 3D-prining
Wenyan Duan a, Xiaowei Yin a,n, Fangxian Cao a, Yinglu Jia a, Yun Xie a, Peter Greil b,
Nahum Travitzky b,nn
a
b

Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xian 710072, China
Department of Materials Science, Institute of Glass and Ceramics, University of Erlangen-Nuernberg, Martensstr. 5, d-91058 Erlangen, Germany

art ic l e i nf o

a b s t r a c t

Article history:
Received 17 February 2015
Received in revised form
22 May 2015
Accepted 28 June 2015
Available online 4 July 2015

Near net- and complex shaped porous silicon nitride (Si3N4) composites reinforced with in-situ formed
twinned silicon carbide (SiC) nanowires (NWs) were successfully fabricated by 3D-printing (3DP) followed by polymer precursor inltration and pyrolysis (PIP) up to 1400 C. An increase of the PIP cycle
number of the printed bodies resulted in a homogeneous distribution of SiC NWs in the fabricated
composites. An increase of SiC NW content in the fabricated composites led to the growth of both the real
and the imaginary parts of permittivity. The formation of twinned SiC NWs with high electrical conductivity led to a minimal electromagnetic wave RC of
57 dB, demonstrating that Si3N4SiC ceramics
with the in-situ formed SiC NWs have a superior microwave absorbing ability.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
Si3N4SiC
3D-printing
PIP
Absorption properties

1. Introduction
Recent years, many research works have been carried out to
investigate the microwave absorption properties of different materials [13] for protecting environment and sensitive circuits from
microwave radiation. When the reection coefcient (RC) of an
electromagnetic wave (EMW) absorbing material is smaller than

10 dB, only 10% of EMW power is reected and 90% is absorbed.
Silicon based ternary polymer-derived ceramics (PDC) have attracted attention for their EMW absorbing properties and stability
with respect to crystallization and decomposition, and oxidation
[4]. Table 1 shows EMW absorbing properties of PDCs [59], which
can be easily tailored. The RC of PDCs can be lowered to less
than
10 dB. In order to obtain improved EMW absorption
property, absorbing materials need to have a promising permittivity [10]. At a frequency of 10 GHz and a sample thickness of
2.86 mm, the optimum and should be equal to 7.3 and 3.3 to
get the minimum RC [11]. However, the permittivity of the already-reported PDCs deviated from this optimizing permittivity.
To optimize permittivity, EMW absorption materials should
contain part of the following components: nano-sized
pores, nano-sized secondary phase, conductive/semi-conductive
n

Corresponding author. Fax: 86 29 88494620.

Corresponding author. Fax: 49 9131 852 8311.
E-mail addresses: yinxw@nwpu.edu.cn (X. Yin),
nahum.travitzky@ww.uni-erlangen.de (N. Travitzky).
nn

http://dx.doi.org/10.1016/j.matlet.2015.06.106
0167-577X/& 2015 Elsevier B.V. All rights reserved.

secondary phase and insulating matrix [10]. Porous silicon nitride

(Si3N4) was selected as the insulating matrix for its excellent
mechanical properties and promising EMW transparent properties. Porous Si3N4 can be fabricated by nitriding silicon powder
compacts in the temperature range 11001450 C [12]. Owing to
the inability of current technology to produce complex-shaped
ceramic, 3D-printing (3DP) is becoming an increasingly important
processing technique. For instance, Fig. 1a and b show the computer-aided design model and the Si3N4 printed part. 3DP enables
user to fabricate such complex-shaped components with high
reliability. By applying 3DP it is possible to design materials with
moderate micro and nano-sized porosity which can be post-inltrated with conductive/semi-conductive secondary phase.
SiC is a wide band gap semiconductor which has many practical
applications in EMW absorption [13]. PDC-SiC nanowires (NWs)
have higher electrical conductivity than grained SiC due to the
special structure of one dimensional NW on a nanometer scale
[14]. EMW absorption property of Si3N4SiC can be substantially
increased for the formation of PDC-SiC NWs in the porous Si3N4
ceramic by precursor inltration and pyrolysis (PIP). It is important
to note that in-situ forming of SiC NWs may avoid health hazards
associated with ne ceramic reinforcement.
In this work, the combination of 3DP and PIP was for the rst
time employed to fabricate Si3N4SiC composites. This approach
enables the near net-shape fabrication, microstructure designing
and improvement of absorption property. The effects of SiC NWs
on the microstructure, dielectric properties, and absorption

258

W. Duan et al. / Materials Letters 159 (2015) 257260

properties of Si3N4SiC ceramics were investigated.

2. Experimental
The fabrication of porous Si3N4 preformed by 3DP combined

with pressureless-sintering was described in the previous work

[15]. The polysiloxane and 5 wt% ferrocene were mixed for 30 min
at 80 C in Ar atmosphere. The Si3N4 specimens, which have an
open porosity of 78%, were dipped into the as-obtained organic
liquid by vacuum infusion process for 30 min. After inltration, the
Si3N4 ceramics with polysiloxane were cross-linked at 300 C for

Table 1
EMW absorbing properties and electrical conductivity of PDCs and other ceamic composites materials.
Materials

Matrix

Absorber

RCmin (dB)

Reference

PDC-SiC
PDC-SiBCN

SiCTi
SiBCN
SiBCN
Si3N4, SiO2
SiOC
SiOC
Porous Si3N4
SiO2
ZrSiO4
Epoxy resin
SiO2
Porous Si3N4

SiC, C
SiC nanoparticles
CNTs
SiC, C
C, SiC
C, SiC nanowires
SiBC
Cage ZnO
AlZnO
SWCNT
CF
SiC nanowires

 11.9
2.77.0
2.715.6
4.314.1
3.6-5.6
3.610.7
4.55
 4.7
5.36.2
 5.5
1924
3.721.5

 4.5
0.11.0
0.115.6
0.26.5
0.11.3
0.112.7
4.53
 0.5
2.7
 1.3
 11
0.3813.5

23

32

53

10

17

23.3

10.7

32

19

10

57

[5]
[6]
[7]
[8]
[9]
[9]
[19]
[2]
[22]
[20]
[21]
This work

PDC-SiCN
PDC-SiOC
Si3N4/SiBC
SiO2/ZnO
ZrSiO4/AlZnO
Epoxy resin/SWCNT
SiO2/CF
Si3N4/SiC

Fig. 1. Computer-aided design model (a) and Si3N4 printed part (b); SEM images of S2 (c) and S3 (d); XRD patterns (e) and TEM image (f) of Si3N4SiC ceramics.

W. Duan et al. / Materials Letters 159 (2015) 257260

Table 2
Physical properties of obtained Si3N4SiC ceramic with different content of SiC.
Materials

Cycle number of PIP

Si3N4 (wt%)

SiC (wt%)

(g cm
3)

P (%)

S1
S2
S3
S4
S5
S6

0
1
2
3
4
5

100
92.5
89.5
81.9
69
67

0
7.5
10.5
18.1
31
33

0.72
1.20
1.26
1.55
1.73
1.78

78
61
55
45
38
34

2 h and annealed at 1400 C for 2 h with Ar atmosphere. The inltration, curing reaction, and heat treatment process were repeated for several times. The as-received samples were designated
as S1, S2, S3, S4, S5, and S6, respectively, corresponding to the
inltration cycle numbers of 0, 1, 2, 3, 4, and 5.
The crystal structure was identied by X-ray diffractometer
(XPert Pro, Philips), using CuKa ( 1.54 ) radiation. The complex
permittivity ( - j, is the real part and is the imaginary

259

part) of samples with dimensions of 22.86  10.16  2.86 mm3 at

frequencies of 8.212.4 GHz was obtained by a vector network
analyzer (VNA, MS4644A, Anritsu, Kanagawa, Japan) using the
waveguide method. The EMW absorbing property was discussed
by calculating the EMW RC as follows:
Zin = tan h(j2 fd/c ) , RC (dB) = 20 log10 (Zin 1)/(Zin + 1)

(1)
where c is the speed of light; f is the microwave frequency; Zin,
d, and are the normalized input impedence, thickness, and
permeability of materials. Here is taken as 1 considering the
negligible magnetic properties of Si3N4SiC ceramic.

3. Results and discussion

SEM images of S2 (Fig. 1c) and S3 (Fig. 1d) show that SiC NWs
which were formed in the porous Si3N4 ceramics composed of rodlike -Si3N4 grains intercrossing with each other. The diameter of
SiC NWs was less than 100 nm. With the increase of inltration

Fig. 2. The real part (a) and imaginary part (b) of permittivity of Si3N4SiC ceramics; the RC of Si3N4SiC ceramics (c) with a thickness of 2.5 mm; The RC of Si3N4SiC
ceramics of S2 (d), S3 (e) and S4 (f).

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W. Duan et al. / Materials Letters 159 (2015) 257260

cycle number, more SiC NWs were formed. Table 2 lists physical
properties of the porous Si3N4 ceramics after inltration. As the
inltration cycle number increased, the weight gain and the
density of the porous Si3N4SiC ceramic increased.
Fig. 1e shows the XRD patterns of Si3N4SiC in dependence on
the inltration cycle number. The original porous Si3N4 ceramic
was composed of -Si3N4 with little amount of Lu2Si2O7. After
inltration, the whole samples showed the crystalline peaks at 2
of 35.6, 60.0 and 71.8, which referred to the diffraction from the
(111), (220) and (311) lattice planes of -SiC. As the inltration
cycle number increased, the peak intensity of -SiC increased
gradually with the peaks intensity of -Si3N4 decreasing slowly.
The TEM images (Fig. 1f) of SiC NWs shows they all have a
zigzag surface morphology. The zigzag part exhibited a periodically angled prole, which is approximately 141, and the periodicity is about 18 nm in distance. The interplanar spacing of different crystal planes was 0.25 nm, which corresponds to the (111)
plane of -SiC. Indexing the diffraction spots gave two symmetrical sets of face-centered cubic lattices, suggesting that the zigzag
part was composed of (111) twinning structures. The structures of
twinned SiC nanowires were similar to that in previous works
[16,17].
Fig. 2a and b show the real permittivity and the imaginary
permittivity of Si3N4SiC ceramics in dependence on the inltration cycle. When the inltration cycle number was one, 7.5 wt% SiC
was added to the porous Si3N4, and the average and of Si3N4
SiC increased to 6.9 and 2.6. When the inltration cycle number
increased to ve, the average and increased to 21.2 and 13.5.
The of composites was affected by the frequency dependence on
the polarization mechanisms. One way to change is by varying
the number of polarizable group per unit volume. From the
equation:
log c = Vi log i (2)
where c is the relative permittivity of the composite, Vi and i
are the volume fractions and the relative permittivity of phase. We
deduce that the of composites increased with increasing SiC
content. The increased with the increase of electrical conductivity of material due to the formation of SiC NWs which offered the mobile charge carriers channels to move and interact
with the electromagnetic eld over a the short range [14].
To reveal the EMW absorption properties of the Si3N4SiC
composite, RC is calculated according to Eq. (1). The EMW absorption capability of a material is inuenced by complex permittivity. When the permittivity meets the impedance match requirement, the incident EM wave can enter absorbing materials,
leading to better EMW absorption properties. Fig. 2c shows the RC
of Si3N4SiC ceramics with a sample thickness of 2.5 mm. When
the content of SiC was 10.5 wt%, the RC of S3 reached
45 dB. S5
and S6 with more content of SiC had higher permittivity which
was harmful to the impedance match, leading to strong reection
and weak absorption [18]. As a result, they had the worse absorption property. The EM absorption capability is also related to
the thickness of the material. The RCthickness relation curves of
sample S2, S3 and S4 are shown in Fig.2(d), (e) and (f), the RCmin of
which attained
20.4,
57 and -13.6 dB. Table 1 also summarizes
the absorption properties of other ceramic composites materials
[2,11,1922]. Therefore, Si3N4SiC ceramics with the in-situ

formed SiC NWs show very promising absorption property.

4. Conclusion
In this study, twinned SiC NWs were in-situ formed in porous
Si3N4 ceramics by PIP. By increasing the content of SiC NWs, which
acted as high-concentration carriers and thus improved polarization capability and electric conductivity, both the real permittivity
and imaginary permittivity of Si3N4SiC increased. Due to the
distinctive microstructure of SiC NWs, the lowest RC of Si3N4SiC
ceramics with 10.5 wt% of SiC attained
57 dB (it means 99.999%
of EMW power is absorbed) at sample thickness of 2.3 mm, which
was lower than that of the already-reported PDCs. It was demonstrated that SiC NWs reinforced Si3N4SiC ceramic is a promising EM absorbing material.

Acknowledgment
This work was nancially supported by the National Natural
Science Foundation of China (Grant nos. 51332004 and 51221001),
the National University Student Innovation Program fund (No.
201410699023), and the 111 Project (B08040).

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