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Journal of Alloys and Compounds 578 (2013) 67–71

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Journal of Alloys and Compounds


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Letter

Microstructure and mechanical properties of high-pressure sintered


Al2O3/SiC nanocomposites
Yuancheng Teng a,⇑, Zhiping Sun b, Kuibao Zhang a,⇑, Weiyuan Lu c
a
State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
b
Maanshan Iron and Steel Co. Ltd., Maanshan 243000, Anhui, China
c
Sichuan Yijing Changyun Super-Hard Materials Co. Ltd., Mianyang 621000, Sichuan, China

a r t i c l e i n f o a b s t r a c t

Article history: Al2O3/SiC nanocomposites were synthesized by high-pressure sintering using a-Al2O3 and b-SiC nano-
Received 25 February 2013 powders as the raw materials. Microstructure and mechanical properties of the sintered samples were
Received in revised form 24 April 2013 investigated using X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Atomic Force Micro-
Accepted 2 May 2013
scope (AFM) et al. The results indicate that high-pressure sintering is an effective sintering technique,
Available online 9 May 2013
which can densify Al2O3/SiC nanocomposites at high pressure (4.5 GPa) and relatively low temperature
(1000–1230 °C). Rapid grain growth of Al2O3 is mainly restrained by the separation effect of nanosized
Keywords:
SiC grains. Grain boundary, grain boundary-intragranular and nano-nano structured Al2O3/SiC nanocom-
High-pressure sintering
Nanocomposite
posites can be achieved by controlling the sintering temperature and b-SiC content. The highly densified
Microstructure Al2O3/SiC nanocomposite (AS5-1170) exhibits excellent mechanical properties as 429.9 GPa in elastic
Mechanical property modulus and 30.7 GPa in nano-hardness.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction grain size of 40–70 nm under pressure of 4 GPa, 1000–1200 °C


with holding time of 2 min. M. J. Gasch [5] et al. has obtained equi-
Al2O3 based ceramics are widely used in mechanical, chemical axial Si3N4/SiC nano-nanostructured composites with mean grain
engineering, metallurgy, military and electronic fields because of size of 50 nm from high-pressure sintering. Lu [6] and Li [7] have
their outstanding properties in high-temperature mechanical, employed high-pressure sintering to synthesize highly densified
dielectric, anti-oxidation, thermal and chemical stability. micro-crystalline AlN ceramic materials. Spark plasma sintering
Compared with Al2O3 ceramics in microsized grains, the nano- (SPS) [2,8], hot-press sintering (HP) [9,10] and high-pressure sin-
structured counterparts exhibit much higher performance in bend- tering [11,12] were considered as the main sintering approaches
ing strength, fracture toughness, hardness et al. [1,2]. Thus, Al2O3 to prepare nanocomposite ceramics. However, there is no report
based nanocomposites can find applications in various fields and about the high-pressure sintering of Al2O3 based nanocomposites
tremendous attention has been attracted to produce these up to now.
materials. In this research, Al2O3/SiC nanocomposites were synthesized by
High-pressure (1–8 GPa) sintering, which are mainly used for two anvil high-pressure sintering equipment using nanosized
synthesis of artificial polycrystal diamond, can be achieved by six a-Al2O3 and nanosized b-SiC powders as the raw materials. Micro-
anvil and two anvil pressure devices. High-pressure sintering is structure and mechanical properties of the as-prepared Al2O3
considered as a effective technique to resolve the densification dif- based nanocomposites were investigated as well.
ficulties in nanocrystalline ceramics and other covalent-bonded
ceramic materials (such as high-purity Al2O3, SiC, Si3N4, BN, AlN
2. Experimental details
et al.). Liao et al. [3] has prepared highly densified nanocrystalline
Al2O3 ceramics (grain size < 50 nm and relative density > 98%) Nanosized a-Al2O3 (purity P 99.9%, grain size 6 80 nm, Nanjing Haitai Nano
under sintering condition of 1–8 GPa in pressure, 400–800 °C with Co., Ltd.) and b-SiC (purity P 99%, grain size 6 50 nm, Hefei Kaier Nano Co., Ltd.)
holding time of 15–30 min. Yuan et al. [4] has synthesized nano- were employed as the raw materials. Ingredient contents of the prepared samples
are listed and nominated in Table 1. The raw powders were mixed 10 h in
crystalline ZrO2(4Y) ceramics with relative density of 99.3% and
QM-1SP planetary ball miller at 150 rpm using 95 porcelain balls as the milling
medium and ethanol as the dispersion agent. The obtained slurry was dried, prilled
and poured into stainless mould to preform U28.6  10 mm pellets under 10 MPa
⇑ Corresponding authors. Tel./fax: +86 816 2419201. pressure. The preformed pellets were pressed under 200 MPa in cold isostatic
E-mail addresses: tyc239@163.com (Y. Teng), xiaobao0320@yahoo.com.cn pressing(CIP) equipment. The blank samples were subsequently sintered under
(K. Zhang). 3000 tons two anvil high pressure device. Installment configuration of the sample

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.05.009
68 Y. Teng et al. / Journal of Alloys and Compounds 578 (2013) 67–71

Table 1 are in relative density of 97.6%, 96.8% and 97.1%, while other sam-
Experimental data of as-prepared samples. ples show relative density higher than 98%. The AS20-1230 speci-
No Composition Sintering Relative density men exhibits the highest relative density of 99.6%, which is very
of samples temperature (°C) of samples (%) close to the theoretical density of Al2O3-20 vol.%SiC composite.
A-1000 Al2O3 1000 97.6 This result demonstrates that high-pressure sintering is a low tem-
A-1230 Al2O3 1230 96.8 perature and rapid densification technique as reported previously
AS0.5-1100 Al2O3-0.5 vol.%SiC 1100 97.1 [3–7]. The ceramic particles or grains are imposed with very high
AS0.5-1230 Al2O3-0.5 vol.%SiC 1230 98.5
AS5-1000 Al2O3-5 vol.%SiC 1000 98.0
shear and compression stress under high-pressure sintering, which
AS5-1100 Al2O3-5 vol.%SiC 1100 98.2 results in grain boundary slipping, tight cohesion and broken of
AS5-1170 Al2O3-5 vol.%SiC 1170 98.3 particles or even grains. Thus, rapid densification of covalent
AS5-1230 Al2O3-5 vol.%SiC 1230 98.0 bonded ceramics can be readily achieved from effective mass
AS10-1230 Al2O3-10 vol.%SiC 1230 98.6
transfer of plastic flow [14].
AS20-1230 Al2O3-20 vol.%SiC 1230 99.6

Relative density of sample(RD) = density of sample/ theoretic density of sample
3.2. XRD analysis of Al2O3-20 vol.%SiC before and after sintering
(TD) ⁄ 100% TD = (TD of a-Al2O3 + x ⁄ TD of b-SiC)/(1 + x) = (3.987 + 3.239x)/(1 + x)
x: volume fraction of b-SiC in sample.
The nanocomposite powder of Al2O3-20 vol.%SiC and its high-
pressure sintered specimen (AS20-1230) were characterized by X-
ray diffraction to analyse their phase composition (as shown in
Fig. 1). The results indicate that both samples are composed of a-
Al2O3 and b-SiC phases. The X-ray intensity of a-Al2O3 in nanocom-
posite powder is much higher than the as-densified sample.
The grain sizes of a-Al2O3 and b-SiC have been calculated from
X-ray peak broadening using Scherrer’s formula after eliminating
the instrumental contribution:

D ¼ KkB cos h

where D is grain size, K is Scherrer constant, k is the wavelength of


X-ray(k = 0.1541 nm), B is full width at half maximum (FWHM) of
the diffraction peaks, h is the diffraction angle. Grain sizes of a-
Al2O3 in the nanocomposite powder and AS20-1230 specimen are
calculated to be 61.1 nm and 50.6 nm, while grain sizes of b-SiC
are 40.4 nm and 43.5 nm. This result reveals no obvious chemical
reaction takes place between a-Al2O3 and b-SiC during the high-
Fig. 1. X-ray diffraction patterns of: (a) Al2O3-20 vol.%SiC nanocomposite powder
and (b) high-pressure sintered AS20-1230 specimen.
pressure sintering process, and nano–nano structured Al2O3/SiC
composite is obtained for AS20-1230 sample. As the grain size of
in high pressure chamber is illustrated in Ref. [13]. The specimens were sintered at a-Al2O3 is reduced after sintering, we can conclude that high-pres-
various temperatures under pressure of 4.5 GPa and holding time of 30 min. Sinter-
sure sintering leads to grain broken of a-Al2O3. Meanwhile, b-SiC
ing temperature and relative density of the as-prepared samples are listed in Table
1.
grains demonstrate no obvious grain growth as the samples show
Phase compositions of the prepared samples were characterized by X-ray dif- similar grain size before and after high-pressure sintering.
fraction patterns (Rigaku D/max-RB, Cu Ka, 35 KV, 60 mA). Fracture surface of the
sintered samples were observed by scanning electron microscope (SEM, LEO
S440). Atomic force microscope (AFM, SPI 3800 N) was utilized to analyse the mor-
3.3. SEM results of densified samples
phology and structure in nanosized regions of AS5-1170 sample. Elastic modulous
and nano-hardness were calculated from the results measured by Nanoindenter Fracture surface of the high-pressure sintered samples were ob-
(MTS Nano Indenter XP). served by SEM as the images illustrated in Figs. 2–5. Pure a-Al2O3
sintered at 1000 °C and 1230 °C (A-1000 and A-1230) exhibit sim-
3. Results and discussion ilar structure with uniform grain sized of about 5 lm (Fig. 2). The
microsized grains are in tight compaction, which indicates these
3.1. Analysis of the densification condition samples are well sintered with relatively high density. This result
proves that pure a-Al2O3 is capable to be rapidly densified under
It is demonstrated in Table 1 that all samples are well densified high pressure of 4.5 GPa and relatively low temperature of 1000–
with high relative density. A-1000, A-1230 and AS0.5-1100 samples 1230 °C with holding time of 30 min. However, the nanosized

Fig. 2. SEM images of: (a) A-1000 sample and (b) A-1230 sample.
Y. Teng et al. / Journal of Alloys and Compounds 578 (2013) 67–71 69

Fig. 3. SEM fracture surface images of: (a) AS0.5-1100 sample (inserted picture with magnification  5000, scale bar: 10 lm) and (b) AS0.5-1230 sample.

Fig. 4. SEM fracture surface images of: (a) AS5-1000, (b) AS5-1100, (c) AS5-1170 and (d) AS5-1230 (scale bar: 1 lm).

Fig. 5. SEM fracture surface images of: (a) AS10-1230 and (b) AS20-1230 (scale bar: 1 lm).

grains are coarsened dramatically to about 5 lm. This phenome- 1100 sample (Fig. 3a) contains many small grains with grain size
non is totally different from tranditional theory that slow grain less than 1 lm. The doped b-SiC nanoparticles impede the grain
growth takes place at relatively low temperature (<1300 °C). The boundary movement of a-Al2O3 under high-pressure sintering,
mechanism of rapid grain growth for a-Al2O3 under high-pressure which leads grain coarsening significantly be depressed and small
sintering will be investigated in our future research. grains can be maintained. The sub-microsized grains are located at
Compared with pure a-Al2O3, samples with b-SiC nanoparticle grain boundaries or be enclosed by large grains, resulting in grain-
addition exhibit much different microstructure with inhomoge- boundary typed nanocomposite structure. The amount of sub-
neous and refined grains after high-pressure sintering. The AS0.5- microsized grains decreases obviously as the sintering temperature
70 Y. Teng et al. / Journal of Alloys and Compounds 578 (2013) 67–71

Fig. 6. 2-D top-view and 3-D AFM images in 500 nm  500 nm region of AS5-1170 sample.

increases to 1230 °C (Fig. 3b). The grain boundary movement is Al2O3 based nanostructured ceramics will be distinctly impacted
accelerated as the sintering temperature be elevated, which makes as well. It can be concluded that grain-boundary typed, grain
Al2O3 grain boundary capable to move across the doped SiC parti- boundary-intragranular typed and nano–nano typed Al2O3/SiC
cles and grain growth of Al2O3 is promoted. The grain growth takes nanocomposite ceramics can be obtained from high-pressure sin-
place rapidly along with the decrement of small grains. Nanosized tering under the controlling of SiC content and sintering
b-SiC grains are partly enclosed by large Al2O3 grains and grain- temperature.
boundary typed nanocomposite structure transforms to grain
boundary-intragranular typed nanocomposite morphology. 3.4. AFM analysis of AS5-1170 sample
The 5 vol% b-SiC doped sample were sintered at 1000, 1100,
1170 and 1230 °C with fracture surface images presented in The microstructure of AS5-1170 sample was characterized by
Fig. 4. All samples exhibit similar morphology with high relative AFM with the images illustrated in Fig. 6. It can be observed in
density, no obvious pores and nanosized grains. Integrated grains the microzone (200 nm  200 nm) that the sample surface is
and clear grain boundaries can hardly be observed in these sam- highly densified with low roughness. The grains are in irregular
ples, which is much different from normal-pressure sintered shape with grain size smaller than 100 nm. The nanosized grains
microsized ceramics. Grain boundary movement and grain growth are densely cohered with indistinct morphology and boundary,
are greatly restrained as more b-SiC nanoparticles are located which is in agreement with XRD and SEM results.
among the Al2O3 grain matrix with 5 vol.% b-SiC addition. Thus,
the composite transforms to nano–nano typed microstructure as
3.5. Mechanical properties of AS5-1170 sample
SiC content increases from 0.5 vol.% to 5 vol.%.
Higher SiC addition, such as 10 vol.% and 20 vol.% in AS10-1230
The relationship curves of elastic modulous and hardness ver-
and AS20-1230 (Fig. 5a and b), also results in nano–nano structured
sus surface displacement for AS5-1170 sample are presented in
composites with similar microstructure as AS5-1000, AS5-1100,
Fig. 7a and b. Elastic modulous and nano-hardness exhibit high
AS5-1170 and AS5-1230. The AS10-1230 specimen exhibits very
uniformity for AS5-1170 in the surface displacement range of sta-
uniform morphology with mean grain size lower than 100 nm,
ble measurement. The sample exhibits high elastic modulous and
which is in agreement with the previous result calculated from
hardness from the microzone analysis. The mean elastic modulous
Scherrer’s formula. However, tetragonal grains with particle size
of AS5-1170 reaches 429.9 GPa and the mean nano-hardness
of about 200–500 nm precipitate from the nanostructured matrix
achieves 30.7 GPa, which reveals this sample possesses excellent
in the AS20-1230 specimen. This phenomenon reveals that grain
mechanical properties. The high mechanical properties of AS5-
growth of Al2O3 is restrained effectively with high SiC addition
1170 sample can be related with its high relative density and
(P5 vol.%). The microstructure and grain size distribution of
nano–nanocomposite structure.

Fig. 7. Nanoindenter measurement of AS5-1170 sample: (a) modulus vs. displacement to surface and (b) hardness vs. displacement to surface.
Y. Teng et al. / Journal of Alloys and Compounds 578 (2013) 67–71 71

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