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Synthesis of silicon carbide/aluminium tetroxycarbide nanobres for reinforcement of glass matrix composites: Material properties
Pattamaporn Prapitpongwanich, Kamonpan Pengpat, Pisith Singjai
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

a r t i c l e
Article history:

i n f o

a b s t r a c t
Silicon carbide/aluminium tetroxycarbide (SiC/Al4 O4 C) nanobres were synthesized in a large-scale by current heating of pencil rods. Scanning electron microscopy and X-ray diffraction results conrm that the as-grown bres consist of both SiC and Al4 O4 C phases with diameters ranging from 40 to 300 nm. The bre-reinforced glass matrix composites were then prepared by a conventional glass melting method at the bre/matrix ratio ranging from 0.1 to 1.0 wt.%. The Knoop hardness of the composites increased with the bre/glass ratio whereas the bending strength decreased due to the presence of high porosity and

Received 30 October 2006 Received in revised form 5 November 2007 Accepted 14 November 2007

Keywords: Nanobres Nanocomposites Ceramic matrix composites Mechanical properties

aggregated bres. 2007 Elsevier B.V. All rights reserved.

1.

Introduction

Ceramic matrix composites (CMCs) consist of a ceramic matrix and imbedded micro- and nanostructures, such as carbon nanotubes (CNTs), ceramic bres, whiskers, and particles. The matrix is usually made from ceramics such as Si3 N4 (Desmarres et al., 1991), SiO2 (Ning et al., 2003, 2004), SiC (Igawa et al., 2005), Al2 O3 (Sun et al., 2005) and glassceramics (Todd et al., 1999; Vicens et al., 2003; Bansal, 2003). The use of monolithic ceramics for high pressure and high temperature applications is always limited by their lower toughness. Hence, particular attention is now being paid to investigations of the bre-reinforced CMCs mainly for the automotive components and aerospace systems, such as windshields and gas turbine blades (Yilmaz, 2007; Boccaccini et al., 2003). However, many works have been devoted to glass and glassceramic matrix composites reinforced with commercially available

bres, such as basalt, glass and crystalline oxide ceramic bres (Boccaccini et al., 2003; Bernardo et al., 2006) due to their relative ease of processing at a lower temperature. Reinforcements with ceramic bres and CNTs have been extensively investigated over the last decade because of their unique properties at high temperature. For example the glassceramic matrix composites prepared by the hotpressed method at higher temperatures such as the work of Bansal (2003) have achieved the high composite density, as well as a surfactant-assisted processing is also needed to disperse CNTs and create the homogeneous body (Ning et al., 2004). Moreover, a better mechanical interlocking bond and a higher specic interfacial area between the nanobres and the matrix, such as beaded carbon tubes and nanobres are the ideal choices to provide such a high interfacial strength for nanocomposites (Ting and Lan, 1999; Singjai et al., 2002a,b).

Corresponding author. Fax: +66 53 892271. E-mail address: singjai@chiangmai.ac.th (P. Singjai). 0924-0136/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jmatprotec.2007.11.101

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added with 1 vol.% polyvinyl alcohol (PVA) before sintering for 1 min at a temperature of 800 C under vacuum. The assintered specimens were cut and mirror-like polished to the nal sizes of 2 mm 5 mm 25 mm (The European Standard, 1998). The hardness of the samples was tested using the Knoop microhardness tester (Matsuzawa Seika, MXT-CX) with a load of 50 g (ASTM, 1993). The bending strength was measured by three-point method with a 12-mm span and a crosshead speed of 1 mm min1 (Lloyd, LR 50 K). The porosity and the density of the samples were examined by FESEM and the Archimedes immersion method in distilled water, respectively.

3.
3.1.

Results and discussion

Characterization of the nanobres

Fig. 1 Schematic diagram of the current heating apparatus.

In this paper, SiC/Al4 O4 C nanobres were synthesized in a large-scale by current heating of pencil rods and were used for reinforcement in borosilicate glass (BSG) matrix. Mechanical properties, such as hardness and bending strength of the composites were tested.

2.
2.1.

Experimental details
Materials

The pencil rods (Staedtler EE, Germany) of 5 mm in diameter were cut into a length of 25 mm. The nanobres of SiC/Al4 O4 C were synthesized using the current heating method (Singjai et al., 2002a,b). However, the apparatus in this present paper has been developed to produce the bres in gram-scale production (Fig. 1). In brief, the synthesis was done under an argon atmosphere at the gas ow rate of 2 l/min. To synthesize the nanobres, the pencil rod was placed between two copper electrodes, preheated at 45 W (30 V, 1.5 A) (power supply, Agilent 6553A) for 5 min and gradually heated upto 1400 C (Pyrometer, Ultimax infrared thermometer ux-20P) at 350 W (35 V, 10 A) for 30 min. The as-grown product was then characterized using eld emission scanning electron microscope (FESEM, JEOL JSM-6335F) and X-ray diffractometer (XRD, Bruker D8 Advance).

The product formed on the rod surface (10 wt.% of the rod) could be easily separated from the pencil core and seen by naked eyes as the light grey powder (Fig. 2). The microstructure of the as-grown product observed by SEM is shown in Fig. 3. The product was found to be nanobres with sizes of 40300 nm in diameter and several 10 m in length. It is noted that the mean diameter of the as-grown bres can be decreased with decreasing the synthesis time. The beaded nanobres were also observed as indicated by the arrows. As stated in our previous publication concerning the mass production of the bres (Singjai et al., 2002a,b); fortunately, we have successfully obtained several grams of the bres within a single day by repeating the lab-scale synthesis. Therefore, their applications as a reinforcer in composites have been preliminarily investigated in this present paper. The XRD patterns of the as-grown bres and the pencil rod as the raw materials are shown in Fig. 4. The result shows that the nanobres consist of cubic SiC (JCPDF No. 73-1665) and orthorhombic Al4 O4 C (JCPDF No. 48-1583) whereas the peaks from the raw materials are indexed as Al2 O3 , SiO2 and graphite peaks. In the spectrum of the raw materials, between 20 and 25 is seen a broad plateau of mixed amorphous SiO2 , but in the spectrum from the nanobres the plateau disappears. The

2.2.

Methods

The SiC/Al4 O4 C nanobres and the BSG powder were mixed in different bre/glass ratio, ranging from 0.1 to 1.0 wt.%. In order to get a homogenous mixture, the powder was crushed by alumina-ball milling for 30 min and sieved with a 150-mesh sieve. The monolithic glass and the mixture powder were then

Fig. 2 Photograph of the as-grown product, which could be easily separated (indicated by arrows) from the pencil cores and seen as the light grey powder.

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Fig. 3 SEM micrograph of SiC/Al4 O4 C nanobres and their beaded structures indicated by arrows.

Fig. 5 SEM micrograph of the composites, the aggregated bres (left-hand side) and the pores (indicated by arrows) are apparently seen.

XRD results are in good agreement with the previous report (Singjai et al., 2002a,b), unless the presence of Al4 O4 C phase. As it is evident from the work of Seangkwamsawang et al. (2003), the high content of Al2 O3 in the pencil rod is a possible reason for the formation of Al4 O4 C.

3.2.

Possible growth mechanism

Since the growth mechanism for both phases is governed by a solid-vapor phase carbothermal sublimation technique, the vapor phases were generated inside the pencil core through these reactions: SiO2(s) + C(s) SiO(v) + CO(v) Al2 O3(s) + 2C(s) Al2 O(v) + 2CO(v) (1) (2) Fig. 6 Relative density and porosity of the composites as a function of the bre/glass ratio in wt.%.

Consequently, the nanobres as the solid phases are deposited on the rod surface at a lower temperature by a

vaporsolid (VS) mechanism through these reactions: SiO(v) + 3CO(v) SiC(s) + 2CO2(v) 2Al2 O(v) + CO2(v) Al4 O4 C(s) (3) (4)

3.3.

Mechanical properties of glass matrix composites

Fig. 4 XRD patterns of the as-grown nanobres (upper one) and the pencil rods as the raw materials (lower one).

According to the composite processing, unfortunately, this present work is failed to disperse the bres homogeneously in the glass matrix as shown in Fig. 5. The aggregated bres (left-hand side) and pores (indicated by arrows) are apparently seen which have the negative role on the mechanical properties of the composites. Fig. 6 shows the relative density and the porosity of the composites as a function of the bre/glass ratio in wt.%. It is seen that the relative density decreased from 70 to 50% with increasing the bre/glass fraction from 0.1 to 1.0 wt.% whereas the porosity increased from

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(40%) due to the poor relative density (50%) of the composites.

Acknowledgements
This work was supported by the Thailand Research Fund and the Commission on Higher Education.

references

Fig. 7 Mean hardness and bending strength as a function of the bre/glass ratio in wt.%.

8 to 35%. This trend is in good agreement with the result of Ning et al. (2003). It is known that the sintering mechanism of glass matrix composites is a viscous ow (Boccaccini, 1995), in which SiC/Al4 O4 C bres act as inclusions and reduce the densication. Moreover, the bres tangle and interact each other through van der Waals force, which cause the aggregation of the bres. Fig. 7 shows the hardness and the bending strength of the 0.11.0 wt.% of SiCAl4 O4 C bre/BSG matrix composites and monolithic BSG. It can be seen that both properties were altered by the bre/glass fraction. The mean Knoop hardness (Hk ) obtained from the monolithic BSG ceramics is 545Hk , which is the same order of magnitude as in Ref. Quinn et al. (2003), and that of the 1.0 wt.% bre/glass composites is 626Hk . It is noted that the hardness increases with the bre/glass ratio while the bending strength was decreased due to the presences of high porosity and aggregated bres. Maximum bending strength obtained from the monolithic BSG ceramics is 5.7 MPa and that of the 1.0 wt.% of bre/glass ratio composites is 3.4 MPa. This result is also in good agreement with that of Ref. Ning et al. (2003), but only in the case of the CNT/SiO2 ratio is higher than 5 vol.%. A possible reason is that even at the lowest bre/glass ratio (0.1 wt.%) of our samples, the relative density is as low as 70% (Fig. 6) whereas that of Ref. Ning et al. (2003) is higher (98%) even at 5 vol.% CNT/SiO2 ratio.

4.

Conclusions

In summary, SiC/Al4 O4 C nanobres with diameters ranging from 40 to 300 nm were successfully synthesized in a large-scale from the pencil rods by using current heating deposition. The nanobres were used for reinforcement in BSG matrix, prepared by a conventional glass melting method. The mean Knoop hardness of the 1.0 wt.% of bre/glass ratio composites compared with that of the monolithic glass was increased from 545 to 626Hk (15%) and the bending strength was degraded from 5.7 to 3.4 MPa

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