Effect of acrylamide monomer concentration in low temperature magnesiothermic synthesis of mesoporous silicon carbide from MCM-48/ PAAM nanocomposite

precursor
Z. Saeedifar*1, A. A. Nourbakhsh2 and M. Saeedifar3
Mesoporous silicon carbide with high specific surface area was successfully synthesised from a MCM-48/polyacrylamide nanocomposite precursor in two temperature ranges of 650700uC and 800850uC by a magnesiothermic reduction process. The MCM-48/polyacrylamide precursor nanocomposite was prepared by in situ polymerisation. Heat treatment using low concentrations of acrylamide monomer in the temperature range of 650700uC and using high concentration of acrylamide monomer was carried in two temperature ranges of 650700uC and 800850uC. The products were characterised by X-ray diffraction, TEM and N2 adsorptiondesorption. The results show that synthesised SiC in both temperature ranges of 650700uC and 800850uC is mesoporous and has specific surface of 194/60 and 167/84 m2 g21 respectively. The results also show that the value of carbon content and the concentration of acrylamide monomer (factor affecting the amount of contact surface of carbon and silica) impress the starting temperature of the reaction.
Keywords: Silicon carbide, Nanocomposite, Mesoporous, Magnesiothermic reduction, In situ polymerisation, Concentration of acrylamide monomer

Introduction
The high thermal conductivity, oxidation resistance, mechanical strength and chemical inertness of silicon carbide makes it suitable for a variety of applications as a biomaterial, in semi conductive devices for high temperature use and as a lightweight/high strength catalyst. If it can be prepared with an average surface area of 20 100 m2 g21 and appropriate pore size distribution, it would be an excellent candidate for heterogeneous catalysis. Thus, in recent years, research on the synthesis of SiC with a high specic surface area has been of high priority.1 An ordered mesoporous silicate with large pores (250 nm), high volume and surface area and a narrow pore size distribution would be an ideal precursor for porous SiC with a high specic surface area.1,2 MCM48 is a mesoporous silica with the advantage of cubically ordered pores and a three-dimensional structure providing inner surfaces with improved exposure to guest molecules and less pore faces to be clogged.2,3 Appropriate method for synthesising mesoporous SiC is the low temperature direct conversion of SiO2/C
1 Department of Materials Engineering, Najafabad Branch, Islamic Azad University, P.O. Box 517, Isfahan, Iran 2 Department of Materials Engineering, Shahreza Branch, Islamic Azad University, Isfahan, Iran 3 Department of Materials Engineering, Foolad Institute of Technology, Fooladshahr, Isfahan, Iran

*Corresponding author, zahra.saeedifar@yahoo.com

nanocomposite structures into related SiC materials without destroying their structural morphology. This low temperature reaction can be achieved by magnesiothermic reduction by the use of Mg metal.46 Shi et al. demonstrated the magnesiothermic reduction method for nanostructured SiC materials using a SiO2/carbon nanocomposite as the precursor and Mg as the reducing agent at 600900uC.5 Zhao et al. synthesised mesoporous SiC by magnesiothermic reduction of a sacharose/ SBA-15 composite 600uC.4 Polymer/mesoporous silica nanocomposite precursors can be prepared by several methods, including solgel processing, blending and in situ polymerisation.711 In situ polymerisation in the presence of a mesoporous matrix is an appropriate method for increasing the contact surface between the mesoporous matrix and carbon, and the resulting uniform distribution of carbon and silica retains the porous structure of the resulting SiC. The present study utilises magnesiothermic reduction to synthesise mesoporous SiC from a precursor nanocomposite of MCM-48 with polyacrylamide in the temperature range of 650700uC using low concentration of acrylamide monomer and in the temperature range of 800850uC using high concentration of acrylamide monomer. The MCM-48/polyacrylamide precursor nanocomposite was prepared by in situ polymerisation of acrylamide monomer in the presence of mesoporous MCM-48 synthesised by the solgel

2014 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 15 October 2013; accepted 24 December 2013 DOI 10.1179/1743676113Y.0000000136

Advances in Applied Ceramics

2014

VOL

113

NO

167

Saeedifar et al.

Low temperature magnesiothermic synthesis of mesoporous SiC

1 X-ray diffraction pattern in low angles of a MCM-48 and b polyacrylamide/MCM-48 nanocomposite (low concentration of acrylamide monomer)

2 X-ray diffraction pattern in low angles of a MCM-48 and b, c polyacrylamide/MCM-48 nanocomposite (high concentration of acrylamide monomer)

method. The effect of acrylamide monomer concentration during the magnesiothermic reduction process in both temperature ranges will be discussed.

Experimental
Mesoporous MCM-48 was synthesised by dissolving 2?4 g hexadecyltrimethylammonium bromide in 50 mL deionised water and adding 50 mL ethanol and 12 mL 32 wt-% ammonia. After mixing for 10 min, 3?4 g tetraethyl orthosilicate was added and mixed for 2 h at room temperature. The resulting solid product was ltered, washed with deionised water, dried at ambient temperature and calcined at 550uC for ,5 h. This mesoporous MCM-48 product was used to prepare the MCM-48/polyacrylamide nanocomposite by mixing 0?5 g MCM-48 with 0?3944 g acrylamide monomer, 12 mL tetrahydrofuran and 0?0403 g 3 mol.-% benzoyl peroxide in a round bottom ask. The mixture was reuxed at 6570uC for 5 h, and the resulting MCM48/polyacrylamide nanocomposite was ltered, washed with tetrahydrofuran and dried at room temperature (low concentration of acrylamide monomer). This mesoporous MCM-48 product was used to prepare the MCM-48/ polyacrylamide nanocomposite by mixing 1?5 g MCM-48 with1?1826 g acrylamide monomer, 25 mL tetrahydrofuran and 0?1209 g 3 mol.-% benzoyl peroxide in a round bottom ask. The mixture was reuxed at 6570uC for 1 h, and the resulting MCM-48/polyacrylamide nanocomposite was ltered, washed with tetrahydrofuran and dried at room temperature (high concentration of acrylamide monomer). Microporous SiC was then prepared from this MCM48/polyacrylamide nanocomposite precursor by carbonising in an Ar atmosphere at 700uC at a heating rate of 5uC min21 and a holding time of 3 h. The resulting MCM-48/C nanocomposite was mixed with Mg powder in the molar ratio (SiO2/Mg51 : 2). The above steps were repeated for MCM-48/polyacrylamide nanocomposite prepared of high concentration of acrylamide monomer. Then, the mixture obtained in argon atmosphere in the temperature range of 650700uC (low concentration of acrylamide monomer) and in two temperature ranges of 650700uC and 800850uC (high concentration of acrylamide monomer) with heating rates of 5uC min21 and hold time at maximum temperature for 6 h, placed

for synthesis of b-SiC. The product powder was freed from unwanted impurities by room temperature acid treatment in a mixture of 10 wt-%HF and 4M HNO3 for 5 h, ltered, washed with distilled water and dried at room temperature. The nanocomposite precursor and low temperature SiC product were characterised by X-ray diffraction (XRD; Philips PW3040, copper radiation, wavelength of 0?15406 nm, nickel lter), TEM (Zeiss EM10C, Germany) and N2 adsorptiondesorption (BEL Inc Belsorp, Japan).

Results and discussion

Characterisation of MCM-48 and MCM-48/ polyacrylamide nanocomposite precursors
Figures 1a and 2a show the low angle XRD pattern of mesoporous MCM-48 after calcination. The diffraction pattern from MCM-48 contains reections from the (211) and (220) planes in the angular range y2h53u and a broad feature from the (420) and (332) planes at y2h55u. The presence of a separate diffraction peak at 2h53?5u indicates a highly ordered type of mesoporous MCM-48; thus, the XRD pattern includes peaks associated with the space group Ia3d and an ordered cubic structure.1215 Figures 1b and 2b show the low angle XRD pattern of MCM-48/polyacrylamide nanocomposite (conditions different from concentration of acrylamide monomer). The diffraction pattern from MCM-48/polyacrylamide nanocomposite, containing a strong (211) diffraction peak at y2h53u, indicates that the polymerisation of acrylamide in the presence of the MCM-48 has not signicantly degraded the porous structure. Decreased intensities of the MCM-48/polyacrylamide nanocomposite peaks (Figs. 1b and 2b) indicate a decrease in the order of the guest MCM-48 structure (Figs. 1a and 2a).9,13 According to Braggs law, the d space of (211) plane decreased by in situ polymerisation of acrylamide monomers inside of the pore of MCM-48 (low concentration of acrylamide monomer); therefore, the peak position moved to lower angle (Fig. 1b) Braggs law, the d space of (211) plane decreased by in situ polymerisation of acrylamide monomers outside of the pore of MCM-48 (high concentration of acrylamide monomer); therefore, the

168

Advances in Applied Ceramics

2014

VOL

113

NO

Saeedifar et al.

Low temperature magnesiothermic synthesis of mesoporous SiC

Characterization of mesoporous SiC

MCM-48/polyacrylamide nanocomposites prepared of low concentration of acrylamide monomer was heated for 6 h in temperature range of 650700uC, after being carbonised with magnesium with different molar ratios of C/SiO2/Mg5(2 : 1 : 2, 2?5 : 1 : 2). Then, MCM-48/ polyacrylamide nanocomposite prepared of high concentration of acrylamide monomer was heated for 6 h in two temperature ranges of 650700uC and 800 850uC, after being carbonised with magnesium with different molar ratios of C/SiO2/Mg5(2 : 1 : 2, 2?5 : 1 : 2). Figure 4a and b respectively shows XRD pattern of synthesised SiC samples in the temperature range of 650700uC (low concentration of acrylamide monomer) before and after acid etching. Figure 5a and b respectively shows XRD pattern of synthesised samples in two temperature ranges of 650700uC and 800850uC (high concentration of acrylamide monomer) before and after acid etching. According to Fig. 4 in low concentrations of acrylamide monomer, with the in situ polymerisation of acrylamide monomers inside mesoporous MCM-48 holes, there are two results: one side reduced diffusion distance of Mg and SiO2 and the other side increased exposure levels of carbon and SiO2 that ultimately

3 BJH-plot of mesoporous MCM-48

peak position moved to higher angle (Fig. 2b). The specic BrunauerEmmettTeller (BET) surface area, total pore volume and mean pore diameter of the MCM48 sample are 1200 m2g21, 0?7 cm3 g21 and 2?2 nm respectively. Figure 3 shows the pore radius distribution curve in BarretJoynerHalenda (BJH)

a before acid etching; b after acid etching 4 X-ray diffraction pattern of mesoporous b-SiC synthesised in temperature range 650700uC using low concentrations of acrylamide monomer

a before acid etching; b after acid etching 5 X-ray diffraction pattern of mesoporous SiC synthesised in two temperature ranges of 650700uC and 800850uC, using high concentration of acrylamide monomer

Advances in Applied Ceramics

2014

VOL

113

NO

169

Saeedifar et al.

Low temperature magnesiothermic synthesis of mesoporous SiC

6 Images (TEM) of synthesised mesoporous b-SiC at a, b 800850uC (C/SiO2/Mg52 : 1 : 2) and c, d 650700uC (C/SiO2/ Mg52 : 1 : 2)

reduce the starting temperature of the reaction and will facilitate the synthesis of SiC. According to Fig. 5a, in temperature range of 650700uC, weak effects of b-SiC phase were observed in both the molar ratios. In high concentration of acrylamide monomer, the possibility of in situ polymerisation inside the mesoporous MCM-48 holes is decreased. Thus, with the polymerisation outside of the holes, diffusion distance of Mg and SiO2 is increased, resulting in the increase in the starting temperature of the reaction. According to Fig. 5a, in the temperature range of 800850uC, with increase in temperature, the Mg diffusion for access to SiO2 is facilitated. X-ray diffraction patterns of b-SiC powders often exhibit an additional peak at d50?266 nm, high background intensity around the (111) peak and relative intensities for peaks (Fig. 5b), which differ from those predicted from the crystal structure. All these features are due to stacking faults in the powders and not due to the presence of other polytypes in the powders. In this case, b-SiC powder could either consist of two types of particles with different populations of faults and twins, or could consist of a single type of particle that is characterised by clusters of faulted region.16 Figure 6 shows TEM images of mesoporous SiC in the temperature ranges of 650700uC and 800850uC (C/

SiO2/Mg52 : 1 : 2). Using XRD pattern (Figs. 4 and 5), the average sizes of SiC crystallites in the Williamson Hall relation17 calculated ,23 and 55 nm respectively; in two temperature ranges of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer), the crystallite size reduction can be attributed to a decrease in the synthesis temperature. Although the SiC product has the same structure as the mesoporous MCM-48 template, it is less ordered than the silica template, possibly due to fragmentation of the latter during the synthesis reaction.4 Figure 7a and b shows the N2 adsorptiondesorption isotherm and BET plot of synthesised SiC samples in two temperature ranges of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer). The N2 adsorptiondesorption isotherm is of type IV curve shape conrming its mesoporous nature, and the type H3 hysteresis loop does not exhibit any limiting adsorption at high values of P/P0 typical of aggregates of plate-like particles, giving rise to slit shaped pores.18 Table 1 shows the results of the BET plot (Fig. 7b) for the SiC sample.19 Figure 8a and b shows the pore radius distribution curve in BJH plot (adsorption) and the pore size distribution curve in Micropore (MP) plot of SiC

Table 1 BrunauerEmmettTeller data for SiC in two temperature range of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer) BET plot p/p050.050.35 Total pore volume (P/P050.99)/cm3 g21 0.2627 0.2817 Volume of gas absorbed in monolayer (Vm)/cm3(STP) g21 44.70 38.562

Sample SiC 650700uC SiC 800850uC

Mean pore diameter/nm 5.3990 6.7124

BET surface area (aS,BET)/m2 g21 194.60 167.84

BET constant/C 224.74 165.22

170

Advances in Applied Ceramics

2014

VOL

113

NO

Saeedifar et al.

Low temperature magnesiothermic synthesis of mesoporous SiC

7 a N2 adsorptiondesorption isotherm and b BET plot of synthesised SiC samples in two temperature range of 650 700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer)

8 a pore radius distribution curve in BJH plot (adsorption) and b pore size distribution curve in MP plot in temperature ranges of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer)

sample in the temperature ranges of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer). The pore size distributions determined by both BJH and MP analysis indicates that the MCM-48 has very narrow size distribution of ,2 nm. Table 2 shows the results of the BJH plot (Fig. 8a) and MP plot (Fig. 8b) for the SiC sample.18

Conclusions
Mesoporous SiC with high specic surface area was synthesised by magnesiothermic reduction from MCM48/polyacrylamide nanocomposite precursors in the

temperature ranges of 650700uC using low concentration of acrylamide monomer and 800850uC using high concentrations of acrylamide monomer. The TEM images of the resulting SiC showed it to possess a structure similar to its mesoporous MCM-48 precursor, and N2 adsorptiondesorption isotherms conrmed its mesoporosity. The lowering of the synthesis temperature using magnesiothermic reduction was an important factor in securing a mesoporous SiC structure. In low concentration of acrylamide monomer, by in situ polymerisation of acrylamide monomers inside the of pore of mesoporous MCM-48, on the one hand, diffusion distance of Mg and SiO2 is decreased, and on the other hand, the surface area of the contact of carbon

Table 2 Pore size distribution of SiC derived from BJH plot and MP plot in temperature range of 650700uC (low concentration of acrylamide monomer) and 800850uC (high concentration of acrylamide monomer) MP plot MP50.422 nm Micropore volume/cm3 g21 0.0857 0.0622 Total surface area/m2 g21 173.32 160.29 BJH plot BJH .2 nm desorption mesopore volume/cm3 g21 0.2070 0.2395 Mesopore area/m2 g21 106.51 110.25 BJH .2 nm adsorption Mesopore volume/cm3 g21 0.2284 0.2591 Mesopore area/m2 g21 135.38 133.64

Sample SiC 650700uC SiC 800850uC

Advances in Applied Ceramics

2014

VOL

113

NO

171

Saeedifar et al.

Low temperature magnesiothermic synthesis of mesoporous SiC

and SiO2 is increased, which ultimately reduce temperature to start the reaction and facilitate the synthesis of SiC. X-ray diffraction results for samples of differing C contents indicated that increased C content increased the separation distance between the Mg and SiO2 particles by a dilution effect, decreasing the diffraction peak intensity of the b-SiC product.

References
1. J. Parmentier, J. Patarin, J. Dentzer and C. V. Guterl: Formation of SiC via carbothermal reduction of a carbon-containing mesoporous MCM-48 silica phase: a new route to produce high surface area SiC, Ceram. Int., 2002, 28, 17. 2. J. C. Vartuli, W. J. Roth, J. S. Beck, S. B. McCullen and C. T. Kresge: The synthesis and properties of M41S and related mesoporous materials, Mol. Sieves, 1998, 1, 97119. 3. R. Ko hn and M. Fro ba: Nanoparticles of 3d transition metal oxides in mesoporous MCM-48 silica host structures: Synthesis and characterization, Catal. Today, 2001, 68, 227236. 4. B. Zhao, H. Zhang, H. Tao, Z. Tan, Z. Jiao and M. Wu: Low temperature synthesis of mesoporous silicon carbide via magnesiothermic reduction, Mater. Lett., 2011, 65, 15521555. 5. Y. Shi, F. Zhang, Y. S. Hu, X. Sun, Y. Zhang, H. I. Lee, L. D. Chen and G. Stucky: Low-temperature pseudomorphic transformation of ordered hierarchical macro-mesoporous SiO2/C nanocomposite to SiC via magnesiothermic reduction, J. Am. Chem., 2010, 132, 55525553. 6. Z. Saeedifar, A. A. Nourbakhsh, R. J. Kalbasi and E. Karamian: Low-temperature magnesiothermic synthesis of mesoporous silicon carbide from an MCM-48/polyacrylamide nanocomposite precursor, J. Mater. Sci. Technol., 2013, 29, 255260. 7. P. Go mez-Romero and C. Sanchez: Functional hybrid materials, 86121; 2003, Weinheim, Wiley-VCH.

8. L. Wei, N. Hu and Y. Zhang: Synthesis of polymer-mesoporous silica nanocomposites, Materials, 2010, 3, 40664079. 9. R. J. Kalbasi and N. Mosaddegh: Synthesis and characterization of poly(4-vinylpyridine)/MCM-48 catalyst for one-pot synthesis of substituted 4H-chromenes, Catal. Commun., 2011, 12, 12311237. 10. P. Colombo, F. Zordan and E. Medvedovski: Ceramicpolymer composites for ballistic protection, Adv. Appl. Ceram., 2006, 105, 7883. 11. E. V. Bongio, S. L. Lewis, D. R. Welson and W. J. Sherwood: Polymer derived ceramic matrix composites for friction applications, Adv. Appl. Ceram., 2009, 108, 483487. 12. S. E. Dapurkar, S. K. Badamali and P. Selvam: Nanosized metal oxides in the mesopores of MCM-41 and MCM-48 silicates, Catal. Today, 2001, 68, 6368. 13. A. M. Doyle, E. Ahmed and B. K. Hodnett: The evolution of phases during the synthesis of the organically modified catalyst support MCM-48, Catal. Today, 2006, 116, 5055. 14. K. Wang, Y. Lin, M. A. Morris and J. D. Holmes: Preparation of MCM-48 materials with enhanced hydrothermal stability, J. Mater. Chem., 2006, 16, 40514057. 15. K. Schumacher, M. Grun and K. K. Unger: Novel synthesis of spherical MCM-48, Microporous Mesoporous Mater., 1999, 27, 201206. 16. V. V. Pujar and J. D. Cawley: Effect of stacking faults on the Xray diffraction profiles of b-SiC powders, J. Am. Ceram. Soc., 1995, 78, 774782. 17. V. Biju, N. Sugathan, V. Vrinda and S. L. Salini: Estimation of lattice strain in nanocrystalline silver from X-ray diffraction line broadening, J. Mater. Sci., 2008, 43, 11751179. 18. K. S. W. Sing, D. H. Everett, R. Haul, L. Moscou, R. A. Pierotti, J. Rouquerol and T. Siemieniewska: Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity, Pure Appl. Chem., 1982, 54, 22012218. 19. G. A. Tompsett, L. Krogh, D. W. Griffin and W. C. Conner: Hysteresis and scanning behavior of mesoporous molecular sieves, Langmuir, 2005, 21, 82148225.

172

Advances in Applied Ceramics

2014

VOL

113

NO