Preparation of High Specific Surface Area Micro/Meso-porous SiOC Ceramics by the Low Temperature Phase Separation Method

doi:10.15541/jim20180375

Abstract

Abstract:

Micro/meso-porous SiOC ceramics with high surface area and narrow pore size distribution were prepared by the low temperature phase separation method (namely water vapor assisted pyrolysis) followed by etching in hydrofluoric acid (HF) solution. The cross-linked body was made from hydrogen-containing polysiloxane (PHMS), tetramethyl-tetravinylcycletetrasiloxane (D₄^vi) and Pt-complex by thermal cross-linking. Phase compositions, chemical bonds, microstructures, and specific surface area of the prepared SiOC ceramic were investigated by XRD, FT-IR, SEM, and BET, etc. Water vapor can promote the precursor to produce Si-O-Si bonds, SiO₂-rich clusters, and SiO₂ nanocrystals in SiOC ceramics. All of these species act as pore-forming substrate and can be etched away by HF. Water vapor injection and pyrolysis temperature have important effects on phase compositions, microstructures and specific surface area of SiOC porous ceramics, which have a maximum specific surface area of 1845.5 m²/g and pore size distribution of 2.0-10 nm at pyrolysis temperature of 1300℃.

Key words: micro/meso-porous SiOC, low temperature phase separation, phase composition, microstructure, etching

CLC Number:

TQ174

LI Jia-Ke, HAN Xiao-Qi, LIU Xin, WANG Yan-Xiang, GUO Ping-Chun, YANG Zhi-Sheng. Preparation of High Specific Surface Area Micro/Meso-porous SiOC Ceramics by the Low Temperature Phase Separation Method[J]. Journal of Inorganic Materials, 2018, 33(12): 1360-1364.

Figures/Tables 7

Fig. 1 XRD patterns of SiOC ceramics pyrolyzed in Ar +H2O at different temperatures(a) Before etching; (b) After etching

Fig. 2 XRD patterns of SiOC ceramics pyrolyzed in Ar at different temperatures(a) Before etching; (b) After etching

Fig. 3 FT-IR spectra of SiOC ceramics pyrolyzed in Ar+ H2O and Ar at 1300℃ before and after etching

Fig. 4 SEM cross section images of SiOC pyrolyzed at 1300℃ in Ar+H2O before (a) and after (b) etching, in Ar before (c) and after (d) etching

Fig. 5 N2 adsorption (solid symbols) and desorption (open symbols) isotherms for the samples obtained from SiOC ceramics pyrolyzed in (a) Ar +H2O and (b) Ar at 1300℃ after etching

Fig. 6 Cumulative specific surface area (S), interval specific surface area (dS) and pore size distribution (PSD) for SiOC ceramics pyrolyzed in Ar +H2O (a) and in Ar (b) at 1300℃ after etching

Table 1 BET results of SiOC ceramics after etching with different pyrolysis temperatures in Ar and Ar+H2O

Temperature/℃	Specific surface area/ (m²·g^-1)		Average pore size/nm		Pore volume/(cm³·g^-1))
Temperature/℃	Ar	Ar +H₂O	Ar	Ar +H₂O	Ar	Ar +H₂O
900	-	58.6	-	2.05	-	0.105
1100	-	435.23	-	2.16	-	0.142
1200	53.65	654.16	1.43	2.23	0.015	0.202
1300	635.13	1845.50	2.25	2.83	0.282	0.788
1400	632.24	1817.20	2.18	2.75	0.286	0.764
1500	633.52	1805.60	2.15	2.77	0.288	0.756

References 14

[1]	IONESCU E, KLEEBE H J, RIEDEL R.Silicon-containing polymer- derived ceramic nanocomposites (PDC-NCs): preparative approaches and properties.Chem. Soc. Rev., 2012, 41(15): 5032-5052.
[2]	FENG Y, LAI S Y, YANG L,et al. Polymer-derived porous Bi2WO6/SiC (O) ceramic nanocomposites with high photodegradation efficiency towards Rhodamine B. Ceram. Int., 2018, 44(7): 8562-8569.
[3]	COLOMBO P.Conventional and novel processing methods for cellular ceramics.Philos. Trans., 2006, 364(1838): 109-124.
[4]	YAN X J, SAHIMI M, TSOTSIS T T.Fabrication of high-surface area nanoporous SiOC ceramics using preceramic polymer precursors and a sacrificial template: precursor effects.Micropor. Mesopor. Mat., 2017, 241: 338-345.
[5]	VAKIFAHMETOGLU C, COLOMBO P.A direct method for the fabrication of macro-porous SiOC ceramics from preceramic polymers.Adv. Eng. Mater., 2008, 10(3): 256-259.
[6]	DIBANDJO P, DIRE S, BABONNEAU F,et al. Influence of the polymer architecture on the high temperature behavior of SiCO glasses: a comparison between linear- and cyclic-derived precursors. J. Non-Cryst. Solids, 2010, 356(3): 132-140.
[7]	FORTUNIAK W, POSPIECH P, MIZERSKA U,et al. Generation of meso- and microporous structures by pyrolysis of polysiloxane microspheres and by HF etching of SiOC microspheres. Ceram. Int., 2018, 44(1): 374-383.
[8]	VAKIFAHMETOGLU C, PRESSER V, YEON S H,et al. Enhanced hydrogen and methane gas storage of silicon oxycarbide derived carbon. Micropor. Mesopor. Mat., 2011, 144(1): 105-112.
[9]	SORARU G D, PENA-ALONSO R, LEONI M.C-rich micro/ mesoporous Si(B)OC:in situ diffraction analysis of the HF etching process. Micropor. Mesopor. Mat., 2013, 172: 125-130.
[10]	XU T H, MA Q S, CHEN Z H.High-temperature behavior of silicon oxycarbide glasses in air environment.Ceram. Int., 2011, 37(7): 2555-2559.
[11]	SAHA A, RAJ R.Crystallization maps for SiCO amorphous ceramics.J. Am. Ceram. Soc., 2007, 90(2): 578-583.
[12]	LI J K, LU K, LIN T S,et al. Preparation of micro-/meso porous SiOC bulk ceramics. J. Am. Ceram. Soc., 2015, 98(6): 1753-1761.
[13]	WU J Q, LI Y M, CHEN L M,et al. Simple fabrication of micro/ nano-porous SiOC foam from polysiloxane. J. Mater. Chem., 2012, 22(14): 6542-6545.
[14]	LIANG T, LI Y L, SU D,et al. Silicon oxycarbide ceramics with reduced carbon by pyrolysis of polysiloxanes in water vapor. J. Eur. Ceram. Soc., 2010, 30(12): 2677-2682.

[1]	MA Wen, SHEN Zhe, LIU Qi, GAO Yuanming, BAI Yu, LI Rongxing. Preparation of Y₂O₃ Coating by Suspension Plasma Spraying and Its Resistance to Plasma Etching [J]. Journal of Inorganic Materials, 2024, 39(8): 929-936.
[2]	FAN Wugang, CAO Xiong, ZHOU Xiang, LI Ling, ZHAO Guannan, ZHANG Zhaoquan. Anticorrosion Performance of 8YSZ Ceramics in Simulated Aqueous Environment of Pressurized Water Reactor [J]. Journal of Inorganic Materials, 2024, 39(7): 803-809.
[3]	CHEN Qian, SU Haijun, JIANG Hao, SHEN Zhonglin, YU Minghui, ZHANG Zhuo. Progress of Ultra-high Temperature Oxide Ceramics: Laser Additive Manufacturing and Microstructure Evolution [J]. Journal of Inorganic Materials, 2024, 39(7): 741-753.
[4]	JIANG Lingyi, PANG Shengyang, YANG Chao, ZHANG Yue, HU Chenglong, TANG Sufang. Preparation and Oxidation Behaviors of C/SiC-BN Composites [J]. Journal of Inorganic Materials, 2024, 39(7): 779-786.
[5]	ZHENG Yawen, ZHANG Cuiping, ZHANG Ruijie, XIA Qian, RU Hongqiang. Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering [J]. Journal of Inorganic Materials, 2024, 39(6): 707-714.
[6]	XUE Yifan, LI Weijie, ZHANG Zhongwei, PANG Xu, LIU Yu. Process Control of PyC Interphases Microstructure and Uniformity in Carbon Fiber Cloth [J]. Journal of Inorganic Materials, 2024, 39(4): 399-408.
[7]	SUN Chuan, HE Pengfei, HU Zhenfeng, WANG Rong, XING Yue, ZHANG Zhibin, LI Jinglong, WAN Chunlei, LIANG Xiubing. SiC-based Ceramic Materials Incorporating GNPs Array: Preparation and Mechanical Characterization [J]. Journal of Inorganic Materials, 2024, 39(3): 267-273.
[8]	ZHENG Jiaqian, LU Xiao, LU Yajie, WANG Yingjun, WANG Zhen, LU Jianxi. Functional Bioadaptability in Medical Bioceramics: Biological Mechanism and Application [J]. Journal of Inorganic Materials, 2024, 39(1): 1-16.
[9]	HE Danqi, WEI Mingxu, LIU Ruizhi, TANG Zhixin, ZHAI Pengcheng, ZHAO Wenyu. Heavy-Fermion YbAl₃ Materials: One-step Synthesis and Enhanced Thermoelectric Performance [J]. Journal of Inorganic Materials, 2023, 38(5): 577-582.
[10]	WU Shuang, GOU Yanzi, WANG Yongshou, SONG Quzhi, ZHANG Qingyu, WANG Yingde. Effect of Heat Treatment on Composition, Microstructure and Mechanical Property of Domestic KD-SA SiC Fibers [J]. Journal of Inorganic Materials, 2023, 38(5): 569-576.
[11]	XIE Jiaye, LI Liwen, ZHU Qiang. Contrastive Study on in Vitro Antibacterial Property and Biocompatibility of Three Clinical Pulp Capping Agents [J]. Journal of Inorganic Materials, 2023, 38(12): 1449-1456.
[12]	LI Jianbo, TIAN Zhen, JIANG Quanwei, YU Lifeng, KANG Huijun, CAO Zhiqiang, WANG Tongmin. Effects of Different Element Doping on Microstructure and Thermoelectric Properties of CaTiO₃ [J]. Journal of Inorganic Materials, 2023, 38(12): 1396-1404.
[13]	WU Dongjiang, ZHAO Ziyuan, YU Xuexin, MA Guangyi, YOU Zhulin, REN Guanhui, NIU Fangyong. Direct Additive Manufacturing of Al₂O₃-TiC_p Composite Ceramics by Laser Directed Energy Deposition [J]. Journal of Inorganic Materials, 2023, 38(10): 1183-1192.
[14]	ZHANG Ye, ZENG Yuping. Progress of Porous Silicon Nitride Ceramics Prepared via Self-propagating High Temperature Synthesis [J]. Journal of Inorganic Materials, 2022, 37(8): 853-864.
[15]	XIA Qian, SUN Shihao, ZHAO Yiliang, ZHANG Cuiping, RU Hongqiang, WANG Wei, YUE Xinyan. Effect of Boron Carbide Particle Size Distribution on the Microstructure and Properties of Reaction Bonded Boron Carbide Ceramic Composites by Silicon Infiltration [J]. Journal of Inorganic Materials, 2022, 37(6): 636-642.