低温活化合成含硅氮氧化物材料研究进展

doi:10.15541/jim20170401

摘要/Abstract

摘要：

含硅氮氧化物是一类重要的结构/功能一体化材料, 在耐磨耐蚀、高速切削、压力密封、发光基质和碱性催化等领域有重要应用。含硅氮氧化物制备技术经历了高温固相反应法、自蔓延高温合成法、碳热还原氮化法、湿化学合成结合碳热还原氮化法等演变, 呈现持续发展的态势。本文综述了作者研究团队十余年在低温活化合成含硅氮氧化物粉体及纤维的研究进展, 重点介绍基于介孔模板组装的微纳尺度碳热还原氮化法以及SiC还原辅助溶胶-凝胶氮化法制备含硅氮氧化物, 并展望了低温活化合成含硅氮氧化物材料的发展方向和应用前景。

关键词: 含硅氮氧化物, 介孔膜板组装, 碳热还原氮化, SiC还原剂, 溶胶-凝胶, 综述

Abstract:

Si-based oxynitride is an important type of structure/function integrated materials and has got wide applications in the fields of wear resistance, corrosion resistance, high speed cutting, pressure sealing, phosphors host, alkaline catalysis, and so on. The preparation of Si-based oxynitrides powders has undergone different development stages: high temperature solid state reaction (SSR), self-propagating high temperature synthesis (SHS), carbothermal reduction and nitridation (CRN), wet-chemical route combined with CRN, and others, presenting a sustained development trend. In this paper, the research progress in the activated-synthesis of Si-based oxynitrides powders and fibers at low calcination temperatures is reviewed over the past ten years, mainly focusing on the carbothermal reduction nitridation at micro-nano scale based on mesoporous template assembly as well as SiC reduction assisted Sol-Gel nitridation method. The development trend and applications of the low temperature activated-synthesis of Si-based oxynitrides materials are also prospected.

Key words: Si-based oxynitrides, mesoporous template assembling, carbothermal reduction nitridation, SiC reductant, Sol-Gel, review

中图分类号:

刘茜, 周真真. 低温活化合成含硅氮氧化物材料研究进展[J]. 无机材料学报, 2018, 33(2): 129-137.

LIU Qian, ZHOU Zhen-Zhen. Progress in Activated-synthesis of Si-based Oxynitrides
Materials at Low Temperatures[J]. Journal of Inorganic Materials, 2018, 33(2): 129-137.

图/表 11

图1 介孔硬模板法结合纳米浇注及碳热还原氮化合成β-Sialon粉体过程示意图[19]

Fig.1 Schematic processing of β-Sialon powder synthesis via a combination route of mesoporous hard template, nano-casting, and carbothermal reduction nitridation[19]

表1 样品的比表面积, 孔容和平均孔径[19]

Table 1 Surface area, pore volume, and average pore size of samples[19]

Sample	Surface area, S_BET/(m²•g^-1)	Pore volume, V_BJH/(cm³•g^-1)	Average pore size, D_pore/nm
SBA-15 hard template	577.0	0.88	6.1
SBA-15/C/Al₂O₃composited precursor	359.0	0.23	2.6
β-Si₃Al₃O₃N₅product 1420℃/6 h (Z=3)	15.8	0.03	7.7

图2 (a) SBA-15、(b)介孔碳/氧化硅/氧化铝复合前驱物和(c)β-Si3Al3O3N5粉体的SEM照片 [19]

Fig. 2 SEM microscopic images of (a) SBA-15, (b) SBA-15/C/Al2O3 composite precursors and (c) resultant β-Si3Al3O3N5 product powders[19]

图3 SBA-15与Y2O3反应生成Y2SiO5的机理示意图[24]

Fig. 3 Illustration of the reaction scheme of Y2SiO5 formation between Y2O3 and SBA-15[24]

图4 (a)SBA-15颗粒, (b)利用SBA-15/C添加0.5mol% Y2O3在1280℃反应7 h后的Si2N2O单个颗粒, (c)介孔二氧化硅球(MMS), (d)利用MMS/C 添加0.5mol% Y2O3在1280℃反应 7 h后的Si2N2O颗粒的SEM照片[24]

Fig. 4 SEM images of (a) SBA-15 particle, (b) Si2N2O particle prepared using a SBA-15/C composite with 0.5mol% Y2O3 calcined at 1280℃/7 h, (c) mesoporous silica spheres (MMS), and (d) Si2N2O particle prepared using a MMS/C composite with 0.5mol% Y2O3 calcined at 1280℃/7 h[24]

图5 β-Sialon : xEu2+(z=1.00, 掺杂浓度x=0.010’ 0.200)荧光粉的(a)激发光谱 (λem=416及525 nm)和(b)发射光谱(λex=265及275 nm), 粉体合成温度1400℃[38]

Fig. 5 (a) Excitation spectra and (b) emission spectra of β-Sialon : xEu2+ (x=0.010’0.200, z=1.00) phosphor samples with various x values, synthesized at 1400℃(λex=265, 275 nm, λem=416, 525 nm)[38]

图6 β-Sialon : 0.05Eu2+(z=1.00)荧光粉的高温荧光光谱图(T=25’275℃)[38]

Fig. 6 PL emission spectra of as-synthesized β-Sialon : 0.05Eu2+ (z=1.00) phosphor sample synthesized at 1400℃, measured in an increasing temperature range from 25℃ to 275℃[38]

图7 1460℃合成, 以蔗糖为还原剂再被覆活性碳得到的β-Sialon : Eu2+ 纤维的XRD图谱[46]

Fig. 7 XRD patterns of β-Sialon : Eu2+ fibers calcined at 1460℃, using sucrose and carbon powders as duplicate reducing agents[46]

图8 1460℃碳热还原处理, 蔗糖及活性炭粉作为复合还原剂得到的β-Sialon : Eu2+ 纤维形貌的SEM照片[46]

Fig. 8 Morphology image of β-Sialon : Eu2+ fibers calcined at 1460℃, using sucrose and carbon powders as duplicate reducing agents[46]

图9 1560℃煅烧5 h得到的Y5(1-x)Si3O12N : 5xEu2+(x = 0.005~ 0.06)荧光粉的XRD图谱 [47]

Fig. 9 XRD patterns of Y5(1-x)Si3O12N : 5xEu2+ (x = 0.005~ 0.06) calcined at 1560℃ for 5 h[47]

图10 Y5(1-x)Si3O12N : 5xEu2+(掺杂浓度x=0.003~0.06)荧光粉在365 nm波长激发下的归一化发射光谱(a)和发射谱对应的色坐标以及荧光粉在365 nm紫外灯辐照下的发光图片(b) [47]

Fig. 10 (a) Normalized emission spectra (λex=365 nm), (b) corresponding CIE coordinates and photographs under a UV (365 nm) light radiation of Y5(1-x)Si3O12N : 5xEu2+(x=0.003~0.06) phosphors[47]

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