基于硅橡胶基可加工前驱体的低温烧结CaZnSi<sub>2</sub>O<sub>6</sub>玻璃陶瓷

李鹏虎; 金海云; 刘怀东; 王昭; 高乃奎

基于硅橡胶基可加工前驱体的低温烧结CaZnSi₂O₆玻璃陶瓷

西安交通大学　电力设备电气绝缘国家重点实验室, 西安 710049

基金项目: 国家自然科学基金 (52272073)

详细信息

通讯作者:
金海云，博士，教授，博士生导师，研究方向为电介质与绝缘材料　E-mail: hyjin@mail.xjtu.edu.cn

中图分类号: TQ174;TQ333
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出版历程
- 收稿日期: 2022-09-05
- 修回日期: 2022-10-06
- 录用日期: 2022-10-08
- 网络出版日期: 2022-10-31
- 刊出日期: 2023-08-15

Low-temperature sintering of CaZnSi₂O₆ glass ceramics with machinable precursor based on silicone rubber

State Key Laboratory of Electrical Insulation and Power Equipment, Xi’an Jiaotong University, Xi’an 710049, China

Funds: The National Natural Science Foundation of China (52272073)

摘要

摘要: 陶瓷材料的应用由于其烧结温度高、加工性能差而受到限制。硅橡胶基可陶瓷化复合材料在常温下具有良好的加工性能，而在高温下可以转化为陶瓷材料。因此将硅橡胶基可陶瓷化复合材料作为可加工前驱体，可以解决陶瓷材料的加工问题。然而，以往的研究只是将可陶瓷化复合材料作为一种耐火阻燃材料，导致烧结后陶瓷材料的机械强度较低，弯曲强度一般不超过30 MPa。为了将这种陶瓷材料应用于实际工程中，提高陶瓷材料的机械强度是至关重要的。本研究提出了一种具有可加工前驱体、低烧结温度和高机械强度的CaZnSi₂O₆玻璃陶瓷。为此使用硅橡胶基可陶瓷化复合材料作为低温烧结CaZnSi₂O₆玻璃陶瓷的可加工前驱体，研究了前驱体中硅橡胶比例和低熔点玻璃粉含量对陶瓷材料弯曲强度的影响，并得到了前驱体的基础配方。前驱体具有良好的加工性能，可以剪切成不同尺寸不同形状并完成陶瓷材料的烧结。通过加入适量的Bi₂O₃作为辅助助熔剂，提高了陶瓷的致密度和机械强度，弯曲强度由90.54 MPa提升至110.48 MPa，提高了约22%，同时线性收缩率仅增加了1.88%。Bi元素保留在玻璃相中，没有改变陶瓷的晶相物质。玻璃相中的Bi元素能够通过抑制电导和热离子极化，从而抑制损耗随温度升高而增大的趋势。也就是说Bi元素的加入使得材料在高温下的工频损耗显著降低。此外，Bi₂O₃的加入还使材料的工频击穿场强提高了约25%。1(a)不添加Bi₂O₃与(b)添加Bi₂O₃的陶瓷材料表面显微形貌2温度对陶瓷试样工频介电性能的影响
- 可陶瓷化复合材料 /
- 可加工前驱体 /
- 玻璃陶瓷 /
- 显微形貌 /
- 介电性能
Abstract: The applications of ceramics are limited by their high sintering temperatures and poor processability. The ceramizable silicone rubber composites were prepared using kilchoanite as a ceramic filler, low-melting-point glass frit as a flux, and nano SiO₂ as a reinforcing agent. The CaZnSi₂O₆ glass ceramics were sintered at 1000℃ using the ceramizable composites as machinable precursors. The effect of the mass fraction of silicone rubber and the content of glass frit on the mechanical properties of the ceramics was studied. The effect of Bi₂O₃ as a secondary flux on the microstructure, flexural strength and dielectric properties of the ceramics was investigated. The results showed that the flexural strength of the ceramic samples increased first and then decreased with reducing the mass fraction of silicone rubber or increasing the content of glass frit. The maximum flexural strength of the ceramic samples without Bi₂O₃ sintered at 1000℃ was 90.54 MPa, and the linear contraction was only 15%. A proper content of Bi₂O₃ not only improved the density of microstructure and increased the flexural strength to 110.48 MPa, but also decreased the tanδ of the ceramics at power frequency and high temperature obviously, and improved the breakdown strength of the ceramics at power frequency. The precursors in this study had a good processability and could complete the sintering of ceramics with different sizes and shapes.
- ceramizable composites /
- machinable precursors /
- glass ceramics /
- microstructure /
- dielectric properties

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图 1 陶瓷试样的烧结温度程序

Figure 1. Sintering temperature program of the ceramic samples

下载: 全尺寸图片幻灯片

图 2 不同硅橡胶含量下陶瓷试样的弯曲强度

Figure 2. Flexural strength of ceramic samples with different mass fraction of silicon rubber

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图 3 不同硅橡胶含量下陶瓷试样的线性收缩率

Figure 3. Linear contraction of ceramic samples with different mass fraction of silicon rubber

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图 4 不同玻璃粉含量下陶瓷试样的弯曲强度

Figure 4. Flexural strength of ceramic samples with different mass fraction of glass frit

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图 5 不同玻璃粉含量下陶瓷试样的线性收缩率

Figure 5. Linear contraction of ceramic samples with different mass fraction of glass frit

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图 6 可加工前驱体(左)和陶瓷试样(右)的照片

Figure 6. Photos of machinable precursors (left) and ceramic samples (right)

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图 7 陶瓷试样与斜方硅钙石的XRD曲线

Figure 7. XRD patterns of the ceramic samples and kilchoanite

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图 8 陶瓷试样的表面形貌SEM照片

Figure 8. SEM images of surface microstructure of the ceramic samples

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图 9 温度对陶瓷试样工频介电性能的影响

Figure 9. Effect of temperature on the dielectric properties of the ceramic samples at power frequency

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图 10 陶瓷试样工频击穿场强的Weibull分布(F为分布概率，E_b为击穿场强)

Figure 10. Weibull distribution of breakdown strength of the ceramic samples at power frequency (F is the distribution probability, E_b is the breakdown strength)

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表 1 硅橡胶基可陶瓷化复合材料的配方

Table 1. Formula of ceramizable silicone rubber composites

Sample	Mass ratio/g				W_x/wt%
Sample	Silicone rubber	Kilchoanite	Glass frit	Nano SiO₂	W_x/wt%
S1	100	50	30	30	47.62
S2	100	100	60	60	31.25
S3	100	117	70	70	28.04
S4	100	133	80	80	25.42
S5	100	150	90	90	23.26
S6	100	200	120	120	18.52
G1	100	117	65	70	18.47
G2	100	117	70	70	19.61
G3	100	117	75	70	20.72
G4	100	117	80	70	21.80
G5	100	117	90	70	23.87
G6	100	117	100	70	25.84
Notes: W_x is the mass fraction of silicone rubber for S1~S6 and the mass fraction of glass frit for G1~G6.

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参考文献(27)

[1]	柯瑞林, 邹雄, 王金合, 等. 陶瓷化高分子复合材料研究进展[J]. 绝缘材料, 2018, 51(12):1-5. doi: 10.16790/j.cnki.1009-9239.im.2018.12.001 KE Ruilin, ZOU Xiong, WANG Jinhe, et al. Research progress of ceramifiable polymer composites[J]. Insulating Materials,2018,51(12):1-5(in Chinese). doi: 10.16790/j.cnki.1009-9239.im.2018.12.001
[2]	唐红川, 李鹏虎, 匡国文, 等. 陶瓷化硅橡胶研究进展[J]. 绝缘材料, 2019, 52(7):1-9. TANG Hongchuan, LI Penghu, KUANG Guowen, et al. Research progress on ceramic silicone rubber[J]. Insulating Materials,2019,52(7):1-9(in Chinese).
[3]	HANU L G, SIMON G P, MANSOURI J, et al. Development of polymer-ceramic composites for improved fire resistance[J]. Journal of Materials Processing Technology,2004,153-154:401-407. doi: 10.1016/j.jmatprotec.2004.04.104
[4]	MANSOURI J, BURFORD R P, CHENG Y B, et al. Formation of strong ceramified ash from silicone-based compositions[J]. Journal of. Materials Science,2005,40(21):5741-5749. doi: 10.1007/s10853-005-1427-8
[5]	MANSOURI J, BURFORD R P, CHENG Y B. Pyrolysis behaviour of silicone-based ceramifying composites[J]. Materials Science and Engineering A,2006,425(1-2):7-14. doi: 10.1016/j.msea.2006.03.047
[6]	HANU L G, SIMON G P, CHENG Y B. Thermal stability and flammability of silicone polymer composites[J]. Polymer Degradation and Stability,2006,91(6):1373-1379. doi: 10.1016/j.polymdegradstab.2005.07.021
[7]	MANSOURI J, WOOD C A, ROBERT K, et al. Investigation of the ceramifying process of modified silicone silicate compositions[J]. Journal of Materials Science,2007,42(15):6046-6055. doi: 10.1007/s10853-006-1163-8
[8]	HAMDANI S, LONGUET C, PERRIN D, et al. Flame retardancy of silicone-based materials[J]. Polymer Degradation and Stability,2009,94(4):465-495. doi: 10.1016/j.polymdegradstab.2008.11.019
[9]	PĘDZICH Z, BIELIŃSKI D M, ANYSZKA R, et al. Ceramizable composites for fire resistant applications[J]. Key Engineering Materials,2014,602-603:290-295. doi: 10.4028/www.scientific.net/KEM.602-603.290
[10]	YU L, ZHOU S T, ZOU H W, et al. Thermal stability and ablation properties study of aluminum silicate ceramic fiber and acicular wollastonite filled silicone rubber composite[J]. Journal of Applied Polymer Science,2014,131(1):39700.
[11]	GUO J H, ZHANG Y, LI H J, et al. Effect of the sintering temperature on the microstructure, properties and formation mechanism of ceramic materials obtained from polysiloxane elastomer-based ceramizable composites[J]. Journal of Alloys and Compounds,2016,678:499-505. doi: 10.1016/j.jallcom.2016.04.030
[12]	HU S, CHEN F, LI J G, et al. The ceramifying process and mechanical properties of silicone rubber/ammonium polyphosphate/aluminium hydroxide/mica composites[J]. Polymer Degradation and Stability,2016,126:196-203. doi: 10.1016/j.polymdegradstab.2016.02.010
[13]	LOU F P, YAN W, GUO W H, et al. Preparation and properties of ceramifiable flame-retarded silicone rubber composites[J]. Journal of Thermal Analysis and Calorimetry,2017,130(2):813-821. doi: 10.1007/s10973-017-6448-4
[14]	PĘDZICH Z, BUKAŃSKA A, BIELIŃSKI D M, et al. Microstructure evolution of silicone rubber-based composites during ceramization in different conditions[J]. Composites Theory and Practice,2012,12(4):251-255.
[15]	BIELIŃSKI D M, ANYSZKA R, PĘDZICH Z, et al. Ceramizable silicone rubber composites. Influence of type of mineral filler on ceramization[J]. Composites Theory and Practice,2012,12(4):256-261.
[16]	ANYSZKA R, BIELIŃSKI D M, PĘDZICH Z, et al. Influence of surface-modified montmorillonites on properties of silicone rubber-based ceramizable composites[J]. Journal of Thermal Analysis and Calorimetry,2015,119(1):111-121. doi: 10.1007/s10973-014-4156-x
[17]	WANG J H, JI C T, YAN Y T, et al. Mechanical and ceramifiable properties of silicone rubber filled with different inorganic fillers[J]. Polymer Degradation and Stability,2015,121:149-156. doi: 10.1016/j.polymdegradstab.2015.09.003
[18]	IMIELA M, ANYSZKA R, BIELIŃSKI D M, et al. Effect of carbon fibers on thermal properties and mechanical strength of ceramizable composites based on silicone rubber[J]. Journal of Thermal Analysis and Calorimetry,2016,124(1):197-203. doi: 10.1007/s10973-015-5115-x
[19]	ANYSZKA R, BIELIŃSKI D M, PĘDZICH Z, et al. Effect of mineral filler additives on flammability, processing and use of silicone-based ceramifiable composites[J]. Polymer Bulletin,2018,75(4):1731-1751. doi: 10.1007/s00289-017-2113-0
[20]	孟盼, 王雁冰, 魏冲, 等. 硅藻土/硅橡胶可陶瓷化复合材料的制备及性能[J]. 复合材料学报, 2017, 34(1):53-59. doi: 10.13801/j.cnki.fhclxb.20160411.003 MENG Pan, WANG Yanbing, WEI Chong, et al. Preparation and properties of ceramifiable diatomite/silicone rubber composites[J]. Acta Materiae Compositae Sinica,2017,34(1):53-59(in Chinese). doi: 10.13801/j.cnki.fhclxb.20160411.003
[21]	LI P H, JIN H Y, WEI S C, et al. Ceramization mechanism of ceramizable silicone rubber composites with nano silica at low temperature[J]. Materials,2020,13(17):3708. doi: 10.3390/ma13173708
[22]	李函坚, 郭建华, 高伟, 等. 白炭黑对陶瓷化硅橡胶瓷化性能的影响[J]. 有机硅材料, 2015(5):360-365. LI Hanjian, GUO Jianhua, GAO Wei, et al. Effect of silica on ceramifying properties of silicone rubber-based ceramizable composites[J]. Silicone Material,2015(5):360-365(in Chinese).
[23]	孟盼, 张光武, 熊梦, 等. 玻璃料对可陶瓷化硅橡胶基复合材料耐高温性能的影响[J]. 复合材料学报, 2016, 33(10):2205-2214. MENG Pan, ZHANG Guangwu, XIONG Meng, et al. Effect of glass frits on high-temperature resistance properties of ceramifiable silicone rubber matrix composites[J]. Acta Materiae Compositae Sinica,2016,33(10):2205-2214(in Chinese).
[24]	GUO J H, GAO W, WANG Y, et al. Effect of glass frit with low softening temperature on the properties, microstructure and formation mechanism of polysiloxane elastomer-based ceramizable composites[J]. Polymer Degradation and Stability,2017,136:71-79. doi: 10.1016/j.polymdegradstab.2016.12.012
[25]	LOU F P, CHENG L H, LI Q Y, et al. The combination of glass dust and glass fiber as fluxing agents for ceramifiable silicone rubber composites[J]. RSC Advances,2017,7(62):38805-38811. doi: 10.1039/C7RA07432H
[26]	唐红川, 李鹏虎, 匡国文, 等. 玻璃粉含量对陶瓷化硅橡胶性能的影响[J]. 硅酸盐学报, 2020, 38(6):870-876. TANG Hongchuan, LI Penghu, KUANG Guowen, et al. Effect of glass powder content on properties of ceramizable silicone rubber[J]. Journal of the Chinese Ceramic Society,2020,38(6):870-876(in Chinese).
[27]	LI P H, JIN H Y, LIU H D, et al. Low-temperature sintering of CaZnSi₂O₆ glass ceramics with machinable precursor based on silicone rubber and enhanced mechanical strength by Bi₂O₃[J]. Materials Letters,2022,324:132650. doi: 10.1016/j.matlet.2022.132650