纳米ZrB2复相陶瓷粉体表面有机功能改性及其对复合材料热性能的影响

doi:10.7503/cjcu20150145

摘要/Abstract

摘要：

为了提高环氧树脂的热性能, 将熔点高、导热耐热性好的ZrB₂粉体作为增强体加入环氧树脂基体中, 通过原位聚合制备了复合材料. 为了改善ZrB₂粉体在环氧树脂中的分散性, 通过高能球磨法将纳米Al₂O₃引入ZrB₂中, 形成ZrB₂-Al₂O₃复相陶瓷粉体, 再用3-三乙氧基甲硅烷基-1-丙胺、 3-缩水甘油醚氧基丙基三甲氧基硅烷和3-(三甲氧基甲硅烷基)丙基丙烯酸酯分别对ZrB₂-Al₂O₃复相陶瓷粉体表面进行有机功能改性. 通过扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对表面改性ZrB₂-Al₂O₃复相陶瓷粉体进行表征; 利用透射电子显微镜(TEM)、动态热机械分析(DMA)和热重分析(TGA)对复合材料的组织和热性能进行分析. 结果表明, 改性后ZrB₂-Al₂O₃复相陶瓷粉体品质优良, 3种有机偶联剂均在ZrB₂-Al₂O₃复相陶瓷粉体表面形成化学键合; 表面经有机偶联剂改性的ZrB₂-Al₂O₃复相陶瓷粉体在基体环氧树脂中具有较好的分散性, 且3-缩水甘油醚氧基丙基三甲氧基硅烷的改性效果最佳. 表面改性后ZrB₂-Al₂O₃复相陶瓷粉体较改性前复合材料呈现出更高的耐热性能.

关键词: ZrB2-Al2O3复相陶瓷粉体, 表面有机改性, 环氧树脂, 热性能

Abstract:

In order to enhance the thermal properties of the epoxy resin, zirconium diboride(ZrB₂) powders were chosen as reinforcement to add to the epoxy resin matrix to prepare composites by the in-situ polymerization due to its high melting point, good thermal conductivity and good heat resistance. The nano-alumina(Al₂O₃) was introduced in to form ZrB₂-Al₂O₃ multiphase ceramics through the high energy ball milling and by surface organic modification of nano-Al₂O₃ to achieve improved dispersibility of ZrB₂ particles in epoxy resin. The multiphase ceramic particles were modified by γ-aminopropyltriethoxysilane, γ-glycidoxypropyltri-methoxysilane and γ-methacryloxypropyltrimethoxysilane, respectively. The modified multiphase particles were characterized by scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS). The microstructure and thermal properties of composites filled with modified particles were analyzed using transmission electron microscopy(TEM), dynamic thermomechanical analysis(DMA) and thermo gravimetric analysis(TGA). The results show that the quality of multiphase particles is good after modification. The three organic coupling agent molecules are all combined to the surfaces of multiphase particles by the covalent bonds. The multiphase particles modified with organic coupling agents disperse well in epoxy resin matrix and the effect of γ-glycidoxypropyltrimethoxysilane is the best. The Composites filled with modified particles present higher thermal properties compared to unmodified composites.

Key words: ZrB2-Al2O3 multiphase ceramics, Surface organic modification, Epoxy resin, Thermal property

中图分类号:

O633.13

TrendMD:

何延楠, 于志强. 纳米ZrB₂复相陶瓷粉体表面有机功能改性及其对复合材料热性能的影响. 高等学校化学学报, 2015, 36(9): 1846.

HE Yannan, YU Zhiqiang. Effect of Surface Organic Functional Modification of ZrB₂ Nanosize Multiphase Ceramics on the Thermal Properties of Its Composites^†. Chem. J. Chinese Universities, 2015, 36(9): 1846.

图/表 10

Fig.1 FTIR spectra of ZrB2-Al2O3 multiphase particlesa. Unmodified; b. modified with γ-aminopropyltriethoxysilane; c. modified with γ-glycidoxypropyltrimethoxysilane; d. modified with γ-methacryloxypropyltrimethoxysilane.

Fig.2 XPS spectra of ZrB2-Al2O3 multiphase particles(A) Unmodified; (B) modified with γ-aminopropyltriethoxysilane; (C) modified with γ-glycidoxypropyltrimethoxysilane;(D) modified with γ-methacryloxypropyltrimethoxysilane.

Table 1 Binding energy(EB) of elements on the surface of different particles

ZrB₂-Al₂O₃ Multiphase particle	E_B(O₁_s)/eV	E_B(S $i 2 p 3$ )/eV	E_B(Al₂_p)/eV
Unmodified	534.0	103.0	76.0
Modified with γ-aminopropyltriethoxysilane	528.0	97.0	71.0
Modified with γ-glycidoxypropyltrimethoxysilane	531.0	101.0	74.0
Modified with γ-methacryloxypropyltrimethoxysilane	533.0	103.0	75.0

Table 1 Binding energy(EB) of elements on the surface of different particles

ZrB₂-Al₂O₃ Multiphase particle	E_B(O₁_s)/eV	E_B(S $i 2 p 3$ )/eV	E_B(Al₂_p)/eV
Unmodified	534.0	103.0	76.0
Modified with γ-aminopropyltriethoxysilane	528.0	97.0	71.0
Modified with γ-glycidoxypropyltrimethoxysilane	531.0	101.0	74.0
Modified with γ-methacryloxypropyltrimethoxysilane	533.0	103.0	75.0

Fig.3 TEM image(A) and EDS spectrum(B) of unmodified ZrB2-Al2O3 multiphase particles

Fig.4 TEM image(A) and EDS spectrum(B) of surface modified ZrB2-Al2O3 multiphase particles

Scheme 1 Surface modification mechanism diagram of multiphase particles with coupling agents γ-glycidoxypropyltrimethoxysilane

Fig.5 TEM images of composites filled with ZrB2-Al2O3 multiphase particles unmodified(A), modified with γ-aminopropyltriethoxysilane(B), γ-glycidoxypropyltrimethoxysilane(C) and γ-methacryloxypropyltrimethoxysilane(D)

Fig.6 DMA curves of epoxy resin and composites modified by γ-glycidoxypropyltrimethoxy-silanea. Epoxy resin; b. 5% ZrB2-Al2O3; c. 5% modified ZrB2-Al2O3; d. 10% modified ZrB2-Al2O3; e. 15% modified ZrB2-Al2O3.

Fig.7 TGA curves of epoxy resin and composites modified by γ-glycidoxypropyltrimethoxy-silanea. Epoxy resin; b. 5% ZrB2-Al2O3; c. 5% modified ZrB2-Al2O3; d. 10% modified ZrB2-Al2O3; e. 15% modified ZrB2-Al2O3.

Table 2 TGA results of epoxy resin and composites

Filler	T_i/℃	T_e/℃	T_max/℃
Epoxy resin	318.6	392.1	367.8
5% ZrB₂-Al₂O₃	337.6	394.6	375.4
5% Modified ZrB₂-Al₂O₃	367.6	403.9	392.7
10% Modified ZrB₂-Al₂O₃	341.6	399.1	381.1
15% Modified ZrB₂-Al₂O₃	325.2	396.6	375.2

参考文献 15

[1]	Mustata F., Tudorachi N., Bicu I., Composites Part B, 2013, 55(12), 470—478
[2]	Wu Y. Q., Zeng M., Xu Q. G., Hou S. E., Jin H. Y., Fan L. R., Tribol. Int., 2012, 54(10), 51—57
[3]	Guo Q. P., Zheng H. F., Polym., 1999, 40(3), 637—646
[4]	Jin F. L., Park S. J., Polym. Degrad. Stabil., 2012, 97(11), 2148—2153
[5]	Kim K., Kim M., Kim J., Comp. Sci. Tech., 2014, 103(10), 72—77
[6]	Yu Z. Q., You S. L., Baier H., Polym. Comp., 2012, 33(9), 1516—1524
[7]	Radoman T.Dunuzovic' E. S., Mater. Design, 2014, 62(10), 158—167
[8]	Yu Z. Q., You S. L., Yang Z. G., Baier H., Adv. Comp. Mater., 2011, 20(5), 487—502
[9]	Hwang Y., Kim M., Kim J., Chem. Eng. J., 2014, 246(6), 229—237
[10]	Peng W. Y., Huang X. Y., Yu J. H., Jiang P. K., Liu W. H., Composites Part A, 2010, 41(9), 1201—1209
[11]	Ding Z. H., Qiu L. X., Zhang J., Yao B., Cui T., Guan W. M., Zheng W. T., Wang W. Q., J. Alloys Compd., 2012, 521(4), 66—70
[12]	Monteverde F., Bellosi A., Guicciardi S., J. Eur. Ceram. Soc., 2002, 22(3), 279—288
[13]	Wei B. G., Chang Q., Bao C. X., Dai L., Collo. Surf. A: Physicochemical and Engineering Aspects, 2013, 434(10), 276—280
[14]	Yue Y. L., Zhang X. H., Xu Y. C., Mater. Lett., 2014, 136(12), 356—358
[15]	Sroda M., Paluszkiewicz C., Vibra. Spectro., 2008, 48(2), 246—250

纳米ZrB₂复相陶瓷粉体表面有机功能改性及其对复合材料热性能的影响

Effect of Surface Organic Functional Modification of ZrB₂ Nanosize Multiphase Ceramics on the Thermal Properties of Its Composites^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

[1]	高健, 冯奕钰, 方文宇, 王慧, 葛婧, 封伟. 基于低温热释放的烷基接枝相变偶氮苯材料[J]. 高等学校化学学报, 2022, 43(8): 20220146.
[2]	赵君禹, 王春博, 王成杨, 张克, 丛冰, 杨岚, 赵晓刚, 陈春海. 导热膨胀石墨/聚醚酰亚胺复合材料的制备与性能[J]. 高等学校化学学报, 2022, 43(4): 20210800.
[3]	杨隽阁, 高成乾, 李博鑫, 尹德忠. 改性氧化石墨烯稳定Pickering乳液法制备高导热相变整体材料[J]. 高等学校化学学报, 2022, 43(2): 20210593.
[4]	储瑶, 王烁, 张子诺, 王艺博, 蔡以兵. 铜粒子负载泡沫基相变复合材料的制备与性能[J]. 高等学校化学学报, 2022, 43(2): 20210619.
[5]	王献伟, 柯红军, 袁航, 鲁戈舞, 李丽英, 孟祥胜, 宋书林, 王震. 耐高温可溶性聚酰亚胺树脂及其复合材料[J]. 高等学校化学学报, 2021, 42(6): 2041.
[6]	许晓洲, 刘仪, 何民辉, 莫松, 蓝邦伟, 翟磊, 范琳. 共聚结构和分子量对热塑性聚酰亚胺树脂熔融与耐热性能的影响[J]. 高等学校化学学报, 2021, 42(3): 919.
[7]	董璐铭, 苏衍跃, 王春征, 乔亚飞, 陈雅君, 马海云. 微纳米钙钛矿型羟基锡酸钙的合成及对环氧树脂的阻燃性能[J]. 高等学校化学学报, 2021, 42(3): 937.
[8]	王鹏, 毛丹, 万家炜, 祁琪, 杜江, 王丹. 中空多壳层TiO₂填充对环氧树脂复合材料力学性能的影响[J]. 高等学校化学学报, 2021, 42(10): 3218.
[9]	沙迪, 禹旭敏, 赵将, 马小飞, 王汉夫, 刘芳芳, 邱雪鹏. 碳纤维三向织物/环氧树脂复合材料的制备与力学性能[J]. 高等学校化学学报, 2020, 41(4): 838.
[10]	谢璠,王亚芳,卓龙海,秦盼亮,宁逗逗,王丹妮,陆赵情. 高导热氮化硼/芳纶沉析复合薄膜的制备及性能[J]. 高等学校化学学报, 2020, 41(3): 582.
[11]	王晓慧, 王可心, 刘俊平, 洪霞. 介孔结构增强的Fe₃O₄超粒子@介孔SiO₂的光热性能[J]. 高等学校化学学报, 2019, 40(8): 1586.
[12]	张跃发, 邵华锋, 王日国, 贺爱华. 反式丁戊橡胶改性航空轮胎侧胶的结构与性能[J]. 高等学校化学学报, 2019, 40(8): 1733.
[13]	殷平, 闫红强, 程捷, 方征平. 新型生物基苯并噁嗪的合成及性能[J]. 高等学校化学学报, 2019, 40(5): 1071.
[14]	韩涛, 蔡小霞, 李聪, 乔从德, 赵辉. 生物基氢化香豆素增韧环氧树脂的制备及性能[J]. 高等学校化学学报, 2019, 40(5): 1043.
[15]	刘韬, 李文静, 张恩爽, 钟锦洋, 张凡, 刘圆圆, 赵英民. 柔性交联型聚酰亚胺气凝胶的制备及性能[J]. 高等学校化学学报, 2019, 40(2): 403.