蒙脱土-弹性体/聚丙烯复合体系纳米颗粒相区分散对结晶形态与介电性能的影响

高俊国; 姚子恒; 刘艳丽; 刘泓铄; 王然; 刘力伟; 郭宁; 李丽丽

doi:10.13801/j.cnki.fhclxb.20220606.001

蒙脱土-弹性体/聚丙烯复合体系纳米颗粒相区分散对结晶形态与介电性能的影响

doi: 10.13801/j.cnki.fhclxb.20220606.001

哈尔滨理工大学　工程电介质及其应用教育部重点实验室，哈尔滨 150080

基金项目: 国家自然科学基金资助项目(51577045)；黑龙江省博士后科研启动基金(LBH-Q19106)

详细信息

通讯作者:
李丽丽，博士，讲师，研究方向为高电压与绝缘性能测试和模拟等　E-mail: lily_li@hrbust.edu.cn

中图分类号: TM215.92；TB332
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出版历程
- 收稿日期: 2022-04-08
- 修回日期: 2022-05-11
- 录用日期: 2022-05-20
- 网络出版日期: 2022-06-07
- 刊出日期: 2023-04-15

Influence of interphase dispersion state of nanoparticles on crystal morphology and dielectric properties in montmorillonite elastomer/polypropylene composites

Key Laboratory of Engineering Dielectrics and Its Applications, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China

Funds: National Natural Science Foundation of China (51577045); Heilongjiang Postdoctoral Grant (LBH-Q19106)

摘要

摘要: 随着电缆需求量日益加大，环保节能绝缘已成为新的发展趋势，研发改进聚丙烯(PP)成为电介质研究学者们的首选。为改善聚丙烯-弹性体共混物的介电性能，采用两步熔融共混法，使用两种不同的增容剂配合有机化处理蒙脱土(MMT)制备MMT-POE/PP纳米改性共混材料，探讨纳米颗粒在共混物材料不同相区内的分散状态，及其对纳米改性效果的影响。利用SEM、静电力显微镜(EFM)、偏光显微镜(PLM)与DSC表征介质的微观结构、结晶形态与结晶参数，并通过对共混物进行击穿性能测试，探讨相区分散对MMT-POE/PP复合材料性能提升的微观机制。实验结果表明：MMT倾向于PP相分散时，其结晶尺寸减小至4.7 μm，结晶速度与结晶度有所上升，这使介电常数和绝缘电导率明显下降，且交流击穿场强从82.69 kV/mm提升至95.16 kV/mm。通过调控纳米颗粒倾向于PP相均匀分散，方可对共混物材料的介电性能起到正向提升的作用。
- 蒙脱土 /
- 聚丙烯 /
- 相区分散性 /
- 结晶形态 /
- 介电性能 /
- 电缆
Abstract: With the increasing demand for cable, environmental protection and energy-saving insulation has become a new development trend, and the research and development of polypropylene (PP) has become the first choice of dielectric researchers. In order to improve dielectric properties of polypropylene-elastomer blends, MMT-POE/PP nano-modified blends were prepared by two-step melting blending method with two different compatibilizers and organically treated montmorillonite (MMT). And then the effects of interphase dispersion states of nanoparticles in different phase zones on dielectric properties of nano-modified blends were investigated. The microstructure, crystalline morphology and crystallization parameters were characterized by SEM, electrostatic force microscopy (EFM), polarizing microscope (PLM) and DSC. The micro-mechanism of phase dispersion on MMT-POE/PP composites was discussed through the breakdown properties test of the blend sample. The experimental results show that when MMT layers tend to disperse in the PP phase, the crystallization size decreases about 5.9 μm, the crystallization speed increases, and the crystallinity increases about 2.1%. And then the dielectric constant and insulation conductivity decrease obviously, and the alternating current (AC) breakdown field strength increases from 82.69 kV/mm to 95.16 kV/mm. The dielectric properties of nano-modified blends can be positively improved by regulating the tendency of nanoparticles to disperse uniformly in the PP phase.
- montmorillonite /
- polypropylene /
- interphase dispersion state /
- crystal morphology /
- dielectric properties /
- cable

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图 1 两步熔融共混法的工艺过程

Figure 1. Process of two-step melting blending method

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图 2 有机化处理前后MMT的XRD图谱

Figure 2. XRD patterns of MMT before and after organic treatment

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图 3 MMT-POE/PP复合材料的SEM图像

Figure 3. SEM images of MMT-POE/PP composites

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图 4 MMT-POE/PP复合材料的EFM相位图

Figure 4. EFM phase diagram of MMT-POE/PP composites

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图 5 MMT-POE/PP复合材料的结晶形态及尺寸图

Figure 5. Crystal morphologies and size of MMT-POE/PP composites

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图 6 10℃/min升降温速率下MMT-POE/PP复合材料的DSC曲线图

Figure 6. DSC curves of MMT-POE/PP composites at 10℃/min heating and cooling rate

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图 7 MMT-POE/PP复合材料的相对介电常数ε_r (a) 与介电损耗tanδ (b) 随频率的变化

Figure 7. Distribution of relative permittivity ε_r (a) and dielectric loss tanδ (b) vary with frequency of MMT-POE/PP composites

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图 8 MMT-POE/PP复合材料的电导率变化

Figure 8. Change of conductivity of MMT-POE/PP composites

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图 9 MMT-POE/PP复合材料交流击穿电压E₀与形状参数β分布图

Figure 9. E₀ and β distribution of alternating current breakdown of MMT-POE/PP composites

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表 1 蒙脱土-弹性体/聚丙烯复合体系(MMT-POE/PP)试样编号和成分组成

Table 1. Sample number and composition of montmorillonite elastomer/polypropylene composites (MMT-POE/PP)

No.	Mass ratio
No.	PP	MAH-g-PP	POE	MAH-g-POE	MMT	1010
PP	100	−	−	−	−	0.3
20POE/80PP	80	−	20	−	−	0.3
1MMT-20POE/80PP	80	−	20	−	1	0.3
A-1MMT-20POE/75PP	75	5	20	−	1	0.3
B-1MMT-15POE/80PP	80	−	15	5	1	0.3
Notes: MAH—Maleic anhydride; POE—Ethylene-octene copolymer.

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表 2 MMT-POE/PP试样的等温结晶和熔融过程参数

Table 2. Parameters of isothermal crystallization and melting processes of MMT-POE/PP samples

No.	T_m/℃	T_c/℃	ΔT_c/℃	W_c/%
PP	170.4	118.5	5.2	38.3
20POE/80PP	171.6	117.1	5.4	33.6
1MMT-20POE/80PP	171.1	115.1	5.3	35.5
A-1MMT-20POE/75PP	171.6	116.1	4.7	35.7
B-1MMT-15POE/80PP	172.1	112.1	6.1	33.0
Notes: T_m and T_c—Melting temperature and crystallization peak temperature in the first stage; ΔT_c—Exothermic crystallization peak width in the first stage; W_c—Crystallinity in the first stage.

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