Influence of SiO2 particle size factors on the crystallization behavior and electrical properties of polyethylene matrix composites
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摘要: 分别选用粒径分别为1 μm、30 nm和100 nm的SiO2粒子作添加粒子，以低密度聚乙烯(LDPE)为基体，制备三种SiO2/LDPE复合材料。对各复合材料的结晶行为进行分析，分析各材料的结晶度，同时对每种材料在频率影响下的相对介电常数εr和损耗因子tanδ变化情况进行研究，并探究了各材料的电导电流及空间电荷特性。结果表明，添加粒子的尺寸越小，其所形成的复合材料的晶体尺寸与间距就越小。添加30 nm SiO2粒子后，材料结晶度增加显著；添加100 nm SiO2粒子所构成的微观结构能有效限制分子链运动，使复合材料极化建立困难；大尺寸粒子的添加会对原有结晶结构造成破坏，形成的新结晶结构能促进载流子的迁移；这三种SiO2粒子中，30 nm SiO2粒子的添加能有效抑制空间电荷，100 nm SiO2粒子的加入，则会造成电极附近的异极性电荷积聚。Abstract: The SiO2 particles with diameter of 1 μm, 30 nm and 100 nm were used as additive particles and low-density polyethylene (LDPE) as matrix to prepare the three kinds of SiO2/LDPE composites. The crystallization behavior and crystallinity of LDPE and three kinds of SiO2/LDPE composites were analyzed, the relative dielectric constant εr and loss factor tanδ changes of each material with frequency were measured, and the conductance current and space charge characteristics of the composites were investigated. The results show that the smaller the particle size is, the smaller the crystal size and grains spacing of the composite materials are. After adding 30 nm SiO2 particles, the crystallinity increases significantly. The microstructure formed by adding 100 nm SiO2 particles can effectively limit the chain segment movement, which makes it difficult to establish the polarization of the composites. The addition of large size particles can destroy the original crystal structure, and the new crystal structure can promote the carrier migration. Among the three SiO2 particles, the addition of SiO2 particles at 30 nm can effectively inhibit the space charge, while the addition of SiO2 particles at 100 nm can cause the heterogeneous charge accumulation near the electrode.
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Key words:
- different dimension /
- inorganic fillers /
- SiO2 /
- crystallization /
- electrical properties
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图 2 电声脉冲法实验系统
Figure 2. Test system of pulsed electro-acoustic method
DC—Direct current
图 6 SiO2/LDPE复合材料介电常数εr随频率f变化曲线
Figure 6. Variation curves of relative dielectric constant εr with frequency f of SiO2/LDPE composites
图 7 SiO2/LDPE复合材料损耗因子tanδ随频率f变化曲线
Figure 7. Variation curve of loss factor tanδ with frequency f for SiO2/LDPE composites
图 8 LDPE及SiO2/LDPE复合材料的电导电流随场强变化曲线
Figure 8. Curves of the conductance current of LDPE and SiO2/LDPE composites changing with the field intensity
图 9 LDPE及SiO2/LDPE复合材料的电导电流随场强变化拟合曲线
Figure 9. Curves fitting curves of conductance current of LDPE and SiO2/LDPE composites changing with the field intensity
图 10 LDPE及SiO2/LDPE复合材料的空间电荷特性曲线
Figure 10. Space charge characteristic curves of LDPE and SiO2/LDPE composites
表 1 SiO2/LDPE复合材料的组成成分及含量
Table 1. Compositions and contents of SiO2/LDPE composites
Specimen Mass fraction/wt% LDPE 1 μm SiO2 30 nm SiO2 100 nm SiO2 LDPE 100 0 0 0 1 μm SiO2/LDPE 99 1 0 0 30 nm SiO2/LDPE 99 0 1 0 100 nm SiO2/LDPE 99 0 0 1 Note: LDPE—Low-density polyethylene. 
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表 2 SiO2/LDPE复合材料的熔融峰值与结晶度
Table 2. Melting peaks and crystallinities of SiO2/LDPE composites
Sample Tm/℃ Xc/% $ {\Delta H}_{\rm{m}} $/(J·g−1) LDPE 108.18 30.78 90.37 1 μm SiO2/LDPE 107.62 28.45 83.52 30 nm SiO2/LDPE 109.12 37.01 108.66 100 nm SiO2/LDPE 110.31 29.35 86.17 Notes: Tm—Melting temperature Xc—Crystallinity; $ {\Delta H}_{\rm{m}} $—
Melting enthalpy.
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表 3 SiO2/LDPE复合材料的陷阱密度与载流子迁移率
Table 3. Trap density and carrier mobility of SiO2/LDPE composites
Sample d/μm U/kV nt/1018m3 μe /(10−23 m2·V−1·s−1) LDPE 210 4.38 14.9 1.41 1 μm SiO2/LDPE 210 2.29 8.23 3.93 30 nm SiO2/LDPE 210 3.32 12.0 1.13 100 nm SiO2/LDPE 210 3.71 13.0 1.06 Notes: d—Sample thickness; U—Transient voltage; nt—Trap density; μe—Effective carrier mobility.
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