聚偏氟乙烯/石墨烯复合材料的制备及性能研究

doi:10.11949/0438-1157.20190969

摘要/Abstract

摘要：

用溶液共混法制备出聚偏氟乙烯/氧化石墨烯复合材料(PVDF/GO)，经高温热压将GO还原得到聚偏氟乙烯/还原氧化石墨烯复合材料(PVDF/rGO)。研究了填料种类及含量对复合材料电学性能、热稳定性和力学性能的影响。结果表明：随GO和rGO的添加，两种复合材料的介电常数(ε _r)均变大、介电损耗(tanδ)变化不大；低含量下GO和rGO均能提高PVDF的热稳定性，但rGO对PVDF性能的改善效果更好；随填料含量从0增加到8%(质量)，100 Hz下PVDF/rGO复合材料的ε _r从3.60增加到38.30，PVDF/rGO[4%(质量)]复合材料失重率为5%的分解温度较纯PVDF提高了6.44℃。rGO增强了PVDF的刚性，PVDF/rGO复合材料的拉伸强度先增大后减小，杨氏模量逐渐增大，当rGO含量为4%(质量)时拉伸强度最大，拉伸强度和弹性模量分别较纯PVDF提高了35.30%、22.58%。但GO和rGO都降低了复合材料的击穿场强。

关键词: 聚偏氟乙烯, 氧化石墨烯, 还原氧化石墨烯, 复合材料, 性能

Abstract:

A polyvinylidene fluoride/graphene oxide composite material (PVDF/GO) was prepared by a solution blending method, and GO was reduced by hot pressing to obtain a polyvinylidene fluoride/reduced graphene oxide composite material (PVDF/rGO). The effects of filler types and contents on the electrical properties, thermal stability and mechanical properties of composites were studied. The results showed that both the addition of GO and rGO can improve the dielectric constant (ε _r), thermal stability of PVDF at low content, and the dielectric loss (tan δ) of the composites change little, but PVDF/rGO composites always had higher properties than PVDF/GO composites. The ε _r of PVDF/rGO composites increased from 3.60 to 38.30 at 100 Hz with the filler content from 0 to 8%(mass), the decomposition temperature of 5% mass loss in PVDF/rGO [4%( mass)] composites was 6.44℃ higher than that of pure PVDF. The rigidity of PVDF enhanced by rGO, the tensile strength of PVDF/rGO composites increased firstly and then decreased, and the Young modulus of the composites increased gradually. When the content of rGO was 4%(mass), the tensile strength of PVDF/rGO reached the maximum value, tensile strength and Young modulus increased by 35.30% and 22.58% respectively compared with pure PVDF. However, the breakdown strength of the composites decreased with the addition of GO and rGO.

Key words: polyvinylidene fluoride, graphene oxide, reduced graphene oxide, composites, properties

中图分类号:

TB 324

郭华超, 杨波, 黄国家, 徐青永, 李爽, 伍振凌. 聚偏氟乙烯/石墨烯复合材料的制备及性能研究[J]. 化工学报, 2020, 71(4): 1881-1888.

Huachao GUO, Bo YANG, Guojia HUANG, Qingyong XU, Shuang LI, Zhenling WU. Preparation and properties of polyvinylidene fluoride/graphene composites[J]. CIESC Journal, 2020, 71(4): 1881-1888.

图/表 10

图1 天然石墨、GO和rGO的FT-IR谱图

Fig.1 FT-IR spectra of natural graphite, GO and rGO

图2 石墨和GO的微观结构照片

Fig.2 Microstructure photos of graphite and graphene oxide

图3 天然石墨、GO、PVDF/GO、PVDF/rGO复合材料的XRD谱图

Fig.3 XRD patterns of natural graphite, GO, PVDF/GO composite and PVDF/rGO composite

图4 PVDF/GO、PVDF/rGO复合材料介电常数的频率依赖性

Fig.4 Frequency dependence of dielectric constant of PVDF/GO and PVDF/rGO composites

图5 PVDF/GO、PVDF/rGO复合材料损耗角正切随电场频率的变化

Fig.5 Frequency dependence of dielectric loss of PVDF/GO and PVDF/rGO composites

图6 PVDF/GO、PVDF/rGO复合材料的击穿场强

Fig.6 Breakdown strength of PVDF/GO and PVDF/rGO composites

图7 复合材料的TGA曲线

Fig.7 TGA curves of composites

表1 复合材料的热稳定性

Table 1 Thermal stability of composites

样品	T ₅/℃	T ₁₀/℃	T ₅₀/℃
纯PVDF	454.90	463.07	480.21
PVDF/GO[2%(质量)]	457.43	464.41	480.27
PVDF/GO[4%(质量)]	458.80	468.72	483.40
PVDF/GO[8%(质量)]	439.10	467.98	481.58
PVDF/rGO[2%(质量)]	459.41	466.58	480.42
PVDF/rGO[4%(质量)]	461.34	468.35	485.07
PVDF/rGO[8%(质量)]	439.83	461.83	483.40

表2 PVDF/rGO复合材料的力学性能

Table 2 Mechanical properties of PVDF/rGO composites

rGO含量/% (质量)	拉伸强度/MPa	弹性模量/MPa	断裂伸长率/%
0	26.75	607.98	12.86
1	33.24	613.71	12.84
2	35.60	663.63	11.93
4	36.19	745.24	11.33
6	28.31	960.03	6.59
8	23.47	1307.97	3.81

图8 PVDF/rGO复合材料断面的SEM图

Fig.8 Cross-sectional SEM images of PVDF/rGO composites

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