石墨烯纳米片/(酚酞聚芳醚酮-环氧树脂)双逾渗导热复合材料的制备和性能

欧阳泽宇; 王珂珂; 饶琼; 张志龙; 扶碧波; 彭雄奇

doi:10.13801/j.cnki.fhclxb.20200806.003

石墨烯纳米片/(酚酞聚芳醚酮-环氧树脂)双逾渗导热复合材料的制备和性能

doi: 10.13801/j.cnki.fhclxb.20200806.003

1.
上海交通大学　材料科学与工程学院，上海 200030
2.
中国航发湖南动力机械研究所，株洲 412002

基金项目: 国家自然科学基金(11972225)

详细信息

通讯作者:
彭雄奇，博士，教授，博士生导师，研究方向为复合材料及其成形、力学　 E-mail：xqpeng@sjtu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-05-25
- 录用日期: 2020-07-14
- 网络出版日期: 2020-08-06
- 刊出日期: 2021-03-15

Preparation and properties of thermally conductive grapheme nanoplates/(polyetherketone cardo-epoxy) composites with double percolation structures

OUYANG Zeyu^1
,,
WANG Keke^1
,,
RAO Qiong^1
,,
ZHANG Zhilong^2
,,
FU Bibo^2
,,
PENG Xiongqi^{1
, ,}

1.
School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200030, China
2.
AECC Hunan Aviation Powerplant Research Institute, Zhuzhou 412002, China

摘要

摘要: 为在较低的导热填料含量下提高环氧树脂(EP)的热导率，通过溶液法制备了石墨烯纳米片/(酚酞聚芳醚酮-EP) (GNP/(PEK-C-EP))复合材料。基于接触角测量计算并预测了GNP的选择性分布，并通过SEM和激光闪光法研究了GNP和PEK-C含量对GNP/(PEK-C-EP)复合材料的微观结构和热导率的影响。结果表明，当PEK-C的含量为20wt%时，GNP选择性分布在PEK-C中，形成了双逾渗结构的GNP/(PEK-C-EP)复合材料，从而构建了连续导热通道。当GNP含量为1wt%时，GNP/EP复合材料导热率最高达0.375 W(m·K)⁻¹。当GNP含量为0.5wt%时，GNP/(PEK-C-EP)复合材料导热率最高达0.371 W(m·K)⁻¹，较GNP含量为0.5wt%的GNP/EP复合材料热导率高48%，与GNP含量为1wt%的GNP/EP复合材料的热导率基本相同。表明GNP/(PEK-C-EP)复合材料的填料量减少了50%，利用双逾渗效应可以有效减少导热填料用量。此外，比较了纯EP和GNP/(PEK-C-EP)复合材料的玻璃化转变温度、热稳定性和热膨胀系数，结果表明，GNP/(PEK-C-EP)复合材料的热性能优于纯EP。
- 双逾渗效应 /
- 环氧树脂 /
- 酚酞聚芳醚酮 /
- 石墨烯纳米片 /
- 导热性
Abstract: To improve the thermal conductivity of epoxy (EP) with a lower thermally conductive filler content, graphene nanoplates/(polyetherketone cardo-EP) (GNP/(PEK-C-EP)) composites were prepared by the solution method. The selective distribution of GNP was predicted by calculation based on contact angle measurements, and the effects of GNP and PEK-C contents on the microstructures and thermal conductivities of GNP/(PEK-C-EP) composites were investigated by SEM and laser flash method. The results show that double percolation structures are formed in GNP/(PEK-C-EP) composites as the content of PEK-C reaches 20wt%, where GNPs are selectively distributed in PEK-C to build continuous heat conduction paths. For GNP/EP composites, it reaches the highest thermal conductivity of 0.375 W(m·K)⁻¹ at 1wt% GNP. While for GNP/(PEK-C-EP) composites, the content of 0.5wt% GNP reaches highest thermal conductivity of 0.371 W(m·K)⁻¹, which is 48% higher than that of GNP/EP composites at 0.5wt% GNP content and basically the same as that of GNP/EP composites at 1wt% GNP. It indicates that the filler content of GNP/(PEK-C-EP) composites is reduced by 50% owing to the double percolation effect. In addition, the glass transition temperatures, thermal stability and coefficients of thermal expansion of pure EP and GNP/(PEK-C-EP) composites were compared. The results show that the GNP/(PEK-C-EP) composites are superior to pure EP in thermal properties.
- double percolation effect /
- epoxy /
- polyetherketone cardo /
- graphene nanoplates /
- thermal conductivity

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图 1 酚酞聚芳醚酮(PEK-C)和环氧树脂(EP)分别与去离子水和乙二醇的接触角图像

Figure 1. Images of contact angles of polyetherketone cardo (PEK-C) and epoxy (EP) with deionized water and glycol respectively

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图 2 0.5GNP/(10PEK-C-90EP)复合材料断面形貌的SEM图像

Figure 2. SEM images of fracture surfaces of 0.5GNP/(10PEK-C-90EP) composite

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图 3 不同GNP含量时GNP/(PEK-C-EP)复合材料断面微观形貌的SEM图像

Figure 3. SEM imagess of fracture surfaces of GNP/(PEK-C-EP) composites with different GNP contents

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图 4 不同GNP含量的GNP/EP和GNP/(PEK-C-EP)复合材料热导率(a)及热逾渗幂律方程对GNP/(PEK-C-EP)复合材料热导率的拟合曲线(b)

Figure 4. Thermal conductivities of GNP/EP and GNP/(PEK-C-EP) composites with different GNP contents (a) and fitting curve of thermal conductivity of GNP/(PEK-C-EP) composites by thermal percolation power law equation (b)

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图 5 EP和0.5GNP/(20PEK-C-80EP)复合材料的DSC曲线

Figure 5. DSC curves of EP and 0.5GNP/(20PEK-C-80EP) composite

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图 6 EP和0.5GNP/(20PEK-C-80EP)复合材料的TG曲线

Figure 6. TG curves of EP and 0.5GNP/(20PEK-C-80EP) composite

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图 7 EP、0.3GNP/(20PEK-C-80EP)和0.5GNP/(20PEK-C-80EP)复合材料热膨胀曲线

Figure 7. Thermal expansion curves of EP, 0.3GNP/(20PEK-C-80EP) and 0.5GNP/(20PEK-C-80EP) composites

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表 1 试剂表面张力及其色散和极性分量^[12]

Table 1. Surface tensions, dispersive and polarcomponents of chemical reagents

Reagent	$\gamma $/(mN·m^–1)	${\gamma ^{\rm{d}}}$/(mN·m^–1)	${\gamma ^{\rm{p}}}$/(mN·m^–1)
Ethylene glycol	47.5	31.2	16.3
Deionized water	71.5	28.2	43.3
Notes: $\gamma $—Surface tension; ${\gamma ^{\rm{d}}}$, ${\gamma ^{\rm{p}}}$—Dispersive and polar components of surface tension, respectively.

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表 2 EP、PEK-C和石墨烯纳米片(GNP)的表面张力

Table 2. Surface tensions of EP, PEK-C and graphene nanoplate (GNP)

Component	Harmonic			Geometric			Ref.
Component	$\gamma $/(mN·m^–1)	${\gamma ^{\rm{d}}}$/(mN·m^–1)	${\gamma ^{\rm{p}}}$/(mN·m^–1)	$\gamma $/(mN·m^–1)	${\gamma ^{\rm{d}}}$/(mN·m^–1)	${\gamma ^{\rm{p}}}$/(mN·m^–1)	Ref.
EP	43.07	10.35	32.72	40.49	7.71	32.78	Tested
PEK-C	33.84	11.46	22.38	30.04	15.41	14.63	Tested
GNP	23.20	10.80	12.40	22.76	19.49	3.27	[12]
Notes: “Harmonic” indicates that the surface tensions can be obtained from the equation (6); “Geometric” indicates that the surface tensions can be obtained from the equation (7).

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表 3 EP、PEK-C和GNP之间的界面张力

Table 3. Interfacial tensions of EP, PEK-C and GNP

Component couple	${\gamma _{1 - 2}}$/(mN·m⁻¹)
Component couple	Geometric-Geometric	Geometric-Harmonic	Harmonic-Geometric	Harmonic-Harmonic
EP-PEK-C	4.93	1.01	9.51	1.99
EP-GNP	18.11	4.84	29.37	9.16
PEK-C-GNP	4.34	1.47	7.75	2.88
Notes: “Geometric-Geometric” and other similar marks indicate “the formula for the surface tension data source (equation (6) or equation (7))-the formula for calculating the interface tension (equation (4) or equation (5))”.

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表 4 GNP/(PEK-C-EP)复合材料的润湿系数${\omega _\alpha }$

Table 4. Wetting coefficient ω_α of GNP/(PEK-C-EP) composites

${\omega _\alpha }$ calculated from Geometric-Geometric	${\omega _\alpha }$ calculated from Geometric-Harmonic	${\omega _\alpha }$ calculated from Harmonic-Geometric	${\omega _\alpha }$ calculated from Harmonic-Harmonic	Location of GNP
2.79	3.35	2.27	3.15	PEK-C

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表 5 EP和0.5GNP/(20PEK-C-80EP)复合材料的热失重5%的温度(T_5%)、热失重10%的温度(T_10%)和残炭率(R_w)

Table 5. Temperature of 5% mass loss (T_5%), temperature of 10% mass loss (T_10%) and residual carbon ratios (R_w) of EP and 0.5GNP/(20PEK-C-80EP) composite

Sample	T_5%/℃	T_10%/℃	R_w/%
EP	322.7	352.6	24.2
0.5GNP/ (20PEK-C-80EP)	320.1	354.9	30.5

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