多壁碳纳米管@石墨烯复合热塑性动态硫化橡胶材料制备及其热电性能

汤琦; 胡仕腾; 王雪萌; 孙聚杰; 宗成中

doi:10.13801/j.cnki.fhclxb.20220919.002

多壁碳纳米管@石墨烯复合热塑性动态硫化橡胶材料制备及其热电性能

doi: 10.13801/j.cnki.fhclxb.20220919.002

汤琦^{1, 2, ,},
胡仕腾¹,
王雪萌¹,
孙聚杰^{1, 2},
宗成中^{1, 2}

1.
青岛科技大学　高分子科学与工程学院，青岛 266042
2.
橡塑材料与工程教育部重点实验室，青岛 266042

基金项目: 青岛市2021年博士后资助应用研究项目(040304031060092)

详细信息

通讯作者:
汤琦，博士，研究方向为热塑性动态硫化橡胶制备、结构与性能　E-mail: 1181476292@qq.com

中图分类号: TQ334；TB332
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出版历程
- 收稿日期: 2022-08-11
- 修回日期: 2022-09-07
- 录用日期: 2022-09-10
- 网络出版日期: 2022-09-22
- 刊出日期: 2023-07-15

Preparation of multi-walled carbon nanotubes@graphene/thermoplastic vulcanizate composites and study on its thermoelectric properties

TANG Qi^{1, 2
, ,},
HU Shiteng¹,
WANG Xuemeng¹,
SUN Jujie^{1, 2},
ZONG Chengzhong^{1, 2}

1.
School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2.
Key Laboratory of Rubber-Plastics of Ministry of Education, Qingdao 266042, China

Funds: Applied Research Project Supported by Qingdao Postdoctoral Research Center in 2021 (040304031060092)

摘要

摘要: 利用一维和二维两种填料(多壁碳纳米管(MWCNTs)@石墨烯(GE))的协同作用来改善热塑性动态硫化橡胶(TPV)的热电性能(导电和导热性能)和力学性能。本文通过熔融接枝共混法制备MWCNTs@GE/聚丙烯-马来酸酐(PP-MA)母粒，在表征MWCNTs@GE/PP-MA母粒的结构、结晶性和微观形貌的基础上，进一步采用动态硫化方法制备具有独特网络结构的MWCNTs@GE/TPV复合材料，研究了MWCNTs@GE用量对MWCNTs@GE/TPV复合材料的相态结构、导电性能、导热性能及力学性能的影响。研究结果表明：与单组分填料制备的复合母粒相比，MWCNTs@GE并用体系具有协同作用，在PP-MA中分散均匀，与基体结合力强，在结晶过程中作为成核剂能够促进基体结晶，提高基体的结晶峰温度(T_c)和结晶度(X_c)，减小结晶尺寸(L_Crystallite)。MWCNTs@GE/TPV复合材料呈现出明显的“海岛”相结构，交联的丁基橡胶 (IIR)相以微米级颗粒状分散在PP-MA相中。MWCNTs和GE均匀分散在连续相PP-MA中，MWCNTs和GE间距离小于1 µm，形成MWCNTs@GE网络结构。当MWCNTs@GE/TPV复合材料中MWCNTs@GE含量达到3wt%时，交流电导率、导热率、断裂伸长率和拉伸强度达到最佳值。
- 多壁碳纳米管(MWCNTs) /
- 石墨烯(GE) /
- 热塑性动态硫化橡胶(TPV) /
- 复合材料 /
- 动态硫化
Abstract: This work mainly used the synergistic effect of one- and two-dimensional fillers (Multi-walled carbon nanotubes (MWCNTs)@graphene (GE)) to improve the thermoelectric and mechanical properties of thermoplastic vulcanizate (TPV). MWCNTs@GE/polypropylene-maleic anhydride (PP-MA) masterbatch were first prepared by melt-graft blending. The structure, crystallinity and microstructure of MWCNTs@GE/PP-MA masterbatch were characterized. Then MWCNTs@GE/TPV composites with unique network structure were prepared by dynamic vulcanization method. The effects of the amount of MWCNTs@GE on the phase structure, electrical conductivity, thermal conductivity and mechanical properties of MWCNTs@GE/TPV composites were studied. The results show that the combination of MWCNTs and GE has a synergistic effect and can be used as nucleating agent to improve crystallization peak temperature (T_c) and crystallinity of PP (X_c) and reduce crystal size of the PP crystal plane (L_Crystallite) in the crystallization process, compared with the masterbatch prepared with single filler. In the MWCNTs@GE/PP-MA masterbatch, MWCNTs and GE are uniformly dispersed in PP-MA and have strong bonding force with the matrix. The MWCNTs@GE/TPV composites show an obvious "island" structure, and the cross-linked butyl rubber (IIR) rubber is dispersed in the PP-MA phase as micron size particles. MWCNTs and GE are uniformly dispersed in the continuous phase PP-MA, and the distance between MWCNTs and GE is less than 1 µm, forming the MWCNTs@GE network structure. When the content of MWCNTs@GE in MWCNTs@GE/TPV composites reaches 3wt%, the alternating current (AC) electrical conductivity, thermal conductivity, elongation at break and tensile strength reach the best value.
- multi-walled carbon nanotubes (MWCNTs) /
- graphene (GE) /
- thermoplastic vulcanizate (TPV) /
- composites /
- dynamic vulcanization

HTML全文

图 1 (a) 聚丙烯(PP)、PP熔融接枝马来酸酐(PP-MA)、多壁碳纳米管 (MWCNTs)/PP-MA母粒、石墨烯(GE)/PP-MA母粒和MWCNTs@GE/PP-MA母粒的FTIR图谱；(b) MWCNTs、GE、MWCNTs/PP-MA母粒、GE/PP-MA母粒和MWCNTs@GE/PP-MA母粒的Raman图谱

Figure 1. (a) FTIR spectra of polypropylene (PP), PP fusion grafting maleic anhydride (PP-MA), multi-walled carbon nanotubes (MWCNTs)/PP-MA masterbatch, graphene (GE)/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch; (b) Raman spectra of MWCNTs, GE, MWCNTs/PP-MA masterbatch, GE/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch

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图 2 PP、PP-MA、MWCNTs/PP-MA母粒、GE/PP-MA母粒和MWCNTs@GE/PP-MA母粒的XRD图谱

Figure 2. XRD patterns of PP, PP-MA, MWCNTs/PP-MA masterbatch, GE/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch

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图 3 PP、PP-MA、MWCNTs/PP-MA母粒、GE/PP-MA母粒和MWCNTs@GE/PP-MA母粒的DSC图谱：(a) 结晶曲线；(b) 熔融曲线

Figure 3. DSC spectra of PP, PP-MA, MWCNTs/PP-MA masterbatch, GE/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch: (a) Crystallization curves; (b) Melting curves

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图 4 MWCNTs (a)、GE (b)、PP-MA (c)、 MWCNTs/PP-MA母粒(d)、 GE/PP-MA母粒(e)和MWCNTs@GE/PP-MA母粒(f)的SEM图像

Figure 4. SEM images of MWCNTs (a), GE (b), PP-MA (c), MWCNTs/PP-MA masterbatch (d), GE/PP-MA masterbatch (e) and MWCNTs@GE/PP-MA masterbatch (f)

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图 5 不同MWCNTs@GE含量 MWCNTs@GE复合热塑性硫化橡胶(MWCNTs@GE/TPV)复合材料的TEM图像：(a) 1wt%；(b) 3wt%；(c) 5wt%

Figure 5. TEM images of MWCNTs@GE/thermoplastic vulcanizate (TPV) composites with different MWCNTs@GE contents: (a) 1wt%; (b) 3wt%; (c) 5wt%

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图 6 不同MWCNTs@GE含量MWCNTs@GE/TPV复合材料的热电性能：(a) 交流电导率随频率的变化；(b) 不同MWCNTs@GE含量MWCNTs@GE/TPV复合材料在10² Hz下的交流电导率；(c) 介电常数随频率的变化；(d) 导热系数

Figure 6. Thermoelectric properties of MWCNTs@GE/TPV composites with different MWCNTs@GE contents: (a) Alternating current (AC) conductivity vs frequency; (b) AC conductivity of MWCNTs@GE/TPV composites with different MWCNTs@GE contents at 10² Hz; (c) Dielectric permittivity vs frequency; (d) Thermal conductivity

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图 7 不同MWCNTs@GE含量MWCNTs@GE/TPV复合材料的力学性能：(a) 应力-应变曲线；(b) MWCNTs@GE含量对MWCNTs@GE/TPV复合材料拉伸强度、断裂伸长率和弹性模量的影响

Figure 7. Mechanical properties of MWCNTs@GE/TPV composites with different MWCNTs@GE contents: (a) Stress-strain curves; (b) Effect of MWCNTs@GE content on tensile strength, elongation at break and elastic modulus of MWCNTs@GE/TPV composites

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图 8 不同MWCNTs@GE含量MWCNTs@GE/TPV复合材料的拉伸断裂面形貌：(a) 0wt%；(b) 1wt%；(c) 3wt%；(d) 5wt%

Figure 8. Tensile fracture morphology of MWCNTs@GE/TPV composites with different MWCNTs@GE contents: (a) 0wt%; (b) 1wt%; (c) 3wt%; (d) 5wt%

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表 1 PP、PP-MA、MWCNTs/PP-MA母粒、GE/PP-MA母粒和MWCNTs@GE/PP-MA母粒的XRD数据

Table 1. XRD data of PP, PP-MA, MWCNTs/PP-MA masterbatch, GE/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch

Sample	L_Crystallite/nm	I₁₁₀/I₀₄₀
PP	26.5	0.64
PP-MA	25.2	0.60
MWCNTs/PP-MA	24.3	0.52
GE/PP-MA	23.2	0.48
MWCNTs@GE/PP-MA	21.6	0.38
Notes: L_Crystallite—Crystal size of the PP crystal plane (040); I₁₁₀/I₀₄₀—Ratio of diffraction peak intensity of PP crystal plane (110) and crystal plane (040).

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表 2 PP、PP-MA、MWCNTs/PP-MA母粒、GE/PP-MA母粒和MWCNTs@GE/PP-MA母粒的结晶数据

Table 2. Crystallization data of PP, PP-MA, MWCNTs/PP-MA masterbatch, GE/PP-MA masterbatch and MWCNTs@GE/PP-MA masterbatch

Sample	T_c/℃	T_m/℃	△H_m/(J·g⁻¹)	X_c/%
PP	100.2	142.7	93.6	44.8
PP-MA	102.8	141.2	99.5	48.3
MWCNTs/PP-MA	107.6	141.2	103.2	50.9
GE/PP-MA	106.2	141.1	107.6	53.1
MWCNTs@GE/PP-MA	109.3	140.8	115.3	56.9
Notes: T_c and T_m—Crystallization peak temperature and melting temperature; ΔH_m—Enthalpy of PP; X_c—Crystallinity of PP.

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