Effect of graphite micro⁃sheets on crystallization and properties of polychlorotrifluoroethylene

doi:10.19491/j.issn.1001-9278.2023.01.004

Abstract

Abstract:

Polychlorotrifluoroethylene （PCTFE）/graphite micro⁃sheets （GMS） composites were prepared through melt blending， and the effect of GMS content on the crystallization behavior， mechanical properties， microstructure， dynamic thermo⁃mechanical properties， and barrier properties of the composites were investigated. Meanwhile， the mechanisms for the variation of the properties were discussed. The results indicated that the addition of GMS improved the mechanical strength and rigidity of the composites. The PCTFE/GMS composite exhibited tensile strength of 50.5 MPa at a GMS loading of 0.3 wt%. This result is 22 % higher than that of pure PCTFE. When 2 wt% of GMS was added， the PCTFE/GMS⁃2 composite obtained an elastic modulus of 1 091 MPa and a loss modulus of 1 233 MPa， which increased by 36 % and 60 %， respectively， compared to pure PCTFE. Moreover， the glass transition temperatures of the composites were also improved significantly， which was 7~12 ℃ higher than that of pure PCTFE. The change of mechanical properties is attributed to the reinforcing effect of high⁃strength GMS on the PCTFE matrix. Simultaneously， GMS could promote the nucleation of PCTFE， and a small amount of GMS enhanced its crystallinity. In addition， GMS enhanced the barrier performance of PCTFE effectively， and its hydrogen permeation coefficient decreased gradually with an increase in the GMS content. When 2 wt% of GMS was added， the PCTFE/GMS composites obtained a permeation coefficient of 2.78×10^-15 cm³·cm/（cm²·h·Pa）， which was 49 % lower than that of PCTFE.

Key words: polychlorotrifluoroethylene, graphite micro?sheet, crystallization behavior, mechanical property, microst?ructure, barrier property

CLC Number:

TQ325.1

LI Yi, FAN Guiqi, WU Tianyu, YE Haimu. Effect of graphite micro⁃sheets on crystallization and properties of polychlorotrifluoroethylene[J]. China Plastics, 2023, 37(1): 18-25.

Figures/Tables 7

Fig.1. SEM of graphite micro⁃sheets

Fig.2. DSC curves of PCTFE and PCTFE/GMS composites

样品	T_c/℃	ΔH_c/ J·g^-1	T_m/℃	ΔH_m/ J·g^-1	结晶度/ %
PCTFE	180.0	20.50	213.1	20.69	47.6
PCTFE/GMS⁃0.1	182.4	22.04	213.2	22.42	51.6
PCTFE/GMS⁃0.3	183.7	19.58	213.1	19.69	45.4
PCTFE/GMS⁃0.5	185.3	20.40	212.8	20.45	47.2
PCTFE/GMS⁃1	186.9	19.66	213.5	19.85	46.1
PCTFE/GMS⁃2	187.1	19.93	213.2	20.17	47.3

Tab.1. DSC characteristic parameters of PCTFE and PCTFE/GMS composites

Fig.3. Mechanical properties of PCTFE and PCTFE/GMS composites

Fig.4. SEM of the cross sections of PCTFE and PCTFE/GMS composites after tensile test

Fig.5. DMA curves of PCTFE and PCTFE/GMS composites as well as microphase separation of PCTFE/GMS composites

Fig.6. Hydrogen permeability coefficients of PE⁃HD， PCTFE and PCTFE/GMS composites as well as SEM of fracture section of PCTFE/GMS⁃2

References 23

1	LI J， HO M S， XIE C， et al. China's flexibility challenge in achieving carbon neutrality by 2060 ［J］. Renewable and Sustainable Energy Reviews， 2022， 158： 112112.
2	ANKANG M， YUE Y， HAN W， et al. Research on development status and trend of green hydrogen energy technologies under targets of carbon peak and carbon neutrality ［J］. Distributed Energy， 2021， 6（4）： 15⁃24.
3	ZHANG S， CHEN W. Assessing the energy transition in China towards carbon neutrality with a probabilistic framework ［J］. Nature Communication， 2022， 13： 87.
4	ZOU C， XIONG B， XUE H， et al. The role of new energy in carbon neutral ［J］. Petroleum Exploration and Development， 2021， 48（2）： 480⁃491.
5	DHANUMALAYAN E， JOSHI G M. Performance pro⁃perties and applications of polytetrafluoroethylene （PTFE）—a review ［J］. Advanced Composites and Hybrid Materials， 2018， 1（2）： 247⁃268.
6	ZHANG N， LI Q， LI Q， et al. Seat tightness of pneumatic cryogenic control valve ［J］. Science China Technological Sciences， 2013， 56（8）： 2 066⁃2 069.
7	SUI Y， LI J， QIU Z， et al. Effects of the sintering temperature on the superior cryogenic toughness of ultra⁃high molecular weight polyethylene （UHMWPE）［J］. Chemical Engineering Journal， 2022， 444： 136366.
8	TENG H. Overview of the development of the fluoropolymer industry ［J］. Applied Sciences， 2012， 2（2）： 496⁃512.
9	BOSCHET F， AMEDURI B. （Co）polymers of chlorotrifluoroethylene： synthesis， properties， and applications ［J］. Chemical Reviews， 2014， 114（2）： 927⁃980.
10	ZEKRIARDEHANI S， JABARIN S A， GIDLEY D R， et al. Effect of chain dynamics， crystallinity， and free volume on the barrier properties of poly（ethylene terephthalate） biaxially oriented films ［J］. Macromolecules， 2017， 50（7）： 2 845⁃2 855.
11	COMPTON O C， KIM S， PIERRE C， et al. Crumpled graphene nanosheets as highly effective barrier property enhancers ［J］. Advanced Materials， 2010， 22（42）： 4 759⁃4 763.
12	YOO B M， SHIN H J， YOON H W， et al. Graphene and graphene oxide and their uses in barrier polymers ［J］. Journal of Applied Polymer Science， 2014， 131（1）： 39628.
13	XU J Z， CHEN T， YANG C L， et al. Isothermal crystallization of poly（l⁃lactide） induced by graphene nanosheets and carbon nanotubes： a comparative study ［J］. Macromolecules， 2010， 43（11）： 5 000⁃5 008.
14	AOYAMA S， PARK Y T， OUGIZAWA T， et al. Melt crystallization of poly（ethylene terephthalate）： comparing addition of graphene vs. carbon nanotubes ［J］. Polymer， 2014， 55（8）： 2 077⁃2 085.
15	中国国家标准化管理委员会. 塑料拉伸性能的测定第2部分：模塑和挤塑塑料的试验条件：［S］. 北京：中国标准出版社， 2006.
16	中国国家标准化管理委员会. 树脂浇铸体性能试验方法：［S］. 北京：中国标准出版社， 2022.
17	全国塑料制品标准化技术委员会. 塑料薄膜和薄片气体透过性试验方法—压差法：［S］. 北京：中国标准出版社， 2001.
18	季根忠，刘维民，齐陈泽，等. 刚性粒子增韧聚合物机理研究［J］. 高分子通报， 2005 （1）： 50⁃54.
	JI G Z， LIU W M， QI C Z， et al. Study on toughening mechanism of polymer toughened by rigid organic particles ［J］. Polymer Bulletin， 2005 （1）： 50⁃54.
19	Li Y， Wen J H， Wu T Y， et al. Mechanical properties and microstructure of polychloro⁃ trifluoroethylene toughened by polyamide 11 based on intermolecular interaction ［J］. Journal of Applied Polymer Science， 2022， 139（42）： 53028.
20	EHRENSTEING W. 聚合物材料：结构·性能·应用［M］. 张萍，赵树高，译. 北京：化学工业出版社， 2007： 165⁃180.
21	佘亚楠，付烨，朱钦睿，等. 纸浆纤维/聚乳酸复合材料的力学和热学性能［J］. 复合材料学报， 2021， 39： 1⁃12.
	SHE Y N， FU Y， ZHU Q R， et al. Mechanical and thermal properties of pulp fiber/polylactic acid composite ［J］. Acta Materiae Compositae Sinica， 2022， 39（10）： 1⁃12.
22	HOFFMAN J D， WILLIAMS G， PASSAGLIA E. Analysis of the α， β， and γ relaxations in polychlorotrifluoroethylene and polyethylene： dielectric and mechanical properties ［J］. Journal of Polymer Science： Part C， 1966， 14： 173⁃235.
23	于柏峰. 油气输送用柔性增强热塑性管道研究和应用［J］. 纤维复合材料， 2018， 35（4）： 29⁃33.
	YU B F. Research and application of reinforced thermoplastic pipe in oil and gas transmission pipeline ［J］. Fiber Composites， 2018， 35（4）： 29⁃33.

[1]	. Applications and performance of medium carbon chain chlorofaffin in PVC products [J]. , 2023, 37(1): 31-37.
[2]	ZHAO Yiquan, DONG Jinghan, ZHANG Tongzhu, WANG Yanmeng, DIAO Shuai, LI Minghe, XU Changzhu. Study on properties of recycled polypropylene for automobile exterior parts [J]. China Plastics, 2023, 37(1): 112-118.
[3]	JIAO Zhiwei, WANG Kechen, ZHANG Yang, YANG Weimin. Performance of PVC/ABS composites filled with carbon black and talc powders based on carbon nano coating deposition [J]. China Plastics, 2022, 36(8): 10-15.
[4]	ZHANG Taozhong, CHEN Xiaolong, HAO Xiaoyu, YU Fujia. Comparison of mechanical properties and interfacial interactions of polypropylene composites filled with talc， calcium carbonate， and barium sulfate [J]. China Plastics, 2022, 36(8): 36-41.
[5]	YU Changyong, XIN Zhong. Effect of α/β complex nucleating agent based on hexahydrophthalate on properties of polypropylene [J]. China Plastics, 2022, 36(7): 121-128.
[6]	TAN Liqin, LIU Weiqu, LIANG Liyan, WANG Shuo, FENG Zhiqiang, LIN Jiaming. Preparation and performance of epoxy resin modified with mercaptan polysiloxane [J]. China Plastics, 2022, 36(7): 21-29.
[7]	XU Jie, ZHONG Jinfu, TONG Xiaoqian, LI Guangfu, FU Dongliang, LI Chengcheng. Preparation and performance of carboxyl⁃terminated tannic acid/gallic acid⁃based epoxy composite [J]. China Plastics, 2022, 36(7): 44-50.
[8]	LI Kaize, XIN Yong. Properties of thermoplastic polyurethane composites modified with carbon nanotubes [J]. China Plastics, 2022, 36(6): 1-5.
[9]	WANG Shuai, ZHANG Yudi, YANG Fukai, XU Xinyu. Preparation and properties of polyimide/multi⁃walled carbon nanotubes composite foams [J]. China Plastics, 2022, 36(6): 39-45.
[10]	WANG Jinye, TANG Bohu, YANG Lining, XIE Meng, GUO Zechao, YANG Guang. Study on multi⁃jet⁃fusion forming process of PA12 parts [J]. China Plastics, 2022, 36(6): 81-86.
[11]	SUN Wenbo, XIN Chunling, HE Yadong, ZHAI Yujiao, YAN Baorui. Influence of micro⁃foaming injection molding process on cell structure of glass⁃fiber⁃reinforced PBT products [J]. China Plastics, 2022, 36(5): 1-7.
[12]	WANG Ke, LONG Chunguang. Mechanical and tribological properties of ultra⁃high molecular weight polyethylene/sepiolite fiber composites [J]. China Plastics, 2022, 36(5): 19-23.
[13]	CHEN Sheng, LIANG Yingchao, WU Fangjuan, FANG Hui, FAN Xinfeng, CHEN Hui, WANG Yonggang. Preparation and interfacial modification of polyamide 6/bidirectional warp⁃knitted glass fiber composites [J]. China Plastics, 2022, 36(5): 24-28.
[14]	HE Hezhi, XU Li, YANG Yike. Effect of prestress on mechanical properties of PC/CF laminates [J]. China Plastics, 2022, 36(4): 1-5.
[15]	LI Suyuan, LIU Huipeng, GONG Shun, HUANG Guotao, LI Yucai, WU Xin, DENG Jianping, PAN Kai. Preparation and characterization of EVA foaming materials modified with thermoplastic polyamide elastomer [J]. China Plastics, 2022, 36(4): 6-14.