天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能

doi:10.7503/cjcu20160144

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (7): 1402.doi: 10.7503/cjcu20160144

天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能

刘尧华¹, 林宇¹(), 张栋葛¹, 陈春蕾¹, 吴国章¹(), 张衍¹, 栾伟玲²

1. 华东理工大学材料科学与工程学院, 上海市先进聚合物重点实验室, 上海 200237
2. 华东理工大学机械与动力工程学院, 承压系统与安全教育部重点实验室, 上海 200237

收稿日期:2016-03-11 出版日期:2016-07-10 发布日期:2016-06-27
基金资助:
国家重点基础研究发展计划项目(批准号: 2013CB035505)和国家自然科学基金(批准号: 51373053, 51503066)资助

Fabrication of Natural Rubber/Chemically Reduced Graphene Oxide Nanocomposites and Nuclear Radiation Resistant Behavior^†

LIU Yaohua¹, LIN Yu^1,^*(), ZHANG Dongge¹, CHEN Chunlei¹, WU Guozhang^1,^*(), ZHANG Yan¹, LUAN Weiling²

1. Shanghai Key Laboratory of Advanced Polymeric Material, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
2. Key Laboratory of Pressure System and Safety, Ministry of Education, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2016-03-11 Online:2016-07-10 Published:2016-06-27
Contact: LIN Yu,WU Guozhang E-mail:linyu@ecust.edu.cn;wgz@ecust.edu.cn
Supported by:
† Supported by the National Basic Research Program of China(No.2013CB035505) and the National Natural Science Foundation of China(Nos;51373053, 51503066)

摘要/Abstract

摘要：

采用乳液共混和原位还原法制备了天然橡胶(NR)/还原氧化石墨烯(RGO)纳米复合材料, 研究了γ射线辐照对复合材料力学性能和热稳定性的影响. 研究结果表明, RGO以少数几层堆叠片层结构均匀分散于NR基体中. RGO的加入可显著提高NR的力学性能和热稳定性, 加入质量分数为0.6%的RGO可使材料拉伸强度由(22±1.4) MPa提升至(25±1.1) MPa, 质量损失50%对应的温度(T₅₀)升高6.4 ℃. 经200 kGy的γ射线辐射后, 纯NR的拉伸强度和T₅₀分别下降了75%和4.5 ℃, 而NR/RGO-0.6%复合体系仅分别下降了56%和1.2 ℃. 揭示了RGO提高材料耐辐射性能的机理, 由于RGO可捕捉猝灭因辐射产生的自由基, 从而减弱了辐射老化降解和交联反应的发生.

关键词: 天然橡胶/石墨烯纳米复合材料, 耐辐射性, 拉伸强度, 热稳定性, 自由基猝灭剂

Abstract:

Natural rubber(NR)/chemically reduced graphene oxide(RGO) nanocomposites were fabricated by latex mixing plus in situ reduction process. The transmission electron microscopy morphology shows that uniform dispersion of RGO with a few layers of stacked lamellar structure can be observed in the nano-composites. The effect of γ irradiation on the mechanical property and thermal stability of NR matrix by the incorporation of RGO was mainly investigated in detail. Compared to pure NR, the tensile strength increases from (22±1.4) MPa to (25±1.1) MPa and the thermal decomposition temperature of 50% mass loss(T₅₀) is increased by 6.4 ℃ for NR/RGO nanocomposites by the addition of 0.6% RGO before irradiation. After γ irradiation dose of 200 kGy, the tensile strength and T₅₀ of pure NR are decreased by 75% and 4.5 ℃, respectively. However, those of NR/RGO-0.6% nanocomposites are decreased only by 56% and 1.2 ℃, respectively. The radiation resistant mechanism of NR/RGO nanocomposites was also interpreted by electron paramagnetic resonance measurements. The results reveal that RGO can act as free radical scavenger, and the introduction of RGO to NR matrix exhibits much less amount of free radicals.

Key words: Natural rubber/reduced graphene oxide nanocomposite, Radiation resistant behavior, Tensile strength, Thermal stability, Free radical scavenger

中图分类号:

O631
TQ332

TrendMD:

刘尧华, 林宇, 张栋葛, 陈春蕾, 吴国章, 张衍, 栾伟玲. 天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能. 高等学校化学学报, 2016, 37(7): 1402.

LIU Yaohua, LIN Yu, ZHANG Dongge, CHEN Chunlei, WU Guozhang, ZHANG Yan, LUAN Weiling. Fabrication of Natural Rubber/Chemically Reduced Graphene Oxide Nanocomposites and Nuclear Radiation Resistant Behavior^†. Chem. J. Chinese Universities, 2016, 37(7): 1402.

图/表 11

Fig.1 TEM(A), AFM(B) images of GO nanosheet and height profile(C) of (B)

Fig.2 FTIR spectra of GO(a) and RGO(b)

Fig.3 XPS peak of GO(a) and RGO(b)(A), XPS C1s peak of GO(B) and XPS C1s peak of RGO(C)

Table 1 XPS C1s peak position and the relative atomic percentage of GO and RGO

Sample	C₁_s contribution(%)					Molar ratio of C/O
Sample	C—C(284.8 eV)		C—N(285.8 eV)	C—O(286.6 eV)	C O(287.7 eV)	O—C O(289.0 eV)
GO	47.8	0	43.1	6.5	2.6	2.2
RGO	75.1	12.1	8.1	3.4	1.3	9.9

Fig.4 SEM images of pure NR(A) and NR/RGO-0.6% nanocomposites(B)(A') and (B') are the partially enlarged images of (A) and (B), respectively. The marked regions in (B') represent the location of RGO.

Fig.5 TEM images of uncured NR/RGO-0.3%(A), uncured NR/RGO-0.6%(B), cured NR/RGO-0.3%(C) and cured NR/RGO-0.6% nanocomposites (D)The black grains in (C) and (D) are curing agents of ZnO.

Fig.6 Stress-strain curves of NR/RGO nanocomposites before irradiation(A) and after(B) γ irradiation

Fig.7 Tensile strength(A) and elongation at break(B) of NR/RGO nanocomposites before irradiation(a) and after γ irradiation dose of 200 kGy(b)

Fig.8 TGA curves of NR/RGO nanocomposites before irradiation(A) and after γ irradiation dose of 200 kGy(B)a. Pure NR; b. NR/RGO-0.18%; c. NR/RGO-0.3%; d. NR/RGO-0.6%.

Table 2 T50 of NR/RGO nanocomposites before irradiation and after γ irradiation dose of 200 kGy

Sample	T₅₀ (0 kGy)/℃	T₅₀ (200 kGy)/℃	ΔT₅₀/℃
Pure NR	378.9	374.4	4.5
NR/RGO-0.18%	381.7	377.6	4.1
NR/RGO-0.3%	383.6	381.4	2.2
NR/RGO-0.6%	385.3	384.1	1.2

Fig.9 EPR curves of pure NR(a,b) and NR/RGO nanocomposites(c,d) before irradiation(a,c) and after gamma irradiation dose of 200 kGy(b,d)

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天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能

Fabrication of Natural Rubber/Chemically Reduced Graphene Oxide Nanocomposites and Nuclear Radiation Resistant Behavior^†

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天然橡胶/石墨烯纳米复合材料的制备及耐核辐射性能

Fabrication of Natural Rubber/Chemically Reduced Graphene Oxide Nanocomposites and Nuclear Radiation Resistant Behavior†

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Fabrication of Natural Rubber/Chemically Reduced Graphene Oxide Nanocomposites and Nuclear Radiation Resistant Behavior^†