石墨烯/环氧树脂复合涂层的γ射线辐照损伤及其腐蚀防护性能

doi:10.15541/jim20170143

摘要/Abstract

摘要：

用硅烷偶联剂对石墨烯表面进行修饰, 制备石墨烯/环氧树脂复合涂层。通过交流阻抗(EIS)和塔菲尔极化曲线(Tafel slope)等电化学方法分析复合涂层经伽马射线辐照后的腐蚀防护性能。采用电子自旋共振(ESR)和傅里叶红外光谱分析仪(FTIR)等测试复合涂层的γ射线辐照损伤, 探索了石墨烯在环氧树脂中抗辐照损伤的作用机理。Tafel结果显示复合涂层经280 kGy辐照后, 腐蚀电流为6.140×10^-9 A/cm², 而纯环氧树脂涂层的腐蚀电流则为1.340×10^-8 A/cm², 说明石墨烯可以使复合涂层保持较好的腐蚀防护性能。ESR分析表明, 复合涂层中的石墨烯可以降低环氧树脂基体在γ射线辐照过程中产生的过氧自由基, 表明石墨烯可有效吸收辐照过程中的自由基。辐照前后复合涂层的FT-IR图谱没有发生明显变化, 说明石墨烯有效降低了伽马射线对环氧树脂的结构损伤。因此, 可以认为石墨烯能够减缓环氧树脂在高能辐照环境中的老化, 从而延长其使用寿命。

关键词: 硅烷偶联剂, 石墨烯, 复合材料, γ射线辐照, 腐蚀防护性能, 自由基

Abstract:

Polymer networks like epoxy resin, as common protection materials, always experience radiolytic oxidation degradation under gamma irradiation environment. To avoid this, we report a scheme to synthesis EPTES modified graphene oxide, and incorporate it into the epoxy resin, followed by thermal polymerization, then obtain a graphene/epoxy composite coating. Electrochemical tests were performed to prove the influence of γ-ray on a anti-corrosion properties of the Graphene/epoxy composite coating. electron spin resonance (ESR) and Fourier Transform infrared spectroscopy (FT-IR) were used to evaluate the damage degree under the gamma irradiation, as well as to confirm its mechanism of graphene in the epoxy resin matrix during the irradiation. The result of Tafel slope showed that the corrosion current of GEP was 6.140×10^-9 A/cm², smaller than neat epoxy, indicating a better anticorrosion property of the graphene/epoxy composite coating after 280 kGy irradiation. This findings pointed that graphene possesses anti-corrosion property under 280 kGy irradiation. The electron spin resonance and FT-IR detection show that graphene act as radical scavenger, thus decrease damage from gamma irradiation, and slow down ageing process of the coating under the gamma irradiation.

Key words: EPTES, graphene, composite, γ-ray irradiation, anti-corrosion property, radical

中图分类号:

O646

夏伟, 王涛, 宋力, 龚浩, 郭虎, 范晓莉, 高斌, 赵军, 何建平. 石墨烯/环氧树脂复合涂层的γ射线辐照损伤及其腐蚀防护性能[J]. 无机材料学报, 2018, 33(1): 35-40.

XIA Wei, WANG Tao, SONG Li, GONG Hao, GUO Hu, FAN Xiao-Li, GAO Bin, ZHAO Jun, HE Jian-Ping. Graphene/Epoxy Composite Coating Damage under γ-ray Irradiation and Corrosion Protection[J]. Journal of Inorganic Materials, 2018, 33(1): 35-40.

图/表 7

图1 (a)GO表面修饰及修饰流程示意图, (b)GO经过修饰的SEM照片, (c)FGO和GO的FT-IR图谱, (d)FGO和GO的XRD图谱和(e)GO经过修饰的TEM照片和实物照片

Fig. 1 (a) Schematics of EPTES functionlized graphene oxide preparation, (b) SEM image of functionlized graphene oxide, (c) FT-IR spectra of GO and FGO, (d) The wide-angle X-ray diffraction (XRD) patterns of GO and FGO and (e) TEM image of FGO & Photographs of GO and FGO dispersion in epoxy matrix. All the photographs were taken 30 d after their preparation, left: unmodified GO; right: FGO modified by EPTES

图2 FGO/EP样品超薄切片的(a)低倍和(b)高倍TEM照片

Fig. 2 (a) Low and (b) high magnification TEM images of ultrathin section of GEP/0.25% FGO nanocomposite

图3 未经过辐照EP样品(a)和FGO/EP样品(b)表面SEM照片, 经过280 kGy剂量辐照后FGO/EP样品(c)和EP样品(d)表面表面SEM照片

Fig. 3 SEM images of the surface of neat epoxy (a) and FGO/ EP (b) without gamma irradiation, and the surface of EP(c) FGO/ EP(d) after 280 kGy gamma irradiation

图4 辐照剂量为0 kGy时样品的Nyquist图(a)和塔菲尔曲线图(b), 辐照剂量为280 kGy时样品的Nyquist图(c)和塔菲尔曲线图(d), 及其对应的等效电路图(e)

Fig. 4 Nyquist plots (a) and potentiodynamic polarization curves (b) of neat epoxy, FGO/EP before (c) andafter (d) 280 kGy irradiated,with (e) equivalent circuits used for fitting from Nyquist plots

表1 EP, FGO/EP两种样品辐照前后腐蚀电流和腐蚀电位变化

Table 1 Change of corrosion current density (icorr) and corrosion potentials (Ecorr) values before and after 280 kGy irradiation

Sample	E_corr/mV (vs.SCE)	i_corr/(A•cm²)
EP-0 kGy	-0.148	9.756×10^-10
FGO/EP-0 kGy	-0.124	2.415×10^-9
EP-280 kGy	0.003	1.340×10^-8
FGO/EP-280 kGy	0.187	6.140×10^-9

图5 纯环氧树脂(EP)和FGO/EP复合材料经过 280 kGy辐照后ESR图

Fig. 5 X-band ESR spectra measured at RT of neat epoxy, FGO/EP samples after 280 kGy irradiation

图6 EP和FGO/EP复合材料经过 280 kGy辐照后FT-IR图谱

Fig. 6 FT-IR spectra of EP, FGO/EP samples during radiation environment normalized after 280 kGy irradiation

参考文献 24

[1]	SUZUKI N, ZAKARIA M B, CHIANG Y D, et al.Thermally stable polymer composites with improved transparency by using colloidal mesoporous silica nanoparticles as inorganic fillers.Phys. Chem. Chem. Phys., 2012, 14(20): 7427-7432.
[2]	GEIM A K, NOVOSELOV K S.The rise of graphene.Nature Mater., 2007, 6(3): 183-191.
[3]	NOVOSELOV K, GEIM A K, MOROZOV S, et al.Two-dimensional gas of massless dirac fermions in graphene.Nature, 2005, 438(7065): 197-200.
[4]	LIU B, REDDY C, JIANG J, et al.Morphology and in-plane thermal conductivity of hybrid graphene sheets.Appl. Phys. Lett., 2012, 101(21): 211909.
[5]	TAN Z, CHEN G, ZHU Y, et al.Carbon-based supercapacitors produced by the activation of graphene.Nanocarbons for Advanced Energy Storage, 2015, 332(6037): 211-225.
[6]	LEE C, WEI X, KYSAR J W, et al.Measurement of the elastic properties and intrinsic strength of monolayer graphene.Science, 2008, 321(5887): 385-388.
[7]	LIU Q, LI Z F, LIU Y, et al.. Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries.Nat. Commun., 2015(6): 6127.
[8]	ZAN R, RAMASSE Q M, JALIL R, et al.Control of radiation damage in MoS2 by graphene encapsulation.ACS Nano, 2013, 7(11): 10167-10174.
[9]	KOLANTHAI E, BOSE S, BHAGYASHREE K S, et al.Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions.Phys. Chem. Chem. Phys., 2015, 17(35): 22900-22910.
[10]	QIU Y, WANG Z, OWENS A C, et al.Antioxidant chemistry of graphene-based materials and its role in oxidation protection technology.Nanoscale, 2014, 6(20): 11744-11755.
[11]	ZHANG C, CHEN S,ALVAREZ P J J, et al.. Reduced graphene oxide enhances horseradish peroxidase stability by serving as radical scavenger and redox mediator.Carbon, 2015, 94: 531-538.
[12]	HUMMERS JR W S, OFFEMAN R E. Preparation of graphitic oxide.J. Am. Chem. Soc., 1958, 80(6): 1339.
[13]	MONSHI A, FOROUGHI M R, MONSHI M R.Modified Scherrer equation to estimate more accurately nano-crystallite size using XRD.World Journal of Nano Science and Engineering, 2012, 2(3): 154-160.
[14]	ATTA A M, NASSAR I F, BEDAWY H M.Unsaturated polyester resins based on rosin maleic anhydride adduct as corrosion protections of steel.Reactive and Functional Polymers, 2007, 67(7): 617-626.
[15]	CHANG K C, HSU M H, LU H I, et al.Room-temperature cured hydrophobic epoxy/graphene composites as corrosion inhibitor for cold-rolled steel.Carbon, 2014, 66: 144-153.
[16]	KANG P H, PARK J S, NHO Y C.Effect of electron beam and γ-ray irradiation on the curing of epoxy resin,Macromolecular research, 2002, 10(6): 332-338.
[17]	MARRALE M, LONGO A, PANZECA S, et al.ESR response of phenol compounds for dosimetry of gamma photon beams.Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2014, 339: 15-19.
[18]	JAHAN M, WANG C, SCHWARTZ G, et al.Combined chemical and mechanical effects on free radicals in UHMWPE joints during implantation.J. Biomed. Mater. Res., 1991, 25(8): 1005-1017.
[19]	O’NEILL P, BIRKINSHAW C, LEAHY J, et al. The role of long lived free radicals in the ageing of irradiated ultra high molecular weight polyethylene.Polym. Degrad. Stabil., 1999, 63(1): 31-39.
[20]	KATAEV E Y, ITKIS D M, FEDOROV A V, et al.Oxygen reduction by lithiated graphene and graphene-based materials.ACS Nano, 2015, 9(1): 320-326.
[21]	QIU Y, WANG Z, OWENS A C, et al.Antioxidant chemistry of graphene-based materials and its role in oxidation protection technology.Nanoscale, 2014, 6(20): 11744-11755.
[22]	BANHART F, KOTAKOSKI J, KRASHENINNIKOV A V.Structural defects in graphene.ACS Nano, 2010, 5(1): 26-41.
[23]	KHOLMANOV I, CAVALIERE E, CEPEK C, et al.Catalytic chemical vapor deposition of methane on graphite to produce graphene structures.Carbon, 2010, 48(5): 1619-1625.
[24]	GALANT C, FAYOLLE B, KUNTZ M, et al.Thermal and radio- oxidation of epoxy coatings.Prog. Org. Coat., 2010, 69(4): 322-329.
	Supplementary Materials