Applications of Raman spectroscopy in graphene-based polymer nanocomposites
HAO Si-jia1,2, LI Zhe-ling3, REN Zhi-dong1,2, TIAN Jun-peng1,2, SHI Shuang-qiang1,2, XING Yue1,2, YANG Cheng1,2
1. Research Center of Graphene Applications, AECC Beijing Institute of Aeronautical Materials, Beijing 100095, China;
2. Beijing Institute of Graphene Technology Co., Ltd., Beijing 100094, China;
3. National Graphene Institute, University of Manchester, Manchester M13 9PL, UK
Abstract：Raman spectroscopy is well-known for its capability of detecting the physical properties, level of defects and number of layers for graphene-based materials, but far more than that, it's proven to be a versatile and promising tool for characterizing graphene-based polymer composites. This work focuses on the applications of Raman spectroscopy in the field of graphene-based polymer composites. The feature bands in Raman spectroscopy enable direct 2D and 3D imaging of graphene-based nanofillers in the polymer matrix, and even out of other carbonaceous materials. In addition, shifts in the vibrational frequencies of the characteristic bands induced by the strain of graphene could be utilized for analyzing the interactions between graphene-based nanofillers and polymer molecules, for calculating the effective moduli as well as for determining the spatial orientation of graphene-based nanofillers in the matrix. In the meantime, the recent progress of applications of Raman spectroscopy in the field of graphene-based polymer composites is introduced, such as the analysis of micromechanics of graphene-based nanocomposites, the investigation of stress transfer efficiency between the nanofillers and the matrix, and the reveal of key factors affecting material behavior. The Raman spectroscopy researches of graphene-based polymer composites currently are mainly focused on model composites, and the fluorescent effect of the matrix polymer as well limits the further applications of Raman spectroscopy. In order to address such problem, the amplified razor power are often adopted, and the resulted nonlinear effects are capable of increasing the intensity of the Raman signal, thus the Raman spectroscopy will be more widely applied in the field of graphene-based polymer composites.
[1] BALAZS A C,EMRICK T,RUSSELL T P.Nanoparticle polymer composites:where two small worlds meet[J].Science,2006,314(5802):1107-1110.
[2] COLEMAN J N,KHAN U,BLAU W J,et al.Small but strong:a review of the mechanical properties of carbon nanotube-polymer composites[J].Carbon,2006,44(9):1624-1652.
[3] LIN B,GELVES G A,HABER J A,et al.Electrical, rheological, and mechanical properties of polystyrene/copper nanowire nanocomposites[J].Industrial & Engineering Chemistry Research,2007,46(8):2481-2487.
[4] WANG K,CHEN L,WU J,et al.Epoxy nanocomposites with highly exfoliated clay:mechanical properties and fracture mechanisms[J].Macromolecules,2005,38(3):788-800.
[5] YANG C,HAO S J,DAI S L,et al.Nanocomposites of poly(vinylidene fluoride)-controllable hydroxylated/carboxylated graphene with enhanced dielectric performance for large energy density capacitor[J].Carbon,2017,117:301-312.
[6] ZHANG X,JIANG J,SHEN Z,et al.Polymer nanocomposites with ultrahigh energy density and high discharge efficiency by modulating their nanostructures in three dimensions[J].Advanced Materials,2018,30(16):1707269.
[7] BALANDIN A A,GHOSH S,BAO W,et al.Superior thermal conductivity of single-layer graphene[J].Nano Letters,2008,8(3):902-907.
[8] NOVOSELOV K S,GEIM A K,MOROZOV S V,et al.Two-dimensional gas of massless Dirac fermions in graphene[J].Nature,2005,438(7065):197-200.
[9] ZHU Y,MURALI S,CAI W,et al.Graphene and graphene oxide:synthesis,properties,and applications[J].Advanced Materials,2010,22(35):3906-3924.
[10] LEE C,WEI X,KYSAR J W,et al.Measurement of the elastic properties and intrinsic strength of monolayer graphene[J].Science,2008,321(5887):385-388.
[11] DRESSELHAUS M S,DRESSELHAUS G,SAITO R,et al.Raman spectroscopy of carbon nanotubes[J].Physics Reports,2005,409(2):47-99.
[12] MALARD L,PIMENTA M A,DRESSELHAUS G,et al.Raman spectroscopy in graphene[J].Physics Reports,2009,473(5):51-87.
[13] SAITO R,HOFMANN M,DRESSELHAUS G,et al.Raman spectroscopy of graphene and carbon nanotubes[J].Advances in Physics,2011,60(3):413-550.
[14] 吴娟霞,徐华,张锦.拉曼光谱在石墨烯结构表征中的应用[J].化学学报,2014,72(3):301-318. WU J X,XU H,ZHANG J.Raman spectroscopy of graphene[J].Acta Chimica Sinica,2014,72(3):301-318.
[15] WU J B,LIN M L,CONG X,et al.Raman spectroscopy of graphene-based materials and its applications in related devices[J].Chemical Society Reviews,2018,47(5):1822-1873.
[16] LUCCHESE M M,STAVALE F,FERREIRA E H M,et al.Quantifying ion-induced defects and Raman relaxation length in graphene[J].Carbon,2010,48(5):1592-1597.
[17] CASIRAGHI C,HARTSCHUH A,QIAN H,et al.Raman spectroscopy of graphene edges[J].Nano Letters,2009,9(4):1433-1441.
[18] CHEN C F,PARK C H,BOUDOURIS B W,et al.Controlling inelastic light scattering quantum pathways in graphene[J].Nature,2011,471(7340):617-620.
[19] CASIRAGHI C,PISANA S,NOVOSELOV K S,et al.Raman fingerprint of charged impurities in graphene[J].Applied Physics Letters,2007,91(23):3.
[20] YOUNG R J,KINLOCH I A,GONG L,et al.The mechanics of graphene nanocomposites:a review[J].Composites Science and Technology,2012,72(12):1459-1476.
[21] PAPAGEORGIOU D G,KINLOCH I A,YOUNG R J.Mechanical properties of graphene and graphene-based nanocomposites[J].Progress in Materials Science,2017,90:75-127.
[22] FERRALIS N.Probing mechanical properties of graphene with Raman spectroscopy[J].Journal of Materials Science,2010,45(19):5135-5149.
[23] YOUNG R J,LIU M,KINLOCH I A,et al.The mechanics of reinforcement of polymers by graphene nanoplatelets[J].Composites Science and Technology,2018,154:110-116.
[24] KINLOCH I A,SUHR J,LOU J,et al.Composites with carbon nanotubes and graphene:an outlook[J].Science,2018,362(6414):547-553.
[25] KIM Y,POUMIROL J M,LOMBARDO A,et al.Measurement of filling-factor-dependent magnetophonon resonances in graphene using Raman spectroscopy[J].Physical Review Letters,2013,110(22):5.
[26] QIU C Y,SHEN X N,CAO B C,et al.Strong magnetophonon resonance induced triple G-mode splitting in graphene on graphite probed by micromagneto Raman spectroscopy[J].Physical Review B,2013,88(16):12.
[27] MALEKPOUR H,BALANDIN A A.Raman-based technique for measuring thermal conductivity of graphene and related materials[J].Journal of Raman Spectroscopy,2018,49(1):106-120.
[28] FERRARI A C,BASKO D M.Raman spectroscopy as a versatile tool for studying the properties of graphene[J].Nature Nanotechnology,2013,8(4):235-246.
[29] KIM H,ABDALA A A,MACOSKO C W.Graphene/polymer nanocomposites[J].Macromolecules,2010,43(16):6515-6530.
[30] HUANG X,QI X Y,BOEY F,et al.Graphene-based composites[J].Chemical Society Reviews,2012,41(2):666-686.
[31] CHEE W K,LIM H N,HUANG N M,et al.Nanocomposites of graphene/polymers:a review[J].RSC Advances,2015,5(83):68014-68051.
[32] LI Z,WANG L,LI Y,et al.Carbon-based functional nanomaterials:preparation, properties and applications[J].Composites Science and Technology,2019,179:10-40.
[33] SYURIK Y V,GHISLANDI M G,TKALYA E E,et al.Graphene network organisation in conductive polymer composites[J].Macromolecular Chemistry and Physics,2012,213(12):1251-1258.
[34] ALEKSEEV A,EFIMOV A,LU K,et al.Three-dimensional electrical property mapping with nanometer resolution[J].Advanced Materials,2009,21(48):4915-4919.
[35] TANG L C,WAN Y J,YAN D,et al.The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites[J].Carbon,2013,60:16-27.
[36] SHOJAEE S A,ZANDIATASHBAR A,KORATKAR N,et al.Raman spectroscopic imaging of graphene dispersion in polymer composites[J].Carbon,2013,62:510-513.
[37] ZHAO F,LING L,LIU L,et al.The dispersion of graphene in conductive epoxy composites investigated by Raman spectroscopy[J].Journal of Raman Spectroscopy,2017,48(3):432-436.
[38] McCREARY A,AN Q,FORSTER A M,et al.Raman imaging of surface and sub-surface graphene oxide in fiber reinforced polymer nanocomposites[J].Carbon,2019,143:793-801.
[39] WANG B,LI Z,WANG C,et al.Folding large graphene-on-polymer films yields laminated composites with enhanced mechanical performance[J].Advanced Materials,2018,30(35):1707449.
[40] KIM K,COH S,TAN L Z,et al.Raman spectroscopy study of rotated double-layer graphene:misorientation-angle dependence of electronic structure[J].Physical Review Letters,2012,108(24):246103.
[41] BISSETT M A,KONABE S,OKADA S,et al.Enhanced chemical reactivity of graphene induced by mechanical strain[J].ACS Nano,2013,7(11):10335-10343.
[42] BISSETT M A,TSUJI M,AGO H.Strain engineering the pro-perties of graphene and other two-dimensional crystals[J].Physical Chemistry Chemical Physics,2014,16(23):11124-11138.
[43] NI Z H,YU T,LU Y H,et al.Uniaxial strain on graphene:Raman spectroscopy study and band-gap opening[J].ACS Nano,2008,2(11):2301-2305.
[44] PEREIRA V M,CASTRO N A H,PERES N M R.Tight-binding approach to uniaxial strain in graphene[J].Physical Review B,2009,80(4):045401.
[45] SI C,LIU Z,DUAN W,et al.First-principles calculations on the effect of doping and biaxial tensile strain on electron-phonon coupling in graphene[J].Physical Review Letters,2013,111(19):196802.
[46] GALIOTIS C,FRANK O,KOUKARAS E N,et al.Graphene mechanics:current status and perspectives[J].Annual Review of Chemical and Biomolecular Engineering,2015,6(1):121-140.
[47] MOHIUDDIN T M G,LOMBARDO A,NAIR R R,et al.Uni-axial strain in graphene by Raman spectroscopy:G peak splitting, Grüneisen parameters, and sample orientation[J].Physical Review B,2009,79(20):205433.
[48] HUANG Y,YOUNG R J.Effect of fibre microstructure upon the modulus of PAN-and pitch-based carbon fibres[J].Carbon,1995,33(2):97-107.
[49] COOPER C A,YOUNG R J,HALSALL M.Investigation into the deformation of carbon nanotubes and their composites through the use of Raman spectroscopy[J].Composites:Part A,2001,32(3):401-411.
[50] TSOUKLERI G,PARTHENIOS J,PAPAGELIS K,et al.Subjecting a graphene monolayer to tension and compression[J].Small,2009,5(21):2397-2402.
[51] METZGER C,RÉMI S,LIU M,et al.Biaxial strain in graphene adhered to shallow depressions[J].Nano Letters,2010,10(1):6-10.
[52] GONG L,KINLOCH I A,YOUNG R J,et al.Interfacial stress transfer in a graphene monolayer nanocomposite[J].Advanced Materials,2010,22(24):2694-2697.
[53] DING F,JI H,CHEN Y,et al.Stretchable graphene:a close look at fundamental parameters through biaxial straining[J].Nano Letters,2010,10(9):3453-3458.
[54] FRANK O,TSOUKLERI G,RIAZ I,et al.Development of a universal stress sensor for graphene and carbon fibres[J].Nature Communications,2011,2:255.
[55] LI Z,CHU J,YANG C,et al.Effect of functional groups on the agglomeration of graphene in nanocomposites[J].Composites Science and Technology,2018,163:116-122.
[56] RICE C,YOUNG R J,ZAN R,et al.Raman-scattering measurements and first-principles calculations of strain-induced phonon shifts in monolayer MoS2[J].Physical Review B,2013,87(8):081307.
[57] WANG F,KINLOCH I A,WOLVERSON D,et al.Strain-induced phonon shifts in tungsten disulfide nanoplatelets and nanotubes[J].2D Materials,2016,4(1):015007.
[58] MOUNET N,MARZARI N.First-principles determination of the structural, vibrational and thermodynamic properties of diamond, graphite, and derivatives[J].Physical Review B,2005,71(20):205214.
[59] YOON D,SON Y-W,CHEONG H.Strain-dependent splitting of the double-resonance Raman scattering band in graphene[J].Physical Review Letters,2011,106(15):155502.
[60] CHEN C,WU J Z,LAM K T,et al.Graphene nanoribbons under mechanical strain[J].Advanced Materials,2015,27(2):303-309.
[61] ANDROULIDAKIS C,KOUKARAS E N,PARTHENIOS J,et al.Graphene flakes under controlled biaxial deformation[J].Scientific Reports,2015,5:18219.
[62] GONG L,YOUNG R J,KINLOCH I A,et al.Optimizing the reinforcement of polymer-based nanocomposites by graphene[J].ACS Nano,2012,6(3):2086-2095.
[63] LEE J-U,YOON D,CHEONG H.Estimation of Young's modulus of graphene by Raman spectroscopy[J].Nano Letters,2012,12(9):4444-4448.
[64] ZABEL J,NAIR R R,OTT A K,et al.Raman spectroscopy of graphene and bilayer under biaxial strain:bubbles and balloons[J].Nano Letters,2012,12(2):617-621.
[65] CASIRAGHI C,PISANA S,NOVOSELOV K S,et al.Raman fingerprint of charged impurities in graphene[J].Applied Physics Letters,2007,91(23):233108.
[66] GEORGIOU T,BRITNELL L,BLAKE P,et al.Graphene bubbles with controllable curvature[J].Applied Physics Letters,2011,99(9):093103.
[67] JIANG T,HUANG R,ZHU Y.Interfacial sliding and buckling of monolayer graphene on a stretchable substrate[J].Advanced Functional Materials,2014,24(3):396-402.
[68] RAJU A P A,LEWIS A,DERBY B,et al.Wide-area strain sensors based upon graphene-polymer composite coatings probed by Raman spectroscopy[J].Advanced Functional Materials,2014,24(19):2865-2874.
[69] TRUNG T Q,TIEN N T,KIM D,et al.A flexible reduced graphene oxide field-effect transistor for ultrasensitive strain sensing[J].Advanced Functional Materials,2014,24(1):117-124.
[70] CHUN S,CHOI Y,PARK W.All-graphene strain sensor on soft substrate[J].Carbon,2017,116:753-759.
[71] GAO Y,LIU LQ,ZU S Z,et al.The effect of interlayer adhesion on the mechanical behaviors of macroscopic graphene oxide papers[J].ACS Nano,2011,5(3):2134-2141.
[72] SUK J W,PINER R D,AN J,et al.Mechanical properties of monolayer graphene oxide[J].ACS Nano,2010,4(11):6557-6564.
[73] GÓMEZ-NAVARRO C,BURGHARD M,KERN K.Elastic properties of chemically derived single graphene sheets[J].Nano Letters,2008,8(7):2045-2049.
[74] LI Z,KINLOCH I A,YOUNG R J.The role of interlayer adhesion in graphene oxide upon its reinforcement of nanocomposites[J].Philosophical Transactions:A,2016,374(2071):20150283.
[75] CORROD E,TARAVILLO M,BAONZA V G.Nonlinear strain effects in double-resonance Raman bands of graphite, graphene, and related materials[J].Physical Review B,2012,85(3):033407.
[76] VLASSIOUK I,POLIZOS G,COOPER R,et al.Strong and electrically conductive graphene-based composite fibers and laminates[J].ACS Applied Materials & Interfaces,2015,7(20):10702-10709.
[77] YOUNG R J,GONG L,KINLOCH I A,et al.Strain mapping in a graphene monolayer nanocomposite[J].ACS Nano,2011,5(4):3079-3084.
[78] WANG G,DAI Z,LIU L,et al.Tuning the interfacial mechanical behaviors of monolayer graphene/PMMA nanocomposites[J].ACS Applied Materials & Interfaces,2016,8(34):22554-22562.
[79] POLYZOS I,BIANCHI M,RIZZI L,et al.Suspended monolayer graphene under true uniaxial deformation[J].Nanoscale,2015,7:13033-13042.
[80] CORRO D E,KAVAN L,KALBAC M,et al.Strain assessment in graphene through the Raman 2D'mode[J].The Journal of Physical Chemistry C,2015,119(45):25651-25656.
[81] NARULA R,REICH S.Probing LO phonons of graphene under tension via the 2D' Raman mode[J].Physical Review B,2013,87(11):115424.
[82] BERNAL J D.The structure of graphite[J].Proceedings of the Royal Society:A,1924,106(740):749-773.
[83] FRANK O,BOUŠA M,RIAZ I,et al.Phonon and structural changes in deformed bernal stacked bilayer graphene[J].Nano Letters,2012,12(2):687-693.
[84] GONG L,YOUNG R J,KINLOCA H I,et al.Reversible loss of bernal stacking during the deformation of few-layer graphene in nanocomposites[J].ACS Nano,2013,7(8):7287-7294.
[85] MAROM G,DANIEL WAGNER H.Should polymer nanocomposites be regarded as molecular composites?[J].Journal of Materials Science,2017,52(14):8357-8361.
[86] ABOUDI J,ARNOLD S M,BEDNARCYK B A.Chapter 1-introduction, micromechanics of composite materials[M].ABOUDI J, ARNOLD S M,BEDNARCYK B A,ed. Oxford:Butterworth-Heinemann,2013:1-18.
[87] YOUNG R J,LOVELL P A. Introduction to polymers[M]. Boca Raton,USA:CRC Press,2011.
[88] LI Z L,YOUNG R J,KINLOCH I A,et al.Quantitative determination of the spatial orientation of graphene by polarized Raman spectroscopy[J].Carbon,2015,88:215-224.
[89] LI Z,YOUNG R J,WILSON N R,et al.Effect of the orientation of graphene-based nanoplatelets upon the Young's modulus of nanocomposites[J].Composites Science and Technology,2016,123:125-133.
[90] HERMANS J J,HERMANS P H,VERMAAS D,et al.Quantitative evaluation of orientation in cellulose fibres from the X-ray fibre diagram[J].Recueil des Travaux Chimiques des Pays-Bas,1946,65(6):427-447.
[91] KRENCHEL H. Fibre reinforcement theoretical and practical investigations of the elasticity and strength of fibre-reinforced materials[M]. Copenhagen,Danmark:Akademisk Forlag,1964.
[92] VALLÉS C,BECKERT F,BURK L,et al.Effect of the C/O ratio in graphene oxide materials on the reinforcement of epoxy-based nanocomposites[J].Journal of Polymer Science:B,2015,54(2):281-291.
[93] YOUSEFI N,GUDARZI M M,ZHENG Q,et al.Self-alignment and high electrical conductivity of ultralarge graphene oxide-polyurethane nanocomposites[J].Journal of Materials Chemistry,2012,22(25):12709-12717.
[94] BODEN A,BOERNER B,KUSCH P,et al.Nanoplatelet size to control the alignment and thermal conductivity in copper-graphite composites[J].Nano Letters,2014,14(6):3640-3644.
[95] VERMA A,PARASHAR A.Molecular dynamics based simulations to study the fracture strength of monolayer graphene oxide[J].Nanotechnology,2018,29(11):115706.
[96] SHANG J,CHEN Y,ZHOU Y,et al.Effect of folded and crumpled morphologies of graphene oxide platelets on the mechanical performances of polymer nanocomposites[J].Polymer,2015,68:131-139.
[97] LI Z,YOUNG R J,KINLOCH I A.Interfacial stress transfer in graphene oxide nanocomposites[J].ACS Applied Materials & Interfaces,2013,5(2):456-463.
[98] AHMAD S R,XUE C,YOUNG R J.The mechanisms of reinforcement of polypropylene by graphene nanoplatelets[J].Materials Science and Engineering:B,2017,216:2-9.
[99] YOUNG R J,EICHHORN S J.Deformation mechanisms in polymer fibres and nanocomposites[J].Polymer,2007,48(1):2-18.
[100] LI S,LI Z,BURNETT T L,et al.Nanocomposites of graphene nanoplatelets in natural rubber:microstructure and mechanisms of reinforcement[J].Journal of Materials Science,2017,52(16):9558-9572.
[101] WANG R,LI Z,LIU W,et al.Attapulgite-graphene oxide hybrids as thermal and mechanical reinforcements for epoxy composites[J].Composites Science and Technology,2013,87:29-35.
[102] PAPAGEORGIOU D G,KINLOCH I A,YOUNG R J.Hybrid multifunctional graphene/glass-fibre polypropylene composites[J].Composites Science and Technology,2016,137:44-51.
[103] WAN S J,CHEN Y,WANG Y L,et al.Ultrastrong graphene films via long-chain π-bridging[J].Matter,2019,1(2):389-401.
2020, Vol. 48 
