Characterization of nanocellulose–graphene electric heating membranes prepared via ultrasonic dispersion

  • Chuang Shao
  • Xinpu Li
  • Shangui Lin
  • Bing Zhuo
  • Sheng Yang
  • Quanping YuanEmail author
Polymers & biopolymers


Nanofibrillated cellulose (NFC) can enhance the flexibility and mechanical performance of graphene composite, but there are few researches focusing on dispersibility of the composite via different dispersion conditions, which mainly determine their key properties. This presented work concentrated on the influence of ultrasonic power and time on the property of NFC suspension, graphene suspension, and the composite membrane. With the increase in the ultrasonic conditions, particle size of NFC suspension decreased and the static stability of graphene suspension was improved. NFC–graphene suspension exhibited excellent static stability even adopting the low ultrasonic conditions due to the electrostatic repulsive and adhesive effect among NFCs. After enhancing shearing force induced from ultrasonic waves and cavitation, graphene sheets could be effectively detached and dispersed, and then, the planar uniformity and structural integrity of NFC–graphene membrane tended to be better, which was characterized and confirmed by morphology, chemical, and thermal and phase structure analysis. Conductivity uniformity of the seven points on the membrane exhibited an increasing trend with the increase in the ultrasonic power and time, as well as the mechanical performance, while the heating temperature uniformity had no distinct change due to the excellent thermal conductivity of the graphene. The higher ultrasonic condition was conducive to the stability of electric heating performance. Consequently, the ultrasonic treatment with different conditions had impacted the incorporation of graphene into the NFC matrix. This study’s results would be a feasible reference for the improvement of the composite used in various areas.



The work was supported by the National Natural Science Foundation of China (NSFC) (No. 31700496) and the Guangxi Natural Science Foundation of China (No. 2017GXNSFBA198015).

Compliance with ethical standards

Conflict of interest

There are no conflicts to declare.

Supplementary material

10853_2019_4006_MOESM1_ESM.docx (1.3 mb)
Supplementary material 1 (DOCX 1344 kb)


  1. 1.
    Blomquist N, Engstrom AC, Hummelgard M, Andres B, Forsberg S, Olin H (2016) Large-scale production of nanographite by tube-shear exfoliation in water. PLoS ONE 11:e0154686CrossRefGoogle Scholar
  2. 2.
    Andres B, Forsberg S, Dahlstrom C, Blomquist N, Olin H (2014) Enhanced electrical and mechanical properties of nanographite electrodes for supercapacitors by addition of nanofibrillated cellulose. Phys Status Solidi B 251:2581–2586CrossRefGoogle Scholar
  3. 3.
    Yan CY, Wang JX, Kang WB, Cui MQ, Wang X, Foo CY, Chee KJ, Lee PS (2014) Highly stretchable piezoresistive graphene–nanocellulose nanopaper for strain sensors. Adv Mater 26:2022–2027CrossRefGoogle Scholar
  4. 4.
    Ren F, Tan WZ, Duan Q, Jin YL, Pei L, Ren PG, Yan DX (2019) Ultra-low gas permeable cellulose nanofiber nanocomposite films filled with highly oriented graphene oxide nanosheets induced by shear field. Carbohydr Polym 209:310–319CrossRefGoogle Scholar
  5. 5.
    Fall AB, Lindstrom SB, Sundman O, Odberg L, Wagberg L (2011) Colloidal stability of aqueous nanofibrillated cellulose dispersions. Langmuir 27:11332–11338CrossRefGoogle Scholar
  6. 6.
    Wang FZ, Drzal LT, Qin Y, Huang ZX (2015) Multifunctional graphene nanoplatelets/cellulose nanocrystals composite paper. Compos Part B Eng 79:521–529CrossRefGoogle Scholar
  7. 7.
    Luo HL, Xie J, Xiong LL, Zhu Y, Yang ZW, Wan YZ (2019) Fabrication of flexible, ultra-strong, and highly conductive bacterial cellulose-based paper by engineering dispersion of graphene nanosheets. Compos Part B Eng 162:484–490CrossRefGoogle Scholar
  8. 8.
    Shao C, Zhu ZY, Su CW, Yang S, Yuan QP (2018) Thin electric heating membrane constructed with a three-dimensional nanofibrillated cellulose–graphene–graphene oxide system. Materials 11:1727CrossRefGoogle Scholar
  9. 9.
    Osong SH, Dahlstrom C, Forsberg S, Andres B, Engstrand P, Norgren S, Engstrom AC (2016) Nanofibrillated cellulose/nanographite composite films. Cellulose 23:2487–2500CrossRefGoogle Scholar
  10. 10.
    Luong ND, Pahimanolis N, Hippi U, Korhonen JT, Ruokolainen J, Johansson LS, Nam JD, Seppala J (2011) Graphene/cellulose nanocomposite paper with high electrical and mechanical performances. J Mater Chem 21:13991–13998CrossRefGoogle Scholar
  11. 11.
    Xu L, Teng J, Li L, Huang HD, Xu JZ, Li Y, Ren PG, Zhong GJ, Li ZM (2019) Hydrophobic graphene oxide as a promising barrier of water vapor for regenerated cellulose nanocomposite films. ACS Omega 4:509–517CrossRefGoogle Scholar
  12. 12.
    Hadi A, Zahirifar J, Karimi-Sabet J, Dastbaz A (2018) Graphene nanosheets preparation using magnetic nanoparticle assisted liquid phase exfoliation of graphite: the coupled effect of ultrasound and wedging nanoparticles. Ultrason Sonochem 44:204–214CrossRefGoogle Scholar
  13. 13.
    He SH, Zhang JJ, Xiao XT, Hong XM (2018) Effects of ultrasound vibration on the structure and properties of polypropylene/graphene nanoplatelets composites. Polym Eng Sci 58:377–386CrossRefGoogle Scholar
  14. 14.
    Carrasco PM, Montes S, Garcia I, Borghei M, Jiang H, Odriozola I, Cabanero G, Ruiz V (2014) High-concentration aqueous dispersions of graphene produced by exfoliation of graphite using cellulose nanocrystals. Carbon 70:157–163CrossRefGoogle Scholar
  15. 15.
    Pottathara YB, Thomas S, Kalarikkal N, Griesser T, Grohens Y, Bobnar V, Finsgar M, Kokol V, Kargl R (2019) UV-induced reduction of graphene oxide in cellulose nanofibril composites. New J Chem 43:681–688CrossRefGoogle Scholar
  16. 16.
    Zhan Y, Xiong CX, Yang JW, Shi ZQ, Yang QL (2019) Flexible cellulose nanofibril/pristine graphene nanocomposite films with high electrical conductivity. Compos Part A Appl Sci Manuf 119:119–126CrossRefGoogle Scholar
  17. 17.
    Chen YP, Hou X, Kang RY, Liang Y, Guo LC, Dai W, Nishimura K, Lin CT, Jiang N, Yu JH (2018) Highly flexible biodegradable cellulose nanofiber/graphene heat-spreader films with improved mechanical properties and enhanced thermal conductivity. J Mater Chem C 6:12739–12745CrossRefGoogle Scholar
  18. 18.
    Li XP, Shao C, Zhuo B, Yang S, Zhu ZY, Su CW, Yuan QP (2019) The use of nanofibrillated cellulose to fabricate a homogeneous and flexible graphene-based electric heating membrane. Int J Biol Macromol 139:1103–1116CrossRefGoogle Scholar
  19. 19.
    Kim H, Lee S (2018) Characteristics of electrical heating elements coated with graphene nanocomposite on polyester fabric: effect of different graphene contents and annealing temperatures. Fiber Polym 19:965–976CrossRefGoogle Scholar
  20. 20.
    Zhan YH, Meng YY, Li YC (2017) Electric heating behavior of flexible graphene/natural rubber conductor with self-healing conductive network. Mater Lett 192:115–118CrossRefGoogle Scholar
  21. 21.
    Benhamou K, Dufresne A, Magnin A, Mortha G, Kaddami H (2014) Control of size and viscoelastic properties of nanofibrillated cellulose from palm tree by varying the TEMPO-mediated oxidation time. Carbohydr Polym 99:74–83CrossRefGoogle Scholar
  22. 22.
    Boluk Y, Lahiji R, Zhao L, McDermott MT (2011) Suspension viscosities and shape parameter of cellulose nanocrystals (CNC). Colloid Surf A 377:297–303CrossRefGoogle Scholar
  23. 23.
    Wen CX, Yuan QP, Liang H, Vriesekoop F (2014) Preparation and stabilization of d-limonene pickering emulsions by cellulose nanocrystals. Carbohydr Polym 112:695–700CrossRefGoogle Scholar
  24. 24.
    Zhong LX, Fu SY, Peng XW, Zhan HY, Sun RC (2012) Colloidal stability of negatively charged cellulose nanocrystalline in aqueous systems. Carbohydr Polym 90:644–649CrossRefGoogle Scholar
  25. 25.
    Ramanathan T, Abdala AA, Stankovich S, Dikin DA, Herrera-Alonso M, Piner RD, Adamson DH, Schniepp HC, Chen X, Ruoff RS, Nguyen ST, Aksay IA, Prud’Homme RK, Brinson LC (2008) Functionalized graphene sheets for polymer nanocomposites. Nat Nanotechnol 3:327–331CrossRefGoogle Scholar
  26. 26.
    Yen MY, Hsiao MC, Liao SH, Liu PI, Tsai HM, Ma CCM, Pu NW, Ger MD (2011) Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells. Carbon 49:3597–3606CrossRefGoogle Scholar
  27. 27.
    Yang WX, Zhang Y, Liu TY, Huang R, Chai SG, Chen F, Fu Q (2017) Completely green approach for the preparation of strong and highly conductive graphene composite film by using nanocellulose as dispersing agent and mechanical compression. ACS Sustain Chem Eng 5:9102–9113CrossRefGoogle Scholar
  28. 28.
    Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85CrossRefGoogle Scholar
  29. 29.
    Zhu HL, Li YY, Fang ZQ, Xu JJ, Cao FY, Wan JY, Preston C, Yang B, Hu LB (2014) Highly thermally conductive papers with percolative layered boron nitride nanosheets. ACS Nano 8:3606–3613CrossRefGoogle Scholar
  30. 30.
    Zhou T, Chen D, Jiu J, Nge TT, Sugahara T, Nagao S, Koga H, Nogi M, Suganuma K, Wang X, Liu X, Cheng P, Wang T, Xiong D (2013) Electrically conductive bacterial cellulose composite membranes produced by the incorporation of graphite nanoplatelets in pristine bacterial cellulose membranes. Express Polym Lett 7:756–766CrossRefGoogle Scholar
  31. 31.
    Kiziltas EE, Kiziltas A, Rhodes K, Emanetoglu NW, Blumentritt M, Gardner DJ (2016) Electrically conductive nano graphite-filled bacterial cellulose composites. Carbohydr Polym 136:1144–1151CrossRefGoogle Scholar
  32. 32.
    Li YY, Zhu HL, Shen F, Wan JY, Lacey S, Fang ZQ, Dai HQ, Hu LB (2015) Nanocellulose as green dispersant for two-dimensional energy materials. Nano Energy 13:346–354CrossRefGoogle Scholar
  33. 33.
    Shao W, Wang SX, Liu H, Wu JM, Zhang R, Min HH, Huang M (2016) Preparation of bacterial cellulose/graphene nanosheets composite films with enhanced mechanical performances. Carbohydr Polym 138:166–171CrossRefGoogle Scholar
  34. 34.
    Nair SS, Zhu JY, Deng YL, Ragauskas AJ (2014) Hydrogels prepared from cross-linked nanofibrillated cellulose. ACS Sustain Chem Eng 2:772–780CrossRefGoogle Scholar
  35. 35.
    Krajewska A, Pasternak I, Sobon G, Sotor J, Przewloka A, Ciuk T, Sobieski J, Grzonka J, Abramski KM, Strupinski W (2017) Fabrication and applications of multi-layer graphene stack on transparent polymer. Appl Phys Lett 110:041901CrossRefGoogle Scholar
  36. 36.
    Xu XZ, Liu F, Jiang L, Zhu JY, Haagenson D, Wiesenborn DP (2013) Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. ACS Appl Mater Interfaces 5:2999–3009CrossRefGoogle Scholar
  37. 37.
    Inuwa IM, Hassan A, Samsudin SA, Kassim MHM, Jawaid M (2014) Mechanical and thermal properties of exfoliated graphite nanoplatelets reinforced polyethylene terephthalate/polypropylene composites. Polym Compos 35:2029–2035CrossRefGoogle Scholar
  38. 38.
    Lee KY, Tammelin T, Schulfter K, Kiiskinen H, Samela J, Bismarck A (2012) High performance cellulose nanocomposites: comparing the reinforcing ability of bacterial cellulose and nanofibrillated cellulose. ACS Appl Mater Interfaces 4:4078–4086CrossRefGoogle Scholar
  39. 39.
    Shen ZM, Feng JC (2018) Highly thermally conductive composite films based on nanofibrillated cellulose in situ coated with a small amount of silver nanoparticles. ACS Appl Mater Interfaces 10:24193–24200CrossRefGoogle Scholar
  40. 40.
    Rosen H, Novakov T (1977) Raman scattering and the characterisation of atmospheric aerosol particles. Nature 266:708–710CrossRefGoogle Scholar
  41. 41.
    Song N, Jiao DJ, Cui SQ, Hou XS, Ding P, Shi LY (2017) Highly anisotropic thermal conductivity of layer-by-layer assembled nanofibrillated cellulose/graphene nanosheets hybrid films for thermal management. ACS Appl Mater Interfaces 9:2924–2932CrossRefGoogle Scholar
  42. 42.
    Li J, Liu X, Tomaskovic-Crook E, Crook JM, Wallace GG (2019) Smart graphene-cellulose paper for 2D or 3D “origami-inspired” human stem cell support and differentiation. Colloid Surf B 176:87–95CrossRefGoogle Scholar
  43. 43.
    Zheng QF, Cai ZY, Ma ZQ, Gong SQ (2015) Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors. ACS Appl Mater Interfaces 7:3263–3271CrossRefGoogle Scholar
  44. 44.
    Wu HY, Wang ZM, Kumagai A, Endo T (2019) Amphiphilic cellulose nanofiber-interwoven graphene aerogel monolith for dyes and silicon oil removal. Compos Sci Technol 171:190–198CrossRefGoogle Scholar
  45. 45.
    Wang XW, Wu PY (2018) Fluorinated carbon nanotube/nanofibrillated cellulose composite film with enhanced toughness, superior thermal conductivity and electrical insulativity. ACS Appl Mater Interfaces 10:34311–34321CrossRefGoogle Scholar
  46. 46.
    Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN (2008) Superior thermal conductivity of single-layer graphene. Nano Lett 8:902–907CrossRefGoogle Scholar
  47. 47.
    Maiti S, Jayaramudu J, Das K, Reddy SM, Sadiku R, Ray SS, Liu DG (2013) Preparation and characterization of nano-cellulose with new shape from different precursor. Carbohydr Polym 98:562–567CrossRefGoogle Scholar
  48. 48.
    Gedler G, Antunes M, Realinho V, Velasco JI (2012) Thermal stability of polycarbonate–graphene nanocomposite foams. Polym Degrad Stabil 97:1297–1304CrossRefGoogle Scholar
  49. 49.
    Song PG, Cao ZH, Cai YZ, Zhao LP, Fang ZP, Fu SY (2011) Fabrication of exfoliated graphene-based polypropylene nanocomposites with enhanced mechanical and thermal properties. Polymer 52:4001–4010CrossRefGoogle Scholar
  50. 50.
    Hsiao MC, Liao SH, Yen MY, Liu PI, Pu NW, Wang CA, Ma CCM (2010) Preparation of covalently functionalized graphene using residual oxygen-containing functional groups. ACS Appl Mater Interfaces 2:3092–3099CrossRefGoogle Scholar
  51. 51.
    Pham TA, Kim JS, Kim JS, Jeong YT (2011) One-step reduction of graphene oxide with l-glutathione. Colloid Surf A 384:543–548CrossRefGoogle Scholar
  52. 52.
    Fatah IYA, Khalil HPSA, Hossain MS, Aziz AA, Davoudpour Y, Dungani R, Bhat A (2014) Exploration of a chemo-mechanical technique for the isolation of nanofibrillated cellulosic fiber from oil palm empty fruit bunch as a reinforcing agent in compositesmaterials. Polymers 6:2611–2624CrossRefGoogle Scholar
  53. 53.
    Sabbaghan M, Argyropoulos DS (2018) Synthesis and characterization of nano fibrillated cellulose/Cu2O films; micro and nano particlenucleation effects. Carbohydr Polym 197:614–622CrossRefGoogle Scholar
  54. 54.
    Guo WW, Wang X, Zhang P, Liu JJ, Song L, Hu Y (2018) Nano-fibrillated cellulose-hydroxyapatite based composite foams with excellent fire resistance. Carbohydr Polym 195:71–78CrossRefGoogle Scholar
  55. 55.
    Xiang M, Yang RM, Yang JJ, Zhou SL, Zhou J, Dong S (2019) Fabrication of polyamide 6/reduced graphene oxide nano-composites by conductive cellulose skeleton structure and its conductive behavior. Compos Part B Eng 167:533–543CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Resources, Environment and MaterialsGuangxi UniversityNanningChina

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