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Nanocomposite films based on cellulose reinforced with nano-SiO2: microstructure, hydrophilicity, thermal stability, and mechanical properties

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Abstract

Microcrystalline cellulose/nano-SiO2 composite films have been successfully prepared from solutions in ionic liquid 1-allyl-3-methylimidazolium chloride by a facile and economic method. The microstructure and properties were investigated by Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, transmission electron microscopy, water contact angle, thermal gravimetric analyses, and tensile testing. The results revealed that the well-dispersed nanoparticles exhibit strong interfacial interactions with cellulose matrix. The thermal stability and tensile strength of the cellulose nanocomposite films were significantly improved over those of pure regenerated cellulose film. Furthermore, the cellulose nanocomposite films exhibited better hydrophobicity and a lower degree of swelling than pure cellulose. This method is believed to have potential application in the field of fabricating cellulose-based nanocomposite film with high performance, thus enlarging the scope of commercial application of cellulose-based materials.

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References

  • Adebahr J, Best AS, Byrne N, Jacobsson P, MacFarlane DR, Forsyth M (2003) Ion transport in polymer electrolytes containing nanoparticulate TiO2: the influence of polymer morphology. Phys Chem Chem Phys 5:720–725

    Article  CAS  Google Scholar 

  • Ashori A, Sheykhnazari S, Tabarsa T, Shakeri A, Golalipour M (2012) Bacterial cellulose/silica nanocomposites: preparation and characterization. Carbohydr Polym 90:413–418

    Article  CAS  Google Scholar 

  • Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7:183–189

    Article  CAS  Google Scholar 

  • Cai J, Liu SL, Feng J, Kimura S, Wada M, Kuga S, Zhang LN (2012) Cellulose-silica nanocomposite aerogels by in situ formation of silica in cellulose gel. Angew Chem Int Ed 51:2076–2079

    Article  CAS  Google Scholar 

  • Chang HC, Hung TC, Chang SC, Jiang JC, Lin SH (2011) Interactions of silica nanoparticles and ionic liquids probed by high pressure vibrational spectroscopy. J Phys Chem C 115:11962–11967

    Article  CAS  Google Scholar 

  • Cheng G, Varanasi P, Li CL, Liu HB, Melnichenko YB, Simmons BA, Kent MS, Singh S (2011) Transition of cellulose crystalline structure and surface morphology of biomass as a function of ionic liquid pretreatment and its relation to enzymatic hydrolysis. Biomacromolecules 12:933–941

    Article  CAS  Google Scholar 

  • Chirkova J, Andersons B, Andersone I (2004) Determination of standard isotherms of the sorption of some vapors with cellulose. J Colloid Interface Sci 276:284–289

    Article  CAS  Google Scholar 

  • Deng TS, Marlow F (2012) Synthesis of monodisperse polystyrene@vinyl-SiO2 core-shell particles and hollow SiO2 spheres. Chem Mater 24:536–542

    Article  CAS  Google Scholar 

  • Fink H, Weigel P, Purz HJ, Ganster J (2011) Structure formation of regenerated cellulose materials from NMMO-Solutions. Prog Polym Sci 26:1473–1524

    Article  Google Scholar 

  • Ford ENJ, Mendon SK, Thames SF, Rawlins JW (2010) X-ray diffraction of cotton treated with neutralized vegetable oil-based macromolecular crosslinkers. J Eng Fiber Fabr 5:10–20

    Google Scholar 

  • Fox J, Wie JJ, Greenland BW, Burattini S, Hayes W, Colquhoun HM, Mackay ME, Rowan SJ (2012) High-strength, healable, supramolecular polymer nanocomposites. J Am Chem Soc 134:5362–5368

    Article  CAS  Google Scholar 

  • Han DL, Yan LF, Chen WF, Li W, Bangal PR (2011) Cellulose/graphite oxide composite films with improved mechanical properties over a wide range of temperature. Carbohydr Polym 83:966–972

    Article  CAS  Google Scholar 

  • Huang YJ, Qin YW, Zhou Y, Niu H, Yu ZZ, Dong JY (2010) Polypropylene/graphene oxide nanocomposites prepared by in situ Ziegler-Natta polymerization. Chem Mater 22:4096–4102

    Article  CAS  Google Scholar 

  • Hult EL, Larsson PT, Iversen T (2001) Cellulose fibril aggregation-an inherent property of kraft pulps. Polymer 42:3309–3314

    Article  CAS  Google Scholar 

  • Jana SC, Jain S (2011) Dispersion of nanofillers in high performance polymers using reactive solvents as processing aids. Polymer 42:6897–6905

    Article  Google Scholar 

  • Joung YS, Buie CR (2011) Electrophoretic deposition of unstable colloidal suspensions for superhydrophobic surfaces. Langmuir 27:4156–4163

    Article  CAS  Google Scholar 

  • Kadokawa J, Murakami M, Takegawa A, Kaneko Y (2009) Preparation of cellulose-starch composite gel and fibrous material from a mixture of the polysaccharides in ionic liquid. Carbohydr Polym 75:180–183

    Article  CAS  Google Scholar 

  • Kim SH, Ahn SH, Hirai T (2003) Crystallization kinetics and nucleation activity of silica nanoparticle-filled poly(ethylene 2,6-naphthalate). Polymer 44:5625–5634

    Article  CAS  Google Scholar 

  • Kim SJ, Dwiatmoko AA, Choi JW, Suh YW, Suh DJ, Oh M (2010) Cellulose pretreatment with 1-n-butyl-3-methylimidazolium chloride for solid acid-catalyzed hydrolysis. Bioresour Technol 101:8273–8279

    Article  CAS  Google Scholar 

  • Kuang QL, Zhao JC, Niu YH, Zhang J, Wang ZG (2008) Celluloses in an ionic liquid: the rheological properties of the solutions spanning the dilute and semidilute regimes. J Phys Chem B 112:10234–10240

    Article  CAS  Google Scholar 

  • Li R, Chang CY, Zhou JP, Zhang LN, Gu WQ, Li CT, Liu SL, Kuga S (2010) Primarily industrialized trial of novel fibers spun from cellulose dope in NaOH/urea aqueous solution. Ind Eng Chem Res 49:11380–11384

    Article  CAS  Google Scholar 

  • Low SP, Ahmad A, Hamzah H, Rahman MYA (2011) Nanocomposite solid polymeric electrolyte of 49% poly (methyl methacrylate)-grafted natural rubber-titanium dioxide-lithium tetrafluoroborate (MG49-TiO2-LiBF4). J Solid State Electrochem 15:2611–2618

    Article  CAS  Google Scholar 

  • Lue A, Zhang L (2008) Investigation of the scaling law on cellulose solution prepared at low temperature. J Phys Chem B 112:4488–4495

    Article  CAS  Google Scholar 

  • Ma Z, Yu JH, Dai S (2010) Preparation of inorganic materials using ionic liquids. Adv Mater 22:261–285

    Article  CAS  Google Scholar 

  • Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose I β from Synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082

    Article  CAS  Google Scholar 

  • Pinto RJB, Marques PAAP, Barros-Timmons AM, Trindade T, Neto CP (2008) Novel SiO2/cellulose nanocomposites obtained by in situ synthesis and via polyelectrolytes assembly. Compos Sci Tecnol 68:1088–1093

    Article  CAS  Google Scholar 

  • Portugal I, Dias MV, Duarte RF, Evtugui DV (2010) Hydration of cellulose/silica hybrids assessed by sorption isotherms. J Phys Chem B 114:4047–4055

    Article  CAS  Google Scholar 

  • Qi HS, Liu JW, Gao SL, Mäder E (2013) Multifunctional films composed of carbon nanotubes and cellulose regenerated from alkaline-urea solution. J Mater Chem A 1:2161–2168

    Article  CAS  Google Scholar 

  • Quan SL, Kang SG, Chin IJ (2010) Characterization of cellulose fibers electro-spun using ionic liquid. Cellulose 17:223–230

    Article  CAS  Google Scholar 

  • Rao YQ, Pochan JM (2007) Mechanics of polymer-clay nanocomposites. Macromolecules 40:290–296

    Article  CAS  Google Scholar 

  • Rhim JW, Hong SI, Park HM, Ng PK (2006) Preparation and characterization of chitosan-based nanocomposite films with antimicrobial activity. J Agric Food Chem 54:5814–5822

    Article  CAS  Google Scholar 

  • Sahoo NG, Rana S, Cho JW, Li L, Chan SH (2010) Polymer nanocomposites based on functionalized carbon nanotubes. Prog Polym Sci 35:837–867

    Article  CAS  Google Scholar 

  • Salavagione HJ, Martínez G (2011) Importance of covalent linkages in the preparation of effectivereduced graphene oxide–poly(vinyl chloride) nanocomposites. Macromolecules 44:2685–2692

    Article  CAS  Google Scholar 

  • Samayam IP, Hanson BL, Langan P, Schall CA (2011) Ionic liquid induced changes in cellulose structure associated with enhanced biomass hydrolysis. Biomacromolecules 12:3091–3098

    Article  CAS  Google Scholar 

  • Shang XY, Zhu ZK, Yin J, Ma XD (2002) Compatibility of soluble polyimide/silica hybrids induced by a coupling agent. Chem Mater 14:71–77

    Article  CAS  Google Scholar 

  • Shimano S, Zhou HS, Honma I (2007) Preparation of nanohybrid solid-state electrolytes with liquidlike mobilities by solidifying ionic liquids with silica particles. Chem Mater 19:5216–5221

    Article  CAS  Google Scholar 

  • Song HZ, Zhang J, Niu YH, Wang ZG (2010) Phase transition and rheological behaviors of concentrated cellulose/ionic liquid solutions. J Phys Chem B 114:6006–6013

    Article  CAS  Google Scholar 

  • Song HZ, Niu YH, Wang ZG, Zhang J (2011) Liquid crystalline transition and gel-sol transitions for concentrated microcrystalline cellulose (MCC)/1-ethyl-3-methylimidazolium acetate (EMIMAc) solutions. Biomacromolecules 12:1087–1096

    Article  CAS  Google Scholar 

  • Song HZ, Niu YH, Yu J, Zhang J, Wang ZG, He JS (2013) Preparation and morphology of different types of cellulose spherulites from concentrated cellulose ionic liquid solutions. Soft Matter 9:3013–3020

    Article  CAS  Google Scholar 

  • Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975

    Article  CAS  Google Scholar 

  • Tian RH, Seitz O, Li M, Hu WC, Chabal YJ, Ga JM (2010) Infrared characterization of interfacial Si–O bond formation on silanized flat SiO2/Si surfaces. Langmuir 26:4563–4566

    Article  CAS  Google Scholar 

  • Ueno K, Watanabe M (2011) From colloidal stability in ionic liquids to advanced soft materials using unique media. Langmuir 27:9105–9115

    Article  CAS  Google Scholar 

  • van Zyl WE, Garcı′a M, Schrauwen BAG, Kooi BJ, De Hosson JM, Verweij H (2002) Hybrid polyamide/silica nanocomposites: synthesis and mechanical testing. Macromol Mater Eng 287:106–110

    Article  Google Scholar 

  • Wang BG, Lou WJ, Wang XB, Hao JC (2012) Relationship between dispersion state and reinforcement effect of graphene oxide in microcrystalline cellulose–graphene oxide composite films. J Mater Chem 22:12859–12866

    Article  CAS  Google Scholar 

  • Winey KI, Moniruzzaman M (2006) Polymer nanocomposites containing carbon nanotubes. Macromolecules 39:5194–5205

    Article  Google Scholar 

  • Wittmar A, Ruiz-Abad D, Ulbricht M (2012) Dispersions of silica nanoparticles in ionic liquids investigated with advanced rheology. J Nanopart Res 14:1–10

    Article  Google Scholar 

  • Wong MH, Guenther J, Sun LY, Blümel J, Nishimura R, Sue HJ (2012) Synthesis and fabrication of multifunctional nanocomposites: stable dispersions of nanoparticles tethered with short, dense and polydisperse polymer brushes in poly(methyl methacrylate). Adv Funct Mater 22:3614–3624

    Article  CAS  Google Scholar 

  • Wu J, Yuan Q (2002) Gas permeability of a novel cellulose membrane. J Membrane Sci 204:185–194

    Article  CAS  Google Scholar 

  • Wu CL, Zhang MQ, Rong MZ, Friedrich K (2005) Silica nanoparticles filled polypropylene: effects of particle surface treatment, matrix ductility and particle species on mechanical performance of the composites. Compos Sci Technol 65:635–645

    Article  CAS  Google Scholar 

  • Xu ZH, Niu YH, Wang ZG, Li H, Yang L, Qiu J, Wang H (2011) Enhanced nucleation rate of polylactide in composites assisted by surface acid oxidized carbon nanotubes of different aspect ratios. ACS Appl Mater Interfaces 3:3744–3753

    Article  CAS  Google Scholar 

  • Yang QL, Fukuzumi H, Saito T, Isogai A, Zhang LN (2011) Transparent cellulose films with high gas barrier properties fabricated from aqueous alkali/urea solutions. Biomacromolecules 12:2766–2771

    Article  CAS  Google Scholar 

  • Zengeni E, Hartmann PC, Pasch H (2012) Encapsulation of clay by ad-miniemulsion polymerization: the influence of clay size and modifier reactivity on latex morphology and physical properties. ACS Appl Mater Interfaces 4:6957–6968

    Article  CAS  Google Scholar 

  • Zhang H, Wu J, Zhang J, He JS (2005) 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 38:8272–8277

    Article  CAS  Google Scholar 

  • Zhang H, Wang ZG, Zhang ZN, Wu J, Zhang J, He JS (2007) Regenerated cellulose/multi-walled carbon nanotube (MWCNT) composite fibers with enhanced mechanical properties prepared with an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). Adv Mater 19:698–704

    Article  CAS  Google Scholar 

  • Zhang D, Yu W, Hao D, Li L, Liu H, Lu ZL (2012a) Functional nanostructured surfaces in hybrid sol–gel glass in large area for antireflective and super-hydrophobic purposes. J Mater Chem 22:17328–17331

    Article  CAS  Google Scholar 

  • Zhang J, Cao YW, Feng JC, Wu PY (2012b) Graphene-oxide-sheet-induced gelation of cellulose and promoted mechanical properties of composite aerogels. J Phys Chem C 116:8063–8068

    Article  CAS  Google Scholar 

  • Zou H, Wu SS, Shen J (2008) Polymer/silica nanocomposites: preparation, characterization, properties, and applications. Chem Rev 108:3893–3957

    Article  CAS  Google Scholar 

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Acknowledgments

We acknowledge the financial support from the Specialized Research Fund for the Doctoral Program of Higher Education (Grant No. 20121301120004), the Natural Science Foundation of Hebei Province (Grant No. B2013201117), the Plan of Science Technology Research and Development of Hebei Province (Grant No. 12211204), Hebei University (Grant No. Y2011223), and the Baoding Bureau of Science and Technology (Grant No. 12ZG023).

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  1. College of Chemistry and Environmental Science, Hebei University, Baoding, 071002, People’s Republic of China

    Hongzan Song

  2. Baoding Center for Disease Control and Prevention, Baoding, 071000, People’s Republic of China

    Liwei Zheng

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  1. Hongzan Song
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  2. Liwei Zheng
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Correspondence to Hongzan Song.

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Song, H., Zheng, L. Nanocomposite films based on cellulose reinforced with nano-SiO2: microstructure, hydrophilicity, thermal stability, and mechanical properties. Cellulose 20, 1737–1746 (2013). https://doi.org/10.1007/s10570-013-9941-3

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