Abstract
An organic–inorganic functionalized nano-filler (CNC–TiO2), was prepared by loading titanium dioxide nanoparticles (TiO2) onto the crystalline nanocellulose (CNC) surface by using methacrylatesilane as cross-link agent in order to enhance compatibility between nanofiller and matrix (PMMA). Nanocomposite films (PMMA/CNC–TiO2) were prepared by free radical copolymerization of various amount (0–5 wt%) of functionalized nanofiller (CNC–TiO2) with methylmethacrylate (MMA) as main monomer, followed by solvent casting technique. The films were characterized using TEM, FTIR, FEG-SEM, and XRD, TGA, and UV–VIS spectroscopy. The results of TEM and FTIR confirmed the modification of CNC with TiO2 and the interaction between the CNC–TiO2 nanofiller and PMMA. FEG-SEM results showed a uniform dispersion of the nanofiller in the PMMA matrix whereas EDX confirmed the presence of TiO2 in the nanocomposite films. The effect of the nanofiller on the mechanical properties of PMMA was also investigated and the results showed significant improvement in tensile and modulus strengths with increasing amounts of nanofiller. In addition, TGA results demonstrated remarkable improvements in the thermal properties of the PMMA/CNC–TiO2 nanocomposite films UV results showed a response to UV absorbance due to incorporation of TiO2. Nanocomposite films can be beneficial for a variety of applications such as coating materials for windows, shelters, glazing, optical filters, and as hard packaging with UV-blocking properties.
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05 February 2020
A Correction to this paper has been published: https://doi.org/10.1007/s00542-019-04731-6
References
Abdul Khalil HPS, Davoudpour Y, Islam MN et al (2014) Production and modification of nanofibrillated cellulose using various mechanical processes: a review. Carbohydr Polymers 99:649. https://doi.org/10.1016/j.carbpol.2013.08.069
Chatterjee A (2010) Properties improvement of PMMA using nano TiO2. J Appl Polymer Sci 118:2890. https://doi.org/10.1002/app.32567
Chen L-S, Huang Z-M, Dong G-H et al (2009) Development of a transparent PMMA composite reinforced with nanofibers. Polymer Compos 30:239. https://doi.org/10.1002/pc.20551
Cheng S-K, Chen C-Y (2004) Mechanical properties and strain-rate effect of EVA/PMMA in situ polymerization blends. Eur Polymer J 40:1239. https://doi.org/10.1016/j.eurpolymj.2003.11.022
Colom X, Carrillo F, Nogués F, Garriga P (2003) Structural analysis of photodegraded wood by means of FTIR spectroscopy. Polymer Degrad Stabil 80:543. https://doi.org/10.1016/S0141-3910(03)00051-X
Dong H, Strawhecker KE, Snyder JF, Orlicki JA, Reiner RS, Rudie AW (2012) Cellulose nanocrystals as a reinforcing material for electrospun poly (methyl methacrylate) fibers: formation, properties and nanomechanical characterization. Carbohydr Polymers 87:2488. https://doi.org/10.1016/j.carbpol.2011.11.015
El-Zaher N, Melegy M, Guirguis O (2014) Thermal and structural analyses of PMMA/TiO2 nanoparticles composites. Natural Sci 6:859
Fahma F, Hori N, Iwata T, Takemura A (2013) The morphology and properties of poly (methyl methacrylate)-cellulose nanocomposites prepared by immersion precipitation method. J Appl Polymer Sci 128:1563. https://doi.org/10.1002/app.38312
Garside P, Wyeth P (2003) Identification of cellulosic fibres by FTIR spectroscopy-thread and single fibre analysis by attenuated total reflectance. Stud Conserv 48:269
Gibrila ME, Ahmed KK, Lekha P, Sitholec B, Khosla A, Furukawa H (2019) Effect of Nanocrystalline Cellulose and Zinc Oxide Hybrid Organic-Inorganic nanofilleron the physical properties of polycaprolactone nanocomposite films. Microsyst Technol. https://doi.org/10.1007/s00542-019-04497-x(Early access online)
Gorenšek M, Sluga F (2004) Modifying the UV blocking effect of polyester fabric. Text Res J 74:469. https://doi.org/10.1177/004051750407400601
NN Hafizah, LN Ismail, MZ Musa, MH Mamat, M Rusop (2012) Business, engineering and industrial applications (ISBEIA). In: 2012 IEEE Symposium
Hajlane A, Kaddami H, Joffe R, Wallström L (2013) Design and characterization of cellulose fibers with hierarchical structure for polymer reinforcement. Cellulose 20:2765. https://doi.org/10.1007/s10570-013-0044-y
Han G, Huan S, Han J, Zhang Z, Wu Q (2014) Effect of acid hydrolysis conditions on the properties of cellulose nanoparticle-reinforced polymethylmethacrylate composites. Materials 7:16
Isobe N, Sekine M, Kimura S, Wada M, Kuga S (2011) Anomalous reinforcing effects in cellulose gel-based polymeric nanocomposites. Cellulose 18:327
Jia Z, Wang Z, Xu C et al (1999) Study on poly(methyl methacrylate)/carbon nanotube composites. Mater Sci Eng A 271(1–2):395–400. https://doi.org/10.1016/s0921-5093(99)00263-4
Khaled SM, Sui R, Charpentier PA, Rizkalla AS (2007) Formation of titania nanofibers: a direct sol − gel route in supercritical CO2. Langmuir 23:3988. https://doi.org/10.1021/la062879n
Khan A, Khan RA, Salmieri S et al (2012) Mechanical and barrier properties of nanocrystalline cellulose reinforced chitosan based nanocomposite films. Carbohydr Polym 90:1601. https://doi.org/10.1016/j.carbpol.2012.07.037
Krul LP, Yakimtsova LB, Egorova EL, Matusevich YI, Selevich KA, Kurtikova AL (2009) Preparation and thermal degradation of methyl methacrylate-methacrylic acid copolymers. Russian J Appl Chem 82:1636. https://doi.org/10.1134/s1070427209090237
Laachachi A, Cochez M, Ferriol M, Lopez-Cuesta JM, Leroy E (2005) Influence of TiO2 and Fe2O3 fillers on the thermal properties of poly (methyl methacrylate) (PMMA). Mater Lett 59:36. https://doi.org/10.1016/j.matlet.2004.09.014
Litter MI (1999) Heterogeneous photocatalysis: transition metal ions in photocatalytic systems. Appl Catal B Env 23:89. https://doi.org/10.1016/S0926-3373(99)00069-7
Liu H, Liu D, Yao F, Wu Q (2010) Fabrication and properties of transparent polymethylmethacrylate/cellulose nanocrystals composites. Bioresour Technol 101:5685. https://doi.org/10.1016/j.biortech.2010.02.045
Mir SH, Nagahara LA, Thundat T, Mokarian-Tabari P, Furukawa H, Khosla A (2018) Review—organic-inorganic hybrid functional materials: an integrated platform for applied technologies. J Electrochem Soc 165(8):B3137–B3156. https://doi.org/10.1149/2.0191808jes
Nevo Y, Peer N, Yochelis S, Igbaria M, Meirovitch S, Shoseyov O, Paltiel Y (2015) Nano bio optically tunable composite nanocrystalline cellulose films. RSC Advances 5(10):7713–7719. https://doi.org/10.1039/c4ra11840e
Nussbaumer RJ, Caseri WR, Smith P, Tervoort T (2003) Polymer-TiO2 nanocomposites: a route towards visually transparent broadband UV filters and high refractive index materials. Macromol Mater Eng 288:44. https://doi.org/10.1002/mame.200290032
Paul DR, Robeson LM (2008) Polymer nanotechnology: nanocomposites. Polymer 49:3187. https://doi.org/10.1016/j.polymer.2008.04.017
Sain S, Sengupta S, Kar A et al (2014) Effect of modified cellulose fibres on the biodegradation behaviour of in situ formed PMMA/cellulose composites in soil environment: isolation and identification of the composite degrading fungus. Polym Degrad Stabil 99:156. https://doi.org/10.1016/j.polymdegradstab.2013.11.012
Sain S, Ray D, Mukhopadhyay A (2015) Improved mechanical and moisture resistance property of in situ polymerized transparent PMMA/cellulose composites. Polymer Compos 36:1748. https://doi.org/10.1002/pc.23102
Sang L, Zhao Y, Burda C (2014) TiO2 nanoparticles as functional building blocks. Chem Rev 114:9283. https://doi.org/10.1021/cr400629p
Schütz C, Sort J, Bacsik Z et al (2012) Hard and transparent films formed by nanocellulose–TiO2 nanoparticle hybrids. PLoS One 7:e45828. https://doi.org/10.1371/journal.pone.0045828
Sciancalepore C, Cassano T, Curri ML et al (2008) TiO2 nanorods/PMMA copolymer-based nanocomposites: highly homogeneous linear and nonlinear optical material. Nanotechnology 19:205705
Stevanovic A, Büttner M, Zhang Z, Yates JT (2012) Photoluminescence of TiO2: effect of UV light and adsorbed molecules on surface band structure. J Am Chem Soc 134:324. https://doi.org/10.1021/ja2072737
Sukumaran SK, Kobayashi T, Takeda S, Khosla A, Furukawa H, Sugimoto M (2019) Electrical conductivity and linear rheology of multiwalled carbon nanotube/acrylonitrile butadiene styrene polymer nanocomposites prepared by melt mixing and solution casting. J Electrochem Soc 166(9):B3091–B3095. https://doi.org/10.1149/2.0171909jes
Thakur MK, Gupta RK, Thakur VK (2014a) Surface modification of cellulose using silane coupling agent. Carbohydr Polymers 111:849. https://doi.org/10.1016/j.carbpol.2014.05.041
Thakur VK, Vennerberg D, Madbouly SA, Kessler MR (2014b) Bio-inspired green surface functionalization of PMMA for multifunctional capacitors. RSC Adv 4:6677. https://doi.org/10.1039/C3RA46592F
Wang J, Ni X (2008) Interfacial structure of poly (methyl methacrylate)/TiO2 nanocomposites prepared through photocatalytic polymerization. J Appl Polymer Sci 108:3552. https://doi.org/10.1002/app.28020
Wittwer V (1994) Transparent insulation materials: an overview on past, present and future developments. Renew Energy 5:318. https://doi.org/10.1016/0960-1481(94)90389-1
Xu J-C, Liu W-M, Li H-L (2005) Titanium dioxide doped polyaniline. Mater Sci Eng C 25:444. https://doi.org/10.1016/j.msec.2004.11.003
Yuwono AH, Liu B, Xue J et al (2004) Controlling the crystallinity and nonlinear optical properties of transparent TiO2–PMMA nanohybrids. J Mater Chem 14:2978. https://doi.org/10.1039/B403530E
Zhang J, Maurer FHJ, Yang M (2011) In situ formation of TiO2 in electrospun poly (methyl methacrylate) nanohybrids. J Phys Chem C 115:10431. https://doi.org/10.1021/jp201613x
Zhao J, Milanova M, Warmoeskerken MMCG, Dutschk V (2012) Surface modification of TiO2 nanoparticles with silane coupling agents. Colloids Surf A Physicochem Eng Aspects 413:273. https://doi.org/10.1016/j.colsurfa.2011.11.033
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Gibril, M.E., Lekha, P., Andrew, J. et al. Fabrication, physical and optical properties of functionalized cellulose based polymethylmethacrylate nanocomposites. Microsyst Technol 28, 255–265 (2022). https://doi.org/10.1007/s00542-019-04686-8
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DOI: https://doi.org/10.1007/s00542-019-04686-8