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Influence of high loading of cellulose nanocrystals in polyacrylonitrile composite films

Abstract

Polyacrylonitrile-co-methacrylic acid (PAN-co-MAA) and cellulose nanocrystal (CNC) composite films were produced with up to 40 wt% CNC loading through the solution casting method. The rheological properties of the solution/suspensions and the structural, optical, thermal, and mechanical properties of the resulting films were investigated. The viscosity of the composite suspensions increased with higher CNC loadings and with longer aging times. PAN-co-MAA/CNC films maintained a similar level of optical transparency even with up to 40 wt% CNC loading. The glass transition temperature (Tg) increased from 92 to 118 °C, and the composites had higher thermal stability below 350 °C compared to both neat PAN-co-MAA and neat CNC. The mechanical properties also increased with higher CNC loadings, elastic modulus increased from 2.2 to 3.7 GPa, tensile strength increased from 75 to 132 MPa, and the storage modulus increased from 3.9 to 10.5 GPa. Using the Kelly and Tyson model the interfacial shear strength between the PAN-co-MAA and CNC was calculated to be 27 MPa.

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References

  1. Aggour Y, Aziz M (2000) Degradation of polyacrylonitrile by low energy ion beam and UV radiation. Polym Test 19:261–267

  2. Agustin MB, Ahmmad B, De Leon ERP, Buenaobra JL, Salazar JR, Hirose F (2013) Starch-based biocomposite films reinforced with cellulose nanocrystals from garlic stalks. Polym Compos 34:1325–1332

  3. Anderson BJ, Zukoski CF (2009) Rheology and microstructure of entangled polymer nanocomposite melts. Macromolecules 42:8370–8384

  4. Bai H, Wang X, Zhou Y, Zhang L (2012) Preparation and characterization of poly (vinylidene fluoride) composite membranes blended with nano-crystalline cellulose. Prog Nat Sci Mater Int 22:250–257

  5. Battegazzore D, Bocchini S, Frache A (2016) Thermomechanical improvement of glycerol plasticized maize starch with high loading of cellulose, flax and talc fillers. Polym Int 65:955–962

  6. Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180

  7. Chang H, Chien A-T, Liu HC, Wang P-H, Newcomb BA, Kumar S (2015) Gel spinning of polyacrylonitrile/cellulose nanocrystal composite fibers. ACS Biomater Sci Eng 1:610–616

  8. Chang H, Luo J, Bakhtiary Davijani AA, Chien A-T, Wang P-H, Liu HC, Kumar S (2016) Individually dispersed wood-based cellulose nanocrystals. ACS Appl Mater Interfaces 8:5768–5771

  9. Chazeau L, Cavaille J, Perez J (2000) Plasticized PVC reinforced with cellulose whiskers. II. Plastic behavior. J Polym Sci Pol Phys 38:383–392

  10. Chen H, Ding Y, Lapkin A (2009) Rheological behaviour of nanofluids containing tube/rod-like nanoparticles. Powder Technol 194:132–141

  11. Chen S, Schueneman G, Pipes RB, Youngblood J, Moon RJ (2014) Effects of crystal orientation on cellulose nanocrystals–cellulose acetate nanocomposite fibers prepared by dry spinning. Biomacromolecules 15:3827–3835

  12. Cho D, Yoon SB, Drzal T (2009) Cellulose-based natural fiber topography and the interfacial shear strength of henequen/unsaturated polyester composites: influence of water and alkali treatments. Compos Interfaces 16:769–779

  13. Cox H (1952) The elasticity and strength of paper and other fibrous materials. Br J Appl Phys 3:72

  14. Derakhshandeh B, Petekidis G, Sabet SS, Hamad WY, Hatzikiriakos SG (2013) Ageing, yielding, and rheology of nanocrystalline cellulose suspensions. J Rheol 57:131–148

  15. Ebeling T, Paillet M, Borsali R, Diat O, Dufresne A, Cavaille J, Chanzy H (1999) Shear-induced orientation phenomena in suspensions of cellulose microcrystals, revealed by small angle X-ray scattering. Langmuir 15:6123–6126

  16. Eichhorn SJ (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315

  17. Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2007) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65

  18. Fortunati E, Puglia D, Monti M, Santulli C, Maniruzzaman M, Kenny JM (2013) Cellulose nanocrystals extracted from okra fibers in PVA nanocomposites. J Appl Polym Sci 128:3220–3230

  19. Girouard N, Schueneman GT, Shofner ML, Meredith JC (2015) Exploiting colloidal interfaces to increase dispersion, performance, and pot-life in cellulose nanocrystal/waterborne epoxy composites. Polymer 68:111–121

  20. Guo H, Minus ML, Jagannathan S, Kumar S (2010) Polyacrylonitrile/carbon nanotube composite films. ACS Appl Mater Interfaces 2:1331–1342

  21. Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500

  22. Haspel B, Hoffmann C, Elsner P, Weidenmann K (2015) Characterization of the interfacial shear strength of glass-fiber reinforced polymers made from novel RTM processes. Int J Plast Technol 19:333–346

  23. Huang S, Liu Z, Yin C, Wang Y, Gao Y, Chen C, Yang M (2011) Enhancement effect of filler network on isotactic polypropylene/carbon black composite melts. Colloid Polym Sci 289:1673–1681

  24. Jiang L, Morelius E, Zhang J, Wolcott M, Holbery J (2008) Study of the poly (3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhisker composites prepared by solution casting and melt processing. J Compos Mater 42:2629–2645. doi:10.1177/0021998308096327

  25. Kamal MR, Khoshkava V (2015) Effect of cellulose nanocrystals (CNC) on rheological and mechanical properties and crystallization behavior of PLA/CNC nanocomposites. Carbohyd Polym 123:105–114

  26. Karpushkin E, Berkovich A, Artemov M, Sergeev V (2014) Rheological properties of polyacrylonitrile solutions containing highly dispersed carbon nanotubes. Polym Sci Ser A+(56):681–686

  27. Kelly A, Tyson aW (1965) Tensile properties of fibre-reinforced metals: copper/tungsten and copper/molybdenum. J Mech Phys Solids 13:329–350

  28. Khan A et al (2012) Mechanical and barrier properties of nanocrystalline cellulose reinforced chitosan based nanocomposite films. Carbohyd Polym 90:1601–1608

  29. Kiziltas EE, Kiziltas A, Bollin SC, Gardner DJ (2015) Preparation and characterization of transparent PMMA–cellulose-based nanocomposites. Carbohyd Polym 127:381–389

  30. Krenchel H (1964) Fibre reinforcement; theoretical and practical investigations of the elasticity and strength of fibre-reinforced materials. Dissertation, Technical University of Denmark

  31. Kumar A, Negi YS, Choudhary V, Bhardwaj NK (2014) Characterization of cellulose nanocrystals produced by acid-hydrolysis from sugarcane bagasse as agro-waste. J Mater Phys Chem 2:1–8

  32. Lai C et al (2011) Investigation of post-spinning stretching process on morphological, structural, and mechanical properties of electrospun polyacrylonitrile copolymer nanofibers. Polymer 52:519–528

  33. Lee K-Y, Aitomäki Y, Berglund LA, Oksman K, Bismarck A (2014) On the use of nanocellulose as reinforcement in polymer matrix composites. Compos Sci Technol 105:15–27

  34. Li Z, Young RJ, Wilson NR, Kinloch IA, Vallés C, Li Z (2016) Effect of the orientation of graphene-based nanoplatelets upon the Young’s modulus of nanocomposites. Compos Sci Technol 123:125–133

  35. Lin N, Dufresne A (2014) Nanocellulose in biomedicine: current status and future prospect. Eur Polym J 59:302–325

  36. Lin N, Huang J, Chang PR, Feng J, Yu J (2011) Surface acetylation of cellulose nanocrystal and its reinforcing function in poly (lactic acid). Carbohyd Polym 83:1834–1842

  37. Liu JC, Martin DJ, Moon RJ, Youngblood JP (2015) Enhanced thermal stability of biomedical thermoplastic polyurethane with the addition of cellulose nanocrystals. J Appl Polym Sci 132:41970

  38. Ljungberg N, Cavaillé J-Y, Heux L (2006) Nanocomposites of isotactic polypropylene reinforced with rod-like cellulose whiskers. Polymer 47:6285–6292

  39. Loginova EV, Mikheev IV, Volkov DS, Proskurnin MA (2016) Quantification of copolymer composition (methyl acrylate and itaconic acid) in polyacrylonitrile carbon-fiber precursors by FTIR-spectroscopy. Anal Methods 8:371–380

  40. Ma L, Zhang Y, Meng Y, Anusonti-Inthra P, Wang S (2015) Preparing cellulose nanocrystal/acrylonitrile-butadiene-styrene nanocomposites using the master-batch method. Carbohyd Polym 125:352–359

  41. Maqsood HS, Baheti V, Wiener J, Militky J (2016) Reinforcement of enzyme hydrolyzed longer jute micro crystals in polylactic acid. Polym Composite. doi:10.1002/pc.24036

  42. Marcovich N, Auad M, Bellesi N, Nutt S, Aranguren M (2006) Cellulose micro/nanocrystals reinforced polyurethane. J Mater Res 21:870–881

  43. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994

  44. Newcomb BA, Chae HG, Gulgunje PV, Gupta K, Liu Y, Tsentalovich DE, Pasquali M, Kumar S (2014) Stress transfer in polyacrylonitrile/carbon nanotube composite fibers. Polymer 55:2734–2743

  45. Ozkul M, Mark J, Aubert J (1993) The elastic and plastic mechanical responses of microcellular foams. J Appl Polym Sci 48:767–774

  46. Park S-J (2015) Carbon fibers, vol 210. Springer, Dordrecht

  47. Rahaman MSA, Ismail AF, Mustafa A (2007) A review of heat treatment on polyacrylonitrile fiber. Polym Degrad Stabil 92:1421–1432

  48. Reising AB, Moon RJ, Youngblood JP (2012) Effect of particle alignment on mechanical properties of neat cellulose nanocrystal films. J Sci Technol For Prod Process 2:32–41

  49. Rescignano N, Fortunati E, Montesano S, Emiliani C, Kenny JM, Martino S, Armentano I (2014) PVA bio-nanocomposites: a new take-off using cellulose nanocrystals and PLGA nanoparticles. Carbohyd Polym 99:47–58

  50. Roohani M, Habibi Y, Belgacem NM, Ebrahim G, Karimi AN, Dufresne A (2008) Cellulose whiskers reinforced polyvinyl alcohol copolymers nanocomposites. Eur Polym J 44:2489–2498

  51. Schuster P (1969) LCAO–MO studies on hydrogen bonding: the interaction between carbonyl and hydroxyl groups. Int J Quantum Chem 3:851–871

  52. Sehaqui H, Ezekiel Mushi N, Morimune S, Salajkova M, Nishino T, Berglund LA (2012) Cellulose nanofiber orientation in nanopaper and nanocomposites by cold drawing. ACS Appl Mater Interfaces 4:1043–1049

  53. Siqueira G, Bras J, Dufresne A (2010) Cellulosic bionanocomposites: a review of preparation, properties and applications. Polymers 2:728–765

  54. Swentek I, Wood J (2013) Using the lap-shear test to measure polymer composite interfacial strength. In: The 19th international conference on composite materials, proceedings, 2013

  55. Thomason J, Vlug M, Schipper G, Krikor H (1996) Influence of fibre length and concentration on the properties of glass fibre-reinforced polypropylene: part 3. Strength and strain at failure. Compos Part A Appl S 27:1075–1084

  56. Visakh P, Thomas S, Oksman K, Mathew AP (2012) Crosslinked natural rubber nanocomposites reinforced with cellulose whiskers isolated from bamboo waste: processing and mechanical/thermal properties. Compos Part A Appl S 43:735–741

  57. Xu S, Girouard N, Schueneman G, Shofner ML, Meredith JC (2013a) Mechanical and thermal properties of waterborne epoxy composites containing cellulose nanocrystals. Polymer 54:6589–6598

  58. Xu X, Yang Y-Q, Xing Y-Y, Yang J-F, Wang S-F (2013b) Properties of novel polyvinyl alcohol/cellulose nanocrystals/silver nanoparticles blend membranes. Carbohyd Polym 98:1573–1577

  59. Yu H-Y, Qin Z-Y, Liu Y-N, Chen L, Liu N, Zhou Z (2012) Simultaneous improvement of mechanical properties and thermal stability of bacterial polyester by cellulose nanocrystals. Carbohyd Polym 89:971–978

  60. Yu H-y, Qin Z-y, Zhe Z (2011) Cellulose nanocrystals as green fillers to improve crystallization and hydrophilic property of poly (3-hydroxybutyrate-co-3-hydroxyvalerate). Prog Nat Sci Mater Int 21:478–484

  61. Zafeiropoulos NE (2011) Interface engineering of natural fibre composites for maximum performance. Woodhead Publishing, Sawston

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Acknowledgments

This work was financially supported by the Renewable Bioproducts Institute at Georgia Institute of Technology and by the Air Force Office of Scientific Research (Grant# FA9550-14-1-0194).

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Correspondence to Satish Kumar.

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Luo, J., Chang, H., Bakhtiary Davijani, A.A. et al. Influence of high loading of cellulose nanocrystals in polyacrylonitrile composite films. Cellulose 24, 1745–1758 (2017). https://doi.org/10.1007/s10570-017-1219-8

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Keywords

  • Cellulose nanocrystal
  • Nanocomposite
  • Polymer
  • Polyacrylonitrile