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Cellulose

pp 1–16 | Cite as

Birefringence-based orientation mapping of cellulose nanofibrils in thin films

  • Shokoofeh Ghasemi
  • Parinaz Rahimzadeh-Bajgiran
  • Mehdi TajvidiEmail author
  • Stephen M. Shaler
Original Research
  • 18 Downloads

Abstract

Determination of nanofibril orientation is crucial for predicting the properties of films and membranes made from cellulose nanofibrils (CNF) because of their inherent anisotropic nature. A novel method is proposed based on image analysis of the polarized light micrographs to quantify and map nanofibril orientation in the film structure. Thin films (average 30 µm in thickness) of CNF were produced using a filtration method and were wet-stretched to two extension levels. Randomly-oriented films were also produced as the control without applying stretch. Samples were imaged at − 45°, 0° and + 45° between crossed polarizers using a polarized light microscope. A BOI was developed based on the interference color changes between the two angles (+ 45° and − 45°). The proposed BOI values range between − 1 and + 1 differentiating orientation in perpendicular directions. The index was shown to work successfully for mapping of the fibril orientation in CNF films. Statistical analysis of the tensile test results confirmed significant difference between tensile modulus of CNF films produced using different stretch ratios. This difference was also supported by the good agreement between the tensile properties of the films, the BOI and directionality results obtained from the surface analysis of scanning electron micrographs. The method was validated by applying to single pulp fibers with known orientation as well as un-stretched and stretched polyvinyl chloride films and oriented cellulose nanocrystals. The advantages of the proposed method over other conventional methods used for orientation analysis are discussed.

Keywords

Cellulose nanomaterials Fibril orientation Polarized light microscopy Image analysis Birefringence 

Abbreviations

CNF

Cellulose nanofibrils

CNC

Cellulose nanocrystals

PVC

Polyvinyl chloride

PLM

Polarized light microscopy

BOI

Birefringence orientation index

Notes

Acknowledgments

The authors would like to thank USDA National Institute of Food and Agriculture McIntire-Stennis Program for financial support.

Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Shokoofeh Ghasemi, Parinaz Rahimzadeh-Bajgiran and Mehdi Tajvidi developed the method to produce the orientation index. Shokoofeh Ghasemi prepared and tested CNF film samples, Parinaz Rahimzadeh-Bajgiran performed image analysis. All authors contributed to the analysis and discussions.

Funding

This project was funded by the USDA National Institute of Food and Agriculture, McIntire-Stennis project number ME0-41616 through the Maine Agricultural & Forest Experiment Station. Maine Agricultural and Forest Experiment Station Publication Number 3714.

Supplementary material

10570_2019_2821_MOESM1_ESM.docx (48.5 mb)
Supplementary material 1 (DOCX 49701 kb)

References

  1. Abd Manaf ME, Tsuji M, Nobukawa S, Yamaguchi M (2011) Effect of moisture on the orientation birefringence of cellulose esters. Polymers 3(2):955CrossRefGoogle Scholar
  2. Abe H, Funada R (2005) Review—The orientation of cellulose microfibrils in the cell walls of tracheids in conifers. IAWA J 26(2):161CrossRefGoogle Scholar
  3. Amini E, Tajvidi M, Gardner DJ, Bousfield DW (2017) Utilization of cellulose nanofibrils as a binder for particleboard manufacture. BioResources 12:4093–4110CrossRefGoogle Scholar
  4. Arteaga O, Baldrís M, Antó J, Canillas A, Pascual E, Bertran E (2014) Mueller matrix microscope with a dual continuous rotating compensator setup and digital demodulation. Appl Opt 53:2236PubMedCrossRefGoogle Scholar
  5. Bergström J (2015) Mechanics of solid polymers: theory and computational modeling. William Andrew Publishing, New YorkGoogle Scholar
  6. Bi X, Li G, Doty SB, Camacho NP (2005) A novel method for determination of collagen orientation in cartilage by Fourier transform infrared imaging spectroscopy (FT-IRIS). Osteoarthr Cartil 13(12):1050PubMedCrossRefGoogle Scholar
  7. Chowdhury RA, Peng SX, Youngblood J (2017) Improved order parameter (alignment) determination in cellulose nanocrystal (CNC) films by a simple optical birefringence method. Cellulose 24(5):1957CrossRefGoogle Scholar
  8. Davidson MW (2019) The first order (full wave) retardation plate. https://www.olympus-lifescience.com/en/microscope-resource/primer/techniques/polarized/firstorderplate. Accessed 14 June 2019
  9. Duckett KE, Tripp VW (1967) X-ray and optical orientation measurements on single cotton fibers. Text Res J 37(6):517CrossRefGoogle Scholar
  10. Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mater Today 16(6):220CrossRefGoogle Scholar
  11. Dufresne A (2017) Cellulose nanomaterial reinforced polymer nanocomposites. Curr Opin Colloid Interface Sci 29:1CrossRefGoogle Scholar
  12. Ebeling T, Paillet M, Borsali R, Diat O, Dufresne A, Cavaille JY, Chanzy H (1999) Shear-induced orientation phenomena in suspensions of cellulose microcrystals, revealed by small angle X-ray scattering. Langmuir 15(19):6123CrossRefGoogle Scholar
  13. Fall AB, Lindstrom SB, Sprakel J, Wagberg L (2013) A physical cross-linking process of cellulose nanofibril gels with shear-controlled fibril orientation. Soft Matter 9(6):1852CrossRefGoogle Scholar
  14. Ghasemi S, Tajvidi M, Bousfield DW, Gardner DJ, Gramlich WM (2017) Dry-spun neat cellulose nanofibril filaments: influence of drying temperature and nanofibril structure on filament properties. Polymers 9(9):392PubMedCentralCrossRefGoogle Scholar
  15. Ghasemi S, Tajvidi M, Bousfield DW, Gardner DJ (2018a) Reinforcement of natural fiber yarns by cellulose nanomaterials: a multi-scale study. Ind Crops Prod 111:471CrossRefGoogle Scholar
  16. Ghasemi S, Tajvidi M, Gardner DJ, Bousfield DW, Shaler SM (2018b) Effect of wettability and surface free energy of collection substrates on the structure and morphology of dry-spun cellulose nanofibril filaments. Cellulose 25(11):6305CrossRefGoogle Scholar
  17. Gierlinger N, Luss S, Konig C, Konnerth J, Eder M, Fratzl P (2010) Cellulose microfibril orientation of Picea abies and its variability at the micron-level determined by Raman imaging. J Exp Bot 61(2):587PubMedCrossRefPubMedCentralGoogle Scholar
  18. Gilbert M (1994) Crystallinity in poly (vinyl chloride). J Macromol Sci C 34(1):77CrossRefGoogle Scholar
  19. Gindl W, Martinschitz KJ, Boesecke P, Keckes J (2006) Changes in the molecular orientation and tensile properties of uniaxially drawn cellulose films. Biomacromol 7(11):3146CrossRefGoogle Scholar
  20. Gindl W, Reifferscheid M, Adusumalli RB, Weber H, Roder T, Sixta H, Schoberl T (2008) Anisotropy of the modulus of elasticity in regenerated cellulose fibres related to molecular orientation. Polymer 49(3):792CrossRefGoogle Scholar
  21. Hakansson KMO, Fall AB, Lundell F, Yu S, Krywka C, Roth SV, Santoro G, Kvick M, Wittberg LP, Wagberg L, Soderberg LD (2014) Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments. Nat Commun 5:4018PubMedPubMedCentralCrossRefGoogle Scholar
  22. Hassan EA, Hassan ML, Abou-zeid RE, El-Wakil NA (2016) Novel nanofibrillated cellulose/chitosan nanoparticles nanocomposites films and their use for paper coating. Ind Crops Prod 93:219CrossRefGoogle Scholar
  23. Josefsson G, Ahvenainen P, Mushi NE, Gamstedt EK (2015) Fibril orientation redistribution induced by stretching of cellulose nanofibril hydrogels. J Appl Phys 117(21):214311CrossRefGoogle Scholar
  24. Kadimi A, Benhamou K, Ounaies Z, Magnin A, Dufresne A, Kaddami H, Raihane M (2014) Electric field alignment of nanofibrillated cellulose (NFC) in silicone oil: impact on electrical properties. ACS Appl Mater Interfaces 6(12):9418PubMedCrossRefGoogle Scholar
  25. Kobe R, Iwamoto S, Endo T, Yoshitani K, Teramoto Y (2016) Stretchable composite hydrogels incorporating modified cellulose nanofiber with dispersibility and polymerizability: mechanical property control and nanofiber orientation. Polymer 97:480CrossRefGoogle Scholar
  26. Kojima Y, Minamino J, Isa A, Suzuki S, Ito H, Makise R, Okamoto M (2013) Binding effect of cellulose nanofibers in wood flour board. J Wood Sci 59(5):396CrossRefGoogle Scholar
  27. Kuntman E, Arteaga O, Anto J, Cayuela D, Bertran E (2015) Conversion of a polarization microscope into a Mueller matrix microscope application to the measurement of textile fibers. Opt Pura Appl 48(4):309CrossRefGoogle Scholar
  28. Liu Z-Q (1991) Scale space approach to directional analysis of images. Appl Opt 30(11):1369PubMedCrossRefGoogle Scholar
  29. Liu JG, Mason PJ (2016) Image processing and GIS for remote sensing: techniques and applications. Wiley, HobokenCrossRefGoogle Scholar
  30. Mashkour M, Kimura T, Kimura F, Mashkour M, Tajvidi M (2014a) Tunable self-assembly of cellulose nanowhiskers and polyvinyl alcohol chains induced by surface tension torque. Biomacromol 15(1):60CrossRefGoogle Scholar
  31. Mashkour M, Kimura T, Kimura F, Mashkour M, Tajvidi M (2014b) One-dimensional core–shell cellulose-akaganeite hybrid nanocrystals: synthesis, characterization, and magnetic field induced self-assembly. RSC Adv 4(94):52542CrossRefGoogle Scholar
  32. Mashkour M, Kimura T, Mashkour M, Kimura F, Tajvidi M (2019) Printing birefringent figures by surface tension-directed self-assembly of a cellulose nanocrystal/polymer ink components. ACS Appl Mater Interfaces 11(1):1538PubMedCrossRefGoogle Scholar
  33. Mazhari Mousavi SM, Afra E, Tajvidi M, Bousfield DW, Dehghani-Firouzabadi M (2018) Application of cellulose nanofibril (CNF) as coating on paperboard at moderate solids content and high coating speed using blade coater. Prog Org Coat 122:207CrossRefGoogle Scholar
  34. McLean JP, Evans R, Moore JR (2010) Predicting the longitudinal modulus of elasticity of Sitka spruce from cellulose orientation and abundance. Holzforschung 64(4):495CrossRefGoogle Scholar
  35. Mendoza-Galvan A, Tejeda-Galan T, Dominquez-Gomez AB, Mauricio-Sanchez RA, Jarrendahl K, Arwin H (2019) Linear birefringent films of cellulose nanocrystals produced by dip-coating. Nanomaterials 9(1):45CrossRefGoogle Scholar
  36. Newton RH, Brown JY, Meek KM (1996) Polarized light microscopy technique for quantitatively mapping collagen fibril orientation in cornea. In: Optical biopsies and microscopic techniques, vol 2926. International Society for Optics and Photonics, pp 278–284.  https://doi.org/10.1117/12.260805
  37. Nissila T, Karhula SS, Saarakkala S, Oksman K (2018) Cellulose nanofiber aerogels impregnated with bio-based epoxy using vacuum infusion: structure, orientation and mechanical properties. Compos Sci Technol 155:64CrossRefGoogle Scholar
  38. Nobukawa S, Enomoto-Rogers Y, Shimada H, Iwata T, Yamaguchi M (2015) Effect of acetylation site on orientation birefringence of cellulose triacetate. Cellulose 22(5):3003CrossRefGoogle Scholar
  39. Ross RJ (2010) Wood handbook: wood as an engineering material USDA Forest Service, Forest Products Laboratory, General Technical Report FPL-GTR-190Google Scholar
  40. Schneider CA, Rasband WS, Eliceiri KW (2012) NIH Image to ImageJ: 25 years of image analysis. Nat Methods 9:671PubMedPubMedCentralCrossRefGoogle Scholar
  41. Sehaqui H, Mushi NE, Morimune S, Salajkova M, Nishino T, Berglund LA (2012) Cellulose nanofiber orientation in nanopaper and nanocomposites by cold drawing. ACS Appl Mater Interfaces 4(2):1043PubMedCrossRefGoogle Scholar
  42. Sørensen BE (2012) A revised Michel-Lévy interference colour chart based on first-principles calculations. Eur J Mineral 25(1):5CrossRefGoogle Scholar
  43. Sun L, Singh S, Joo M, Vega-Sanchez M, Ronald P, Simmons BA, Adams P, Auer M (2016) Non-invasive imaging of cellulose microfibril orientation within plant cell walls by polarized Raman microspectroscopy. Biotechnol Bioeng 113(1):82PubMedCrossRefGoogle Scholar
  44. Sun W, Tajvidi M, Hunt CG, McIntyre G, Gardner DJ (2019) Fully bio-based hybrid composites made of wood, fungal mycelium and cellulose nanofibrils. Sci Rep 9(1):3766PubMedPubMedCentralCrossRefGoogle Scholar
  45. Tayeb HA, Amini E, Ghasemi S, Tajvidi M (2018) Cellulose nanomaterials-binding roperties and applications: a review. Molecules 23(10):2684PubMedCentralCrossRefPubMedGoogle Scholar
  46. Uetani K, Koga H, Nogi M (2019) Estimation of the intrinsic birefringence of cellulose using bacterial cellulose nanofiber films. ACS Macro Lett 8:250CrossRefGoogle Scholar
  47. Ye C, Sundström MO, Remes K (1994) Microscopic transmission ellipsometry: measurement of the fibril angle and the relative phase retardation of single, intact wood pulp fibers. Appl Opt 33(28):6626PubMedCrossRefGoogle Scholar
  48. Ye DD, Cheng QY, Zhang QL, Wang YX, Chang CY, Li LB, Peng HY, Zhang LN (2017) Deformation drives alignment of nanofibers in framework for inducing anisotropic cellulose hydrogels with high toughness. ACS Appl Mater Interfaces 9(49):43154PubMedCrossRefGoogle Scholar
  49. Yildirim N, Shaler S (2016) The application of nanoindentation for determination of cellulose nanofibrils (CNF) nanomechanical properties. Mater Res Express 3(10):105017CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Laboratory of Renewable Nanomaterials, School of Forest Resources and Advanced Structures and Composites CenterUniversity of MaineOronoUSA
  2. 2.School of Forest ResourcesUniversity of MaineOronoUSA

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