, Volume 25, Issue 1, pp 305–317 | Cite as

Study of humidity-responsive behavior in chiral nematic cellulose nanocrystal films for colorimetric response

  • Nattinee Bumbudsanpharoke
  • Wooseok Lee
  • Uiyoung Chung
  • Seonghyuk Ko
Original Paper


This study focuses on the preparation and characterization of an iridescent chiral nematic cellulose nanocrystal (CNC) film in relation to their use as a humidity-responsive material. A free-standing film with Bragg reflection was successfully prepared. Thermogravimetric analysis demonstrated gradual thermal transitions with two major weight loss regions, while the crystallinity index obtained from X-ray diffraction method was about 78%, implying the presence of disordered regions. A scanning electron microscope confirmed the orientation of CNCs in a chiral nematic pattern with a pitch in the wavelengths of visible light. A dynamic vapor sorption study showed that water vapor can penetrate into the CNC film, leading to an increase of overall mass of up to 20% at 95% RH. The moisture sorption and desorption rates of the CNC film were faster at higher humidity (80% RH). The exposure of CNC film to elevated humidity was simulated to investigate the effect of humidity on their optical semaphore. As the humidity increased, the complementary color was red-shifted upward by about 60–100 nm, which was observable to the naked eye. This is potentially explained by the swelling of the nanocrystals and the expansion of the interspace between the quasi-nematic layers of the CNCs.


Cellulose nanocrystal Humidity-responsive material Water sorption isotherm Chiral nematic structure Colorimetric indicator 



This research was supported by the International Joint R&D Program, the Agency for Korean National Food Cluster, Republic of Korea.


  1. Alothman ZA (2012) A review: fundamental aspects of silicate mesoporous materials. Materials 5:2874–2902. CrossRefGoogle Scholar
  2. Bardet R, Belgacem N, Bras J (2015a) Flexibility and color monitoring of cellulose nanocrystal iridescent solid films using anionic or neutral polymers. ACS Appl Mater Interfaces 7:4010–4018. CrossRefGoogle Scholar
  3. Bardet R, Roussel F, Coindeau S, Belgacem N, Bras J (2015b) Engineered pigments based on iridescent cellulose nanocrystal films. Carbohydr Polym 122:367–375. CrossRefGoogle Scholar
  4. Beck S, Bouchard J, Berry R (2011) Controlling the reflection wavelength of iridescent solid films of nanocrystalline cellulose. Biomacromolecules 12:167–172. CrossRefGoogle Scholar
  5. Beck S, Bouchard J, Chauve G, Berry R (2013) Controlled production of patterns in iridescent solid films of cellulose nanocrystals. Cellulose 20:1401–1411. CrossRefGoogle Scholar
  6. Belbekhouche S, Bras J, Siqueira G, Chappey C, Lebrun L, Khelifi B, Marais S, Dufresne A (2011) Water sorption behavior and gas barrier properties of cellulose whiskers and microfibrils films. Carbohydr Polym 83:1740–1748. CrossRefGoogle Scholar
  7. Boissou F et al (2014) Transition of cellulose crystalline structure in biodegradable mixtures of renewably-sourced levulinate alkyl ammonium ionic liquids, gamma-valerolactone and water. Green Chem 16:2463–2471. CrossRefGoogle Scholar
  8. Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180. CrossRefGoogle Scholar
  9. Borchani KE, Carrot C, Jaziri M (2015) Untreated and alkali treated fibers from Alfa stem: effect of alkali treatment on structural, morphological and thermal features. Cellulose 22:1577–1589. CrossRefGoogle Scholar
  10. Caurie M (2007) Hysteresis phenomenon in foods. Int J Food Sci Technol 42:45–49. CrossRefGoogle Scholar
  11. Cheung CCY, Giese M, Kelly JA, Hamad WY, MacLachlan MJ (2013) Iridescent chiral nematic cellulose nanocrystal/polymer composites assembled in organic solvents. ACS Macro Lett 2:1016–1020. CrossRefGoogle Scholar
  12. Cong HL, Yu B, Zhao XS (2011) Imitation of variable structural color in paracheirodon innesi using colloidal crystal films. Opt Express 19:12799–12808. CrossRefGoogle Scholar
  13. da Silva Perez D, van Heiningen A (2002) Determination of cellulose degree of polymerization in chemical pulps by viscosimetry. In: Seventh European workshop on lignicellulosics and pulp proceedings, pp 393–396Google Scholar
  14. Dagnon KL, Shanmuganathan K, Weder C, Rowan SJ (2012) Water-triggered modulus changes of cellulose nanofiber nanocomposites with hydrophobic polymer matrices. Macromolecules 45:4707–4715. CrossRefGoogle Scholar
  15. Diao YY, Liu XY, Toh GW, Shi L, Zi J (2013) Multiple structural coloring of silk-fibroin photonic crystals and humidity-responsive color sensing. Adv Funct Mater 23:5373–5380. CrossRefGoogle Scholar
  16. Dumanli AG, van der Kooij HM, Kamita G, Reisner E, Baumberg JJ, Steiner U, Vignolini S (2014) Digital color in cellulose nanocrystal films. ACS Appl Mater Interfaces 6:12302–12306. CrossRefGoogle Scholar
  17. Espino-Perez E, Bras J, Almeida G, Relkin P, Belgacem N, Plessis C, Domenek S (2016) Cellulose nanocrystal surface functionalization for the controlled sorption of water and organic vapours. Cellulose 23:2955–2970. CrossRefGoogle Scholar
  18. Fernandes SN et al (2017) Mind the microgap in iridescent cellulose nanocrystal films. Adv Mater 29:1–7. Google Scholar
  19. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. CrossRefGoogle Scholar
  20. French AD, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index. Cellulose 20:583–588. CrossRefGoogle Scholar
  21. Gaspar D et al (2014) Nanocrystalline cellulose applied simultaneously as the gate dielectric and the substrate in flexible field effect transistors. Nanotechnology 25:094008. CrossRefGoogle Scholar
  22. Gonçalves MC, Griol A (2016) Photonic bandgap glass-based structures. In: Vasconcelos HC, Gonçalves MC (eds) Overall aspects of non-traditional glasses: synthesis, properties and applications. Bentham Science Publishers, Sharjah, p 107Google Scholar
  23. Gray DG (2016) Recent advances in chiral nematic structure and iridescent color of cellulose nanocrystal films. Nanomaterials 6:213. CrossRefGoogle Scholar
  24. Guo J, Catchmark JM (2012) Surface area and porosity of acid hydrolyzed cellulose nanowhiskers and cellulose produced by Gluconacetobacter xylinus. Carbohydr Polym 87:1026–1037. CrossRefGoogle Scholar
  25. Guo L, Xiao L, Shan X, Zhang X (2016) Modeling adsorption with lattice Boltzmann equation. Sci Rep 6:27134. CrossRefGoogle Scholar
  26. Hill CAS, Norton A, Newman G (2009) The water vapor sorption behavior of natural fibers. J Appl Polym Sci 112:1524–1537. CrossRefGoogle Scholar
  27. Howsmon JA (1949) Water sorption and the poly-phase structure of cellulose fibers. Text Res J 19:152–162. CrossRefGoogle Scholar
  28. Ifuku S, Nogi M, Abe K, Handa K, Nakatsubo F, Yano H (2007) Surface modification of bacterial cellulose nanofibers for property enhancement of optically transparent composites: dependence on acetyl-group DS. Biomacromolecules 8:1973–1978. CrossRefGoogle Scholar
  29. Ioelovich M (2012) Optimal conditions for isolation of nanocrystalline cellulose particles. Nanosci Nanotechnol 2:9–13. CrossRefGoogle Scholar
  30. Ji Y, Vanska E, Van Heiningen A (2009) Rate determining step and kinetics of oxygen delignification. Pulp Pap Can 110:29–35Google Scholar
  31. Kargarzadeh H, Ahmad I, Abdullah I, Dufresne A, Zainudin SY, Sheltami RM (2012) Effects of hydrolysis conditions on the morphology, crystallinity, and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers. Cellulose 19:855–866. CrossRefGoogle Scholar
  32. Kelly JA, Shukaliak AM, Cheung CC, Shopsowitz KE, Hamad WY, MacLachlan MJ (2013) Responsive photonic hydrogels based on nanocrystalline cellulose. Angew Chem Int Ed Engl 52:8912–8916. CrossRefGoogle Scholar
  33. Lagerwall JPF, Schutz C, Salajkova M, Noh J, Park JH, Scalia G, Bergstrom L (2014) Cellulose nanocrystal-based materials: from liquid crystal self-assembly and glass formation to multifunctional thin films. NPG Asia Mater 6:e80. CrossRefGoogle Scholar
  34. Liu H, Liu D, Yao F, Wu Q (2010) Fabrication and properties of transparent polymethylmethacrylate/cellulose nanocrystals composites. Bioresour Technol 101:5685–5692. CrossRefGoogle Scholar
  35. Liu DG, Wang S, Ma ZS, Tian DL, Gu MY, Lin FY (2014a) Structure-color mechanism of iridescent cellulose nanocrystal films. RSC Adv 4:39322–39331. CrossRefGoogle Scholar
  36. Liu Y, Li Y, Chen HM, Yang G, Zheng XT, Zhou SB (2014b) Water-induced shape-memory poly(D, L-lactide)/microcrystalline cellulose composites. Carbohydr Polym 104:101–108. CrossRefGoogle Scholar
  37. Lu P, Hsieh YL (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82:329–336. CrossRefGoogle Scholar
  38. Luzi F, Fortunati E, Puglia D, Lavorgna M, Santulli C, Kenny JM, Torre L (2014) Optimized extraction of cellulose nanocrystals from pristine and carded hemp fibres. Ind Crops Prod 56:175–186. CrossRefGoogle Scholar
  39. Majoinen J, Kontturi E, Ikkala O, Gray DG (2012) SEM imaging of chiral nematic films cast from cellulose nanocrystal suspensions. Cellulose 19:1599–1605. CrossRefGoogle Scholar
  40. Man Z, Muhammad N, Sarwono A, Bustam MA, Kumar MV, Rafiq S (2011) Preparation of cellulose nanocrystals using an ionic liquid. J Polym Environ 19:726–731. CrossRefGoogle Scholar
  41. Mihranyan A, Llagostera AP, Karmhag R, Stromme M, Ek R (2004) Moisture sorption by cellulose powders of varying crystallinity. Int J Pharm 269:433–442. CrossRefGoogle Scholar
  42. Morgado DL, Frollini E (2011) Thermal decomposition of mercerized linter cellulose and its acetates obtained from a homogeneous reaction. Polimeros 21:111–117. Google Scholar
  43. Mu XY, Gray DG (2014) Formation of chiral nematic films from cellulose nanocrystal suspensions is a two-stage process. Langmuir 30:9256–9260. CrossRefGoogle Scholar
  44. Mu XY, Gray DG (2015) Droplets of cellulose nanocrystal suspensions on drying give iridescent 3-D “coffee-stain” rings. Cellulose 22:1103–1107. CrossRefGoogle Scholar
  45. Nakamura K, Hatakeyama T, Hatakeyama H (1981) Studies on bound water of cellulose by differential scanning calorimetry. Text Res J 51:607–613. CrossRefGoogle Scholar
  46. Nan FC, Chen Q, Liu P, Nagarajan S, Duan YX, Zhang JM (2016) Iridescent graphene/cellulose nanocrystal film with water response and highly electrical conductivity. RSC Adv 6:93673–93679. CrossRefGoogle Scholar
  47. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:1–10. CrossRefGoogle Scholar
  48. Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules 5:1671–1677. CrossRefGoogle Scholar
  49. Sangwichien C, Aranovich GL, Donohue MD (2002) Density functional theory predictions of adsorption isotherms with hysteresis loops. Colloids Surf A 206:313–320. CrossRefGoogle Scholar
  50. Stuart MA et al (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113. CrossRefGoogle Scholar
  51. Wang H, Zhang KQ (2013) Photonic crystal structures with tunable structure color as colorimetric sensors. Sensors 13:4192–4213. CrossRefGoogle Scholar
  52. Wang N, Ding EY, Cheng RS (2007) Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups. Polymer 48:3486–3493. CrossRefGoogle Scholar
  53. Wu Q, Meng YJ, Concha K, Wang SQ, Li YJ, Ma LF, Fu SY (2013) Influence of temperature and humidity on nano-mechanical properties of cellulose nanocrystal films made from switchgrass and cotton. Ind Crops Prod 48:28–35. CrossRefGoogle Scholar
  54. Wu T, Frydrych M, O’Kelly K, Chen B (2014) Poly(glycerol sebacate urethane)-cellulose nanocomposites with water-active shape-memory effects. Biomacromolecules 15:2663–2671. CrossRefGoogle Scholar
  55. Wu TH, Li JD, Li JT, Ye SM, Wei J, Guo JB (2016) A bio-inspired cellulose nanocrystal-based nanocomposite photonic film with hyper-reflection and humidity-responsive actuator properties. J Mater Chem C 4:9687–9696. CrossRefGoogle Scholar
  56. Yuan W, Zhou N, Shi L, Zhang KQ (2015) Structural coloration of colloidal fiber by photonic band gap and resonant Mie scattering. ACS Appl Mater Interfaces 7:14064–14071. CrossRefGoogle Scholar
  57. Zhang S, Chen Y (2015) Nanofabrication and coloration study of artificial Morpho butterfly wings with aligned lamellae layers. Sci Rep 5:16637. CrossRefGoogle Scholar
  58. Zhang YP, Chodavarapu VP, Kirk AG, Andrews MP (2013) Structured color humidity indicator from reversible pitch tuning in self-assembled nanocrystalline cellulose films. Sens Actuators B Chem 176:692–697. CrossRefGoogle Scholar
  59. Zhang K, Geissler A, Standhardt M, Mehlhase S, Gallei M, Chen L, Thiele CM (2015) Moisture-responsive films of cellulose stearoyl esters showing reversible shape transitions. Sci Rep 5:1–12. Google Scholar
  60. Zhu Y, Hu JL, Luo HS, Young RJ, Deng LB, Zhang S, Fan Y, Ye GD (2012) Rapidly switchable water-sensitive shape-memory cellulose/elastomer nano-composites. Soft Matter 8:2509–2517. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2017

Authors and Affiliations

  1. 1.Department of PackagingYonsei UniversityWonju-siRepublic of Korea

Personalised recommendations