A Nano-Ink for gel pens based on scalable CNC preparation

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Recently, gel pens have been the most popular writing instrument all over the world because of their excellent writing performance. However, the gel ink of the pen is difficult to manufacture because the composition of the ink is complicated with specific rheological properties and high-stability requirements. This is the first report of an easily manufactured Nano-Ink for gel pens that is based on cellulose nanocrystals (CNCs) grafted to reactive dyes. The obtained Nano-Ink exhibits proper rheological properties and writing performance when the concentration of CNCs in this ink is 5.96%. For the potential commercial application of this Nano-Ink, a method for large-scale production of CNCs is also developed in our laboratory, including pretreatment of raw material with sulfuric acid, purification of the treated cellulosic fiber with ammonium bicarbonate (AH-NH4HCO3), and then homogenization. In AH-NH4HCO3 method, the “ultrafine fibers” are retained in the presence of NH4HCO3 during centrifugation, and the added NH4HCO3 is removed by vacuum distillation. The final CNC yield after homogenization is above 90%, which is much higher than that in previous reports, when dissolving pulp as feedstock is treated with 58% sulfuric acid at 55 °C for 45 min. Therefore, the Nano-Ink based on CNCs is promisingly going to commercial production.

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  1. Abraham E, Kam D, Nevo Y et al (2016) Highly modified cellulose nanocrystals and formation of epoxy-nanocrystalline cellulose (CNC) nanocomposites. ACS Appl Mater Interfaces 8:28086–28095.

  2. Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloids Surf A Physicochem Eng Asp 142:75–82.

  3. Atteke C, Mounguengui S, Saha Tchinda J-B et al (2013) Biodegradation of reactive blue 4 and orange G by Pycnoporus sanguineus strain isolated in Gabon. J Bioremed Biodeg  4(7):206(1–7).

  4. Barton AFM (1991) CRC handbook of solubility parameters and other cohesion parameters, vol 739. ISBN: 9780849301766 - CAT# 176

  5. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054.

  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. Brinchi L, Cotana F, Fortunati E, Kenny JM (2013) Production of nanocrystalline cellulose from lignocellulosic biomass: technology and applications. Carbohydr Polym 94:154–169.

  8. Chen L, Wang Q, Hirth K et al (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22:1753–1762.

  9. Dong XM, Revol JF, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5:19–32.

  10. Gernandt MN, Urlaub JJ (1996) An Introduction to the Gel Pen. J Forensic Sci 41:503–504.

  11. Gorgieva S, Vogrinčič R, Kokol V (2015) Polydispersity and assembling phenomena of native and reactive dye-labelled nanocellulose. Cellulose 22:3541–3558.

  12. Gratson GM, Lewis JA (2005) Phase behavior and rheological properties of polyelectrolyte inks for direct-write assembly. Langmuir 21:457–464.

  13. Grishkewich N, Mohammed N, Tang J, Tam KC (2017) Recent advances in the application of cellulose nanocrystals. Curr Opin Colloid Interface Sci 29:32–45.

  14. Habibi Y, Lucia LA, Rojas OJ (2009) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500.

  15. Halonen H, Larsson PT, Iversen T (2013) Mercerized cellulose biocomposites: a study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties. Cellulose 20:57–65.

  16. Hamad WY, Hu TQ (2010) Structure-process-yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88:392–402.

  17. Hasani M, Cranston ED, Westman G, Gray DG (2008) Cationic surface functionalization of cellulose nanocrystals. Soft Matter 4:2238–2244.

  18. Marchessault RH, Morehead FF, Koch MJ (1961) Some hydrodynamic properties of neutral suspensions of cellulose crystallites as related to size and shape. J Colloid Sci 16:327–344.

  19. Mazzella WD, Buzzini P (2005) Raman spectroscopy of blue gel pen inks. Forensic Sci Int 152:241–247.

  20. Miyamoto M, Miyazaki S, Takeuchi Y (2004) Ink for ball-point pen and ball-point pen.

  21. Morais JPS, Rosa MDF, De Souza Filho MDSM et al (2013) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym 91:229–235.

  22. Mori Y, Kushino M, Ideda H et al (1991) Carbon black-graft polymer, method for production thereof, and use thereof.

  23. Mukherjee SM, Woods HJ (1953) X-ray and electron microscope studies of the degradation of cellulose by sulphuric acid. Biochim Biophys Acta 10:499–511.

  24. Napper DH (1970) Colloid stability. Ind Eng Chem Prod Res Dev 9:467–477.

  25. Nguyen VT, Bellmann G, Boussel F (1985) Low viscosity stable aqueous dispersion of graft carbon black.

  26. Nickerson RF, Habrle JA (1947) Cellulose intercrystalline structure. Ind Eng Chem 39:1507–1512.

  27. Ojstršek A, Doliška A, Fakin D (2008) Analysis of reactive dyestuffs and their hydrolysis by capillary electrophoresis. Anal Sci 24:1581–1587.

  28. Orts WJ, Godbout L, Marchessault RH, Revol J-F (1998) Enhanced ordering of liquid crystalline suspensions of cellulose microfibrils: a small angle neutron scattering study. Macromolecules 31:5717–5725.

  29. Osada T (1999) Aqueous gel ink-filled ball point pen.

  30. Ottewill RH (1989) Colloid stability and instability: “order disorder”. Langmuir 5:4–11.

  31. Overbeek JTG (1977) Recent developments in the understanding of colloid stability. J Colloid Interface Sci 58:408–422.

  32. Phair JW, Lundberg M, Kaiser A (2009) Leveling and thixotropic characteristics of concentrated zirconia inks for screen-printing. Rheol Acta 48:121–133.

  33. Politova N, Tcholakova S, Golemanov K et al (2012) Effect of cationic polymers on foam rheological properties. Langmuir 28:1115–1126.

  34. Prathapan R, Thapa R, Garnier G, Tabor RF (2016) Modulating the zeta potential of cellulose nanocrystals using salts and surfactants. Colloids Surf A Physicochem Eng Asp 509:11–18.

  35. Qian JJ, Chen AP, Liu ZX, Li CZ (2009) The rheological characterization of the writing performance of carbon black gel ink. Fine Chem 66:139–142.

  36. Ränby B (1951) The colloidal properties of cellulose micelles. Discuss Faraday Soc 11:158–164.

  37. Rebouillat S, Pla F (2013) State of the art manufacturing and engineering of nanocellulose: a review of available data and industrial applications. J Biomater Nanobiotechnol 04:165–188.

  38. Rooki R, Ardejani FD, Moradzadeh A et al (2012) Optimal determination of rheological parameters for Herschel–Bulkley drilling fluids using genetic algorithms (GAs). Korea Aust Rheol J 24:163–170.

  39. Roux C, Novotny M, Evans I, Lennard C (1999) A study to investigate the evidential value of blue and black ballpoint pen inks in Australia. Forensic Sci Int 101:167–176.

  40. Speakman JB, Smith SG (1936) Society of dyers and colourists. J Soc Dye Colour 52:121–135.

  41. Tabak A, Baltas N, Afsin B et al (2010) Adsorption of reactive red 120 from aqueous solutions by cetylpyridinium-bentonite. J Chem Technol Biotechnol 85:1199–1207.

  42. Tam KY, Smith ER, Booth J et al (1997) Kinetics and mechanism of dyeing processes: the dyeing of cotton fabrics with a procion blue dichlorotriazinyl reactive dye. J Colloid Interface Sci 186:387–398.

  43. Valleau JP, Ivkov R, Torrie GM (1991) Colloid stability: the forces between charged surfaces in an electrolyte. J Chem Phys 95:520–532.

  44. Wang QQ, Zhu JY, Reiner RS et al (2012) Approaching zero cellulose loss in cellulose nanocrystal (CNC) production: recovery and characterization of cellulosic solid residues (CSR) and CNC. Cellulose 19:2033–2047.

  45. Williams RS, Fisher PC (1988) Pressurized roller pens and inks for such pens.

  46. Xu M, Lewis JA (2007) Phase behavior and rheological properties of polyamine-rich complexes for direct-write assembly. Langmuir 23:12752–12759.

  47. Xu X, Liu F, Jiang L et al (2013) Cellulose nanocrystals versus cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. ACS Appl Mater Interfaces 5:2999–3009.

  48. Yeh AG, Eiseman MJ, Held RP et al (2005) Self-dispersing pigment and process of making and use of same.

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This work was supported by National Natural Science Foundation of China (31570569), the Science and Technology Program of Guangzhou (201704020038) and the foundation of State Key Laboratory of Pulp and Paper Engineering (2017QN01).

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Correspondence to Shiyu Fu.

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Wang, W., Fu, S., Leu, S. et al. A Nano-Ink for gel pens based on scalable CNC preparation. Cellulose 25, 6465–6478 (2018).

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  • CNC preparation
  • Dyed CNCs
  • Nano-Ink
  • Gel pen
  • Rheological property
  • Writing performance