Abstract
Hydroxyethyl cellulose (HEC) fibers with low degree of substitution were prepared by wet spinning of solutions in 8 wt% aqueous NaOH solvent. The spinning solution had a classical shear-thinning behavior and a good stability towards gelation according to its rheological behavior. The influence of drawing conditions on the structural characteristics and tensile properties of the resultant HEC fibers was investigated using synchrotron X-ray measurements, scanning electron microscope and tensile tests. HEC fibers exhibited circular cross-sections with soft and deformable surface layer as well as relatively uniform and dense inner structure. Regardless of the different jet stretch or post-drawing conditions, most of the structural features and the tensile properties of HEC fibers were improved as the drawing ratio increased. Post-drawing was confirmed to be the key factor in controlling the fiber structure and tensile properties due to plastic deformation. Excellent tensile properties were found for HEC fibers prepared at relatively low jet ratio associated with high post-drawing ratio.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548. doi:10.1002/mabi.200400222
Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7:183–189. doi:10.1021/bm0505585
Crawshaw J, Cameron R (2000) A small angle X-ray scattering study of pore structure in Tencel cellulose fibres and the effects of physical treatments. Polymer 41:4691–4698. doi:10.1016/S0032-3861(99)00502-9
Ducos F, Biganska O, Christian Schuster K, Navard P (2006) Influence of the Lyocell fibers structure on their fibrillation. Cell Chem Technol 40:299–311
Fink H, Weigel P, Purz H, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524. doi:10.1016/S0079-6700(01)00025-9
Fischer E, Herchenröder P, Manley R, Stamm M (1978) Small-angle neutron scattering of selectively deuterated cellulose. Macromolecules 11:213–217. doi:10.1021/ma60061a039
Guinier A, Fournet G, Walker CB, Yudowitch KL (1955) Small-angle scattering of X-rays. Wiley, New York
Gupta V, Kothari V (1997) Manufactured fibre technology. Springer, The Netherlands
Heikens D (1959) A quantitative investigation on the X-ray small angle scattering of cellulose fibers. Part I. The concept of scattering power and a method for its determination in electron units. J Polym Sci 35:139–143. doi:10.1002/pol.1959.1203512811
Jellinek M, Soloman E, Fankuchen I (1946) Measurement and analysis of small-angle X-ray scattering. Ind Eng Chem Anal 18:172–175. doi:10.1021/i560151a005
Jiang G, Huang W, Li L, Wang X, Pang F, Zhang Y, Wang H (2012a) Structure and properties of regenerated cellulose fibers from different technology processes. Carbohydr Polym 87:2012–2018. doi:10.1016/j.carbpol.2011.10.022
Jiang G, Yuan Y, Wang B, Yin X, Mukuze K, Huang W, Zhang Y, Wang H (2012b) Analysis of regenerated cellulose fibers with ionic liquids as a solvent as spinning speed is increased. Cellulose 19:1075–1083. doi:10.1007/s10570-012-9716-2
Kaburagi M, Bin Y, Zhu D, Xu C, Matsuo M (2003) Small angle X-ray scattering from voids within fibers during the stabilization and carbonization stages. Carbon 41:915–926. doi:10.1016/S0008-6223(02)00407-4
Langan P, Sukumar N, Nishiyama Y, Chanzy H (2005) Synchrotron X-ray structures of cellulose Iβ and regenerated cellulose II at ambient temperature and 100 K. Cellulose 12:551–562. doi:10.1007/s10570-005-9006-3
Li R et al (2010) Primarily industrialized trial of novel fibers spun from cellulose dope in NaOH/urea aqueous solution. Ind Eng Chem Res 49:11380–11384. doi:10.1021/ie101144h
Li F, Wang W, Wang X, Yu J (2014) Changes of structure and property of alkali soluble hydroxyethyl celluloses (HECs) and their regenerated films with the molar substitution. Carbohydr Polym 114:206–212. doi:10.1016/j.carbpol.2014.08.015
Liu C, Cuculo J, Smith B (1989) Coagulation studies for cellulose in the ammonia/ammonium thiocyanate (NH3/NH4SCN) direct solvent system. J Polym Sci B Polym Phys 27:2493–2511. doi:10.1002/polb.1989.090271208
Liu W, Budtova T, Navard P (2011) Influence of ZnO on the properties of dilute and semi-dilute cellulose-NaOH-water solutions. Cellulose 18:911–920. doi:10.1007/s10570-011-9552-9
Moseley WW (1960) The measurement of molecular orientation in fibers by acoustic methods. J Appl Polym Sci 3:266–276. doi:10.1002/app.1960.070030902
Moss C, Butler M, Müller M, Cameron R (2002) Microfocus small-angle X-ray scattering investigation of the skin–core microstructure of lyocell cellulose fibers. J Appl Polym Sci 83:2799–2816. doi:10.1002/app.10256
Philipp B (1993) Organic solvents for cellulose as a biodegradable polymer and their applicability for cellulose spinning and derivatization. J Macromol Sci Part A 30:703–714. doi:10.1080/10601329308021256
Ran S, Zong X, Fang D, Hsiao BS, Chu B, Phillips RA (2001) Structural and morphological studies of isotactic polypropylene fibers during heat/draw deformation by in situ synchrotron SAXS/WAXD. Macromolecules 34:2569–2578. doi:10.1021/ma0016477
Rosenau T, Potthast A, Sixta H, Kosma P (2001) The chemistry of side reactions and byproduct formation in the system NMMO/cellulose (Lyocell process). Prog Polym Sci 26:1763–1837. doi:10.1016/S0079-6700(01)00023-5
Roy C, Budtova T, Navard P (2003) Rheological properties and gelation of aqueous cellulose-NaOH solutions. Biomacromolecules 4:259–264. doi:10.1021/bm020100s
Ruan D, Zhang L, Lue A, Zhou J, Chen H, Chen X, Chu B, Kondo T (2006) A rapid process for producing cellulose multifilament fibers from a NaOH/thiourea solvent system. Macromol Rapid Commun 27:1495–1500. doi:10.1002/marc.200600232
Ruan D, Lue A, Zhang L (2008) Gelation behaviors of cellulose solution dissolved in aqueous NaOH/thiourea at low temperature. Polymer 49:1027–1036. doi:10.1016/j.polymer.2007.12.044
Ruland W (1969) Small-angle scattering studies on carbonized cellulose fibers. J Polym Sci Polym Symp 1:143–151. doi:10.1002/polc.5070280113
Schurz J, Lenz J, Wrentschur E (1995) Inner surface and void system of regenerated cellulose fibers. Die Angewandte Makromolekulare Chemie 229:175–184. doi:10.1002/apmc.1995.052290112
Statton W (1956) Crystallite regularity and void content in cellulose fibers as shown by small-angle x-ray scattering. J Polym Sci 22:385–397. doi:10.1002/pol.1956.1202210204
Um I, Ki C, Kweon H, Lee K, Ihm D, Park Y (2004a) Wet spinning of silk polymer: II. Effect of drawing on the structural characteristics and properties of filament. Int J Biol Macromol 34:107–119. doi:10.1016/j.ijbiomac.2004.03.011
Um I, Kweon H, Lee K, Ihm D, Lee J, Park Y (2004b) Wet spinning of silk polymer: I. effect of coagulation conditions on the morphological feature of filament. Int J Biol Macromol 34:89–105. doi:10.1016/j.ijbiomac.2004.03.007
Van de Witte P, Dijkstra P, Van den Berg J, Feijen J (1996) Phase separation processes in polymer solutions in relation to membrane formation. J Membr Sci 117:1–31. doi:10.1016/0376-7388(96)00088-9
Walczak ZK (2002) Processes of fiber formation. Elsevier, United Kingdom
Wang W, Zhang P, Zhang S, Li F, Yu J, Lin J (2013) Structure and properties of novel regenerated cellulose fibers prepared in NaOH complex solution. Carbohydr Polym 98:1031–1038. doi:10.1016/j.carbpol.2013.06.076
Weng L, Zhang L, Ruan D, Shi L, Xu J (2004) Thermal gelation of cellulose in a NaOH/thiourea aqueous solution. Langmuir 20:2086–2093. doi:10.1021/la035995o
Woodings C (2001) Regenerated cellulose fibres, vol 18. Woodhead Publishing, Cambridge
Yamane C, Mori M, Saito M, Okajima K (1996) Structures and mechanical properties of cellulose filament spun from cellulose/aqueous NaOH solution system. Polym J 28:1039–1047. doi:10.1295/polymj.28.1039
Zeugolis D, Paul G, Attenburrow G (2009) Crosslinking of extruded collagen fibers—a biomimetic three-dimensional scaffold for tissue engineering applications. J Biomed Mater Res A 89:895–908. doi:10.1002/jbm.a.32031
Zhang L, Ruan D, Gao S (2002) Dissolution and regeneration of cellulose in NaOH/thiourea aqueous solution. J Polym Sci B Polym Phys 40:1521–1529. doi:10.1002/polb.10215
Zhang L, Mao Y, Zhou J, Cai J (2005) Effects of coagulation conditions on the properties of regenerated cellulose films prepared in NaOH/urea aqueous solution. Ind Eng Chem Res 44:522–529. doi:10.1021/ie0491802
Zhang S, Li F, Yu J (2010a) Structure and properties of novel cellulose fibres produced from NaOH/PEG-treated cotton linters. Iran Polym J 19:949–957
Zhang S, Li F, Yu J, Hsieh Y (2010b) Dissolution behaviour and solubility of cellulose in NaOH complex solution. Carbohydr Polym 81:668–674. doi:10.1016/j.carbpol.2010.03.029
Acknowledgments
This work has been financially supported by the Fundamental Research Funds for the Central Universities, WAXD and SAXS experiments were performed at 16B1 Beamline station in Shanghai Synchrotron Radiation Facility (SSRF). Authors are grateful to Suzanne Jacomet (CEMEF, Mines ParisTech) for help in SEM observations.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Wang, W., Li, F., Yu, J. et al. Structure and properties of novel cellulose-based fibers spun from aqueous NaOH solvent under various drawing conditions. Cellulose 22, 1333–1345 (2015). https://doi.org/10.1007/s10570-015-0544-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-015-0544-z