Dry Jet-Wet Spinning of Cellulose/N-Methylmorpholine N-oxide Hydrate Solutions and Physical Properties of Lyocell Fibers

Abstract

In dry jet-wet spinning of a cellulose/N-methylmorpholine N-oxide hydrate solution, the effects of the hydration number n in NMMO hydrates and the concentration and molecular weight of cellulose are investigated in terms of the physical properties of the fibers. Dry jet-wet spinning of lyocell fibers is also investigated using three different set-ups; a piston type, an N² gas pressure type, and spinning equipment with an extruder. The effects of spinning conditions such as the spin draw ratio, air gap distance, and composition of the coagulation bath are investigated. The physical properties of the fibers such as birefringence, initial modulus, and tensile strength increase with a decrease in n and an increase in the air gap distance and spin draw ratio. The relationship between the physical properties and the fiber denier is newly suggested in this spinning system. The tensile fracture morphology reveals that fibers from the NMMO hydrate containing less water have more fibrils due to their higher molecular orientation. Further, the orientation structure of the cellulose becomes more noticeable with the decreased hydration levels of the solvent because it produces thicker and longer fibrils when the cellulose fibers are treated with an ultrasonic generator. The crystallite size of the cellulose depends on the composition of NMMO in the coagulation bath. The crystallite size also decreases with the increased air gap distance.

Get full access to this article

View all access options for this article.

References

Alan, S. A., Patrick, W., and Phillip, I. R., Method of Making Crimped Solvent-spun Cellulose Fiber, U.S. patent 5,591,388, 1997.

Bang, Y. H. , Wang, Y. S. , Kim, H. D. , Kim, D. L. , and Cho, H. H. , The Fibrillation and Swelling of Lyocell Fiber , J. Kor. Fiber Soc. 37, 253–258 (2000).

Bang, Y. H. , Lee, S. , Park, J. B. , and Cho, H. H. , Effect of Coagulation Conditions on Fine Structure of Regenerated Cellulosic Films Made from Cellulose/N-Methylmorpholine-N-oxide/H2O Systems , J. Appl. Polym. Sci. 73, 2681–2690 (1999).

Chanzy, H. , Paillet, M. , and Hagege, R. , Spinning of Cellulose from N-methylmorpholine N-oxide in the Presence of Additives,” Polymer 31, 400–405 (1990).

Chanzy, H. , Nawrot, S. , Peguy, A. , Smith, P. , and Chevalier, J. , Phase Behavior of the Quasiternary System N-methyl morpholine-N-oxide, Water and Cellulose , J. Polym. Sci. Polym. Phys. Ed. 20, 1909–1924 (1982).

Chanzy, H. , Noe, P. , Paillet, M. , and Smith, P. , Swelling and Dissolution of Cellulose in Amine Oxide/Water Systems , J. Appl. Polym. Sci. Appl. Polym. Symp. 37, 239–259 (1983).

Chanzy, H. , Peguy, A. , Chaunis, S. , and Monzie, P. , Oriented Cellulose Films and Fibers from a Mesophase System , J. Polym. Sci. Polym. Phys. Ed. 18, 1137–1144 (1980).

Cole, D. , and Jones, A. , Solvent-spun Fibre—A New Member of the Cellulose Fiber Family , Lenz. Ber. 69, 73–77 (1990).

Collier, J. R., Negulescu, I. I., and Collier, B. J., Process for Manufacturing Cellulosic Microfibers, U.S. patent 6,153,136, 2000.

10.

Coulsey, H. A. , and Smith, S. B. , The Formation and Structure of a New Cellulosic Fibre , Lenz. Ber. 75, 51–61 (1996).

11.

Daves, S. , All You Need to Know about Tencel , Textile Horiz. (2), 62–63 (1989).

12.

Federal Trade Commission , Lyocell—A Manufactured Fiber Composed of Precipitated Cellulose and Produced by an Organic Solvent Extrusion Process, FTC File No. P92-8401, 1992.

13.

Fischer, K. , Neues Verfahren zur maßanlytischen Bestimmung des Wassergehaltes von Flussigkeiten und festen Kopern , Angew. Chem. 48, 394–396 (1935).

14.

Jurkovic, R. Firgo, Eichinger, H. D., and Zikeli, S., Method of Producing Shaped Cellulosic Articles, U.S. patent 5,252,284, 1993.

15.

Kim, D. B. , Lee, W. S. , and Kang, H. J. , The Effects of the Thermal Degradation of Cellulose/MMNO Dope on the Physical Properties of Cellulose Fibers , Polymer Kor. 22, 770–778 (1998).

16.

Kim, D. B. , Lee, W. S. , Jo, S. M. , Lee, Y. M. , and Kim, B. C. , Physical Properties of Lyocell Fibers Spun from Different Solution-dope Phases , J. Appl. Polym. Sci. 83, 981–989 (2002).

17.

Kim, D. B. , Lee, W. S. , Jo, S. M. , Lee, Y. M. , and Kim, B. C. , Phase Transition of Cellulose Solutions in N-methylmorpholine-N-oxide Hydrates , Polymer J. 33(1), 18–26 (2001).

18.

Kim, D. B. , Lee, W. S. , Kim, B. C. , Jo, S. M. , Park, J. S. , and Lee, Y. M. , Effects of the Water Level Hydrated in NMMO on the Physical Properties of Cellulose Fiber in Dry-jet Wet Spinning , Polymer Kor. 22(2), 231–239 (1998).

19.

Kreze, T. , Stana-Kleinschek, S. S. , and Ribitsch, V. , Influence of Aqueous Medium on Mechanical Properties of Conventional and New Environmentally Friendly Regenerated Cellulose Fibers , Mater. Res. Innovat. 4, 107–114 (2001).

20.

Lee, W. S., Jo, S. M., Kang, H. J., Kim, D. B., and Park, C. S., Pelletized Pre-dope Granules of Cellulose and Tertiary Amine Oxide, Spinning Solution, of Cellulose and Process for Making Them, U.S. patent 5,584,919, 1996.

21.

Lee, W. S., Kim, B. C., Jo, S. M., Park, J. S., Lee, S. J., Park, Y. G., Lee, S. L., and Oh, Y. S., Process for Preparing a Homogenious Cellulose Solution Using N-methylmorpholine-N-oxide, U.S. patent 6,153,003, 2000.

22.

Lenz, J. , Schurz, J. , and Wrentschur, E. , Properties and Structure of Solvent-spun and Viscose-type Fibers in the Swollen State , Colloid Polym. Sci. 271, 460–468 (1993).

23.

Loubinoux, D. , and Chaunis, S. , An Experimental Approach to Spinning New Cellulose Fibers with N-methylmorpholine-N-oxide as a Solvent , Textile Res. J. 57(12), 61–65 (1987).

24.

Loubinoux, D. , and Chaunis, S. , An Experimental Approach of Spinning New Cellulose Fibers with NMMO as a Solvent of Cellulose , Lenz. Ber. 59, 105–110 (1985).

25.

Mangeng, B., Firgo, H., and Manner, J., Process for Selective Separation of Morpholine, U.S. patent 6,113,799, 2000.

26.

McCorsley, C. C. III, and Varga, J. K., Process for Making a Precursor of a Solution of Cellulose, U.S. patent 4,142,913, 1979.

27.

McCorsley, C. C. III, Shaped Cellulose Article Prepared from a Solution Containing Cellulose Dissolved in a Tertiary Amine N-oxide Solvent and a Process for Making the Article, U.S. patent 4,416,698, 1983.

28.

McCorsley C. C. III, Process for Surface Treating Cellulose Products, U.S. patent 4,261,943, 1981

29.

Mortimer, S. A. , and Peguy, A. A. , Methods for Reducing the Tendency of Lyocell Fibers to Fibrillate , J. Appl. Polym. Sci. 60, 305–316 (1996).

30.

Mortimer, S. A. , and Peguy, A. A. , A Device for On-line Measurement of Fiber Birefringence , Textile Res. J. 64(9), 544–551 (1994).

31.

Mortimer, S. A. , and Peguy, A. A. , The Influence of Air-gap Conditions on the Structure Formation of Lyocell Fibers , J. Appl. Polym. Sci. 60, 1747–1756 (1996).

32.

Navard, P. , and Haudin, J. M. , Spinning of a Cellulose Methylmorpholine Oxide Solution , Polym. Proc. Eng. 3(3), 291–301 (1985).

33.

Newbury, J. P., and Dovey, T., Manufacture of Extruded Articles, U.S. patent 6,093,355, 2000.

34.

Nicolai, M. , Nechwatal, A. , and Mieck, K. P. , Textile Crosslinking Reactions to Reduce the Fibrillation Tendency of Lyocell Fibers , Textile Res. J. 66(9), 575–580 (1996).

35.

Sellars, A., and Quigley, M. C., Monitoring Concentration of Dope in Product Manufacture, U.S. patent 5,354,524, 1994.

36.

Stall, A. D., and Turbak, A. F., Processes for Precipitating Tertiary Amine Oxide Cellulose Solutions Containing Water Soluble Polymers and Products Made Therefrom, U.S. patent 5,951,933, 1999.

37.

Taylor, J. M., Process for Reducing the Fibrillation Tendency of Solvent-spun Cellulose Fiber, U.S. patent 5,310,424, 1994.

38.

Taylor, J. M., Elongate Member Production Method, U.S. patent 5,403,530, 1995.

39.

Wykes, K. A., and Quigley, M. C., Transport of Solutions of Cellulose Through Pipes, U.S. patent 5,354,371, 1994.