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Modification of isotropic coal-tar pitch by acid treatments for carbon fiber melt-spinning

  • Yoo, Mi Jung (Department of Chemical Engineering, Myongji University) ;
  • Ko, Hyo Jun (Department of Materials Science and Engineering, Myongji University) ;
  • Lim, Yun-Soo (Department of Materials Science and Engineering, Myongji University) ;
  • Kim, Myung-Soo (Department of Chemical Engineering, Myongji University)
  • Received : 2014.07.10
  • Accepted : 2014.09.23
  • Published : 2014.10.31

Abstract

In this work, thermal treatment accompanied with different acid treatments was applied to a commercial coal tar pitch (CTP) to obtain a spinnable precursor pitch for carbon fiber. In the case of thermal treatment only, a relatively high reaction temperature of between $380^{\circ}C$ and $400^{\circ}C$ was required to obtain a softening point (SP) range of $220^{\circ}C-260^{\circ}C$ and many meso-phase particles were created during the application of high reaction temperature. When nitric acid or sulfuric acid treatment was conducted before the thermal treatment, the precursor pitch with a proper SP range could be obtained at reaction temperatures of $280^{\circ}C-300^{\circ}C$, which were about $100^{\circ}C$ lower than those for the case of thermal treatment only. With the acid treatments, the yield and SP of the precursor pitch increased dramatically and the formation of meso-phase was suppressed due to the lower reaction temperatures. Since the precursor pitches with acid and thermal treatment were not spinnable due to the inhomogeneity of properties such as molecular weight distribution and viscosity, the CTP was mixed with ethanol before the consecutive nitric acid and thermal treatments. The precursor pitches with ethanol, nitric acid, and thermal treatments were easily spinnable, and their spinning and carbon fiber properties were compared to those of air blowing and thermal treated CTP.

Keywords

References

  1. Wazir AH, Kakakhel L. Preparation and characterization of pitchbased carbon fibers. New Carbon Mater, 24, 83 (2009). http://dx.doi.org/10.1016/S1872-5805(08)60039-6.
  2. Yu B, Wang C, Chen M, Zheng J, Qi J. Two-step chemical conversion of coal tar pitch to isotropic spinnable pitch. Fuel Process Technol, 104, 155 (2012). http://dx.doi.org/10.1016/j.fuproc.2012.05.007.
  3. Yoon SH, Korai Y, Mochida I. Assessment and optimization of the stabilization process of mesophase pitch fibers by thermal analyses. Carbon, 32, 281 (1994). http://dx.doi.org/10.1016/0008-6223(94)90191-0.
  4. Menendez R, Gray EM, Marsh H, Pysz RW, Heintz EA. The influence of primary quinoline insolubles on the development of secondary quinoline insolubles in coal tar pitches. Carbon, 29, 107 (1991). http://dx.doi.org/10.1016/0008-6223(91)90101-N.
  5. Petrova B, Budinova T, Petrov N, Yardim MF, Ekinci E, Razvigorova M. Effect of different oxidation treatments on the chemical structure and properties of commercial coal tar pitch. Carbon, 43, 261 (2005). http://dx.doi.org/10.1016/j.carbon.2004.09.006.
  6. Blanco C, Santamariia R, Bermejo J, Menendez R. A comparative study of air-blown and thermally treated coal-tar pitches. Carbon, 38, 517 (2000). http://dx.doi.org/10.1016/S0008-6223(99)00131-1.
  7. Zeng SM, Maeda T, Tokumitsu K, Mondori J, Mochida I. Preparation of isotropic pitch precursors for general purpose carbon fibers (GPCF) by air blowing: II. Air blowing of coal tar, hydrogenated coal tar, and petroleum pitches. Carbon, 31, 413 (1993). http://dx.doi.org/10.1016/0008-6223(93)90128-W.
  8. Ko HJ, Park CU, Cho HH, Yoo MJ, Kim MS, Lim YS. Preparation of coal tar pitch as carbon fibers precursor form coal tar. Korean J Mater Res, 23, 276 (2013). http://dx.doi.org/10.3740/MRSK.2013.23.5.276.
  9. Dominguez A, Blanco C, Santamaria R, Granda M, Blanco CG, Menendez R. Monitoring coal-tar pitch composition changes during air-blowing by gas chromatography. J Chromatogr A, 1026, 231 (2004). https://doi.org/10.1016/j.chroma.2003.11.067
  10. Lewis IC. Thermal polymerization of aromatic hydrocarbons. Carbon, 18, 191 (1980). http://dx.doi.org/10.1016/0008-6223(80)90060-3.
  11. Cheng X, Zha Q, Li X, Yang X. Modified characteristics of mesophase pitch prepared from coal tar pitch by adding waste polystyrene. Fuel Process Technol, 89, 1436 (2008). http://dx.doi.org/10.1016/j.fuproc.2008.07.003.
  12. Li T, Liu X, Wang C, Wang H. Structural characteristics of mesophase spheres prepared from coal tar pitch modified by phenolic resin. Chin J Chem Eng, 14, 660 (2006). http://dx.doi.org/10.1016/S1004-9541(06)60131-6.
  13. Lin Q, Li T, Zheng C, Zhao Y, Song S. Carbonization behavior of coal-tar pitch modified with divinylbenzene and optical texture of resultant semi-cokes. J Anal Appl Pyrolysis, 71, 817 (2004). http://dx.doi.org/10.1016/j.jaap.2003.10.009.
  14. Machnikowski J, Kaczmarska H, Gerus-Piasecka I, Diiez MA, Alvarez R, Garcia R. Structural modification of coal-tar pitch fractions during mild oxidation: relevance to carbonization behavior. Carbon, 40, 1937 (2002). http://dx.doi.org/10.1016/S0008-6223(02)00029-5.
  15. Panaitescu C, Predeanu G. Microstructural characteristics of toluene and quinoline-insolubles from coal-tar pitch and their cokes. Int J Coal Geol, 71, 448 (2007). http://dx.doi.org/10.1016/j.coal.2006.11.003.
  16. Granda M, Casal E, Bermejo J, Menendez R. The influence of primary QI on the oxidation behaviour of pitch-based C/C composites. Carbon, 39, 483 (2001). http://dx.doi.org/10.1016/S0008-6223(01)00006-9.
  17. Marsh H, Latham CS, Gray EM. The structure and behaviour of QI material in pitch. Carbon, 23, 555 (1985). http://dx.doi.org/10.1016/0008-6223(85)90092-2.
  18. Guillen MD, Iglesias MJ, Dominguez A, Blanco CG. Fourier transform infrared study of coal tar pitches. Fuel, 74, 1595 (1995). http://dx.doi.org/10.1016/0016-2361(95)00139-V.
  19. Akezuma M, Okuzawa K, Esumi K, Meguro K, Honda H. Physicochemical properties of quinoline-soluble and quinolineinsoluble mesophases. Carbon, 25, 517 (1987). http://dx.doi.org/10.1016/0008-6223(87)90192-8.
  20. Otani S. Mechanism of the carbonization of MP carbon fiber at the low temperature range. Carbon, 5, 219 (1967). http://dx.doi.org/10.1016/0008-6223(67)90003-6.
  21. Gray RJ, Krupinski KC. Pitch production: supply, coking, optical microscopy and application. In: Marsh H, Heintz EA, Rodriguez- Reinoso F, eds. Introduction to Carbon Technologies, Universidad de Alicante, Alicante, Spain, 329 (1997).

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