Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part II: Stabilization reaction kinetics and effect of gas environment

Abstract Gel-spun polyacrylonitrile (PAN) and carbon nanotube (CNT) composite fibers have been stabilized using various processing conditions to study the kinetics of stabilization reactions. Differential scanning calorimetry, infrared spectroscopy, wide angle X-ray diffraction and thermo-gravimetric analysis studies suggest that individual stabilization reactions can be separated at different stabilization stages when inert and oxidative environments are used in sequence. Among various stabilization reactions, it was found that the cross-linking has the highest activation energy, followed by cyclization and oxidation. The oxidation preferentially occurs with the cyclized structure and the shrinkage during stabilization is affected by the gaseous environment. The addition of CNTs reduces both entropic and reaction shrinkages, and improves the maximum tension that a fiber can bear during stabilization in both inert and oxidative environments.

[1]  W. Watt,et al.  Mechanism of oxidisation of polyacrylonitrile fibres , 1975, Nature.

[2]  M. Coleman,et al.  Fourier transform ir studies of the degradation of polyacrylonitrile copolymers—I: Introduction and comparative rates of the degradation of three copolymers below 200°c and under reduced pressure , 1981 .

[3]  Erich Fitzer,et al.  The influence of oxygen on the chemical reactions during stabilization of pan as carbon fiber precursor , 1975 .

[4]  Erich Fitzer,et al.  Optimization of stabilization and carbonization treatment of PAN fibres and structural characterization of the resulting carbon fibres , 1986 .

[5]  R. Mathur,et al.  IR studies of PAN fibres thermally stabilized at elevated temperatures , 1994 .

[6]  P. Budd,et al.  Thermal stabilization of polyacrylonitrile fibres , 1999 .

[7]  Satish Kumar,et al.  Carbon nanotube reinforced small diameter polyacrylonitrile based carbon fiber , 2009 .

[8]  Chengguo Wang,et al.  Microstructural evolution during thermal stabilization of PAN fibers , 2007 .

[9]  H. E. Kissinger.  Reaction Kinetics in Differential Thermal Analysis , 1957 .

[10]  J. Mooney,et al.  Infrared and NMR spectroscopic studies of the thermal degradation of polyacrylonitrile , 1985 .

[11]  Satish Kumar,et al.  The processing, properties, and structure of carbon fibers , 2005 .

[12]  W. Koros,et al.  Effect of structure on the temperature dependence of gas transport and sorption in a series of polycarbonates , 1994 .

[13]  T. Ozawa,et al.  Kinetic analysis of derivative curves in thermal analysis , 1970 .

[14]  Rakesh B. Mathur,et al.  A new approach to thermal stabilisation of PAN fibres , 1992 .

[15]  C. R. Nair,et al.  Differential scanning calorimetric study on the Claisen rearrangement and thermal polymerisation of diallyl ether of bisphenols , 2000 .

[16]  B. C. Ennis,et al.  Thermal Analysis of Polyacrylonitrile. Part I. The Melting of Polyacrylonitrile , 1970 .

[17]  O. P. Bahl,et al.  Shrinkage behaviour of polyacrylonitrile during thermal treatment , 1975 .

[18]  Q. Ouyang,et al.  Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile , 2008 .

[19]  C. R. Nair,et al.  Viscoelastic properties of polyacrylonitrile terpolymers during thermo‐oxidative stabilization (cyclization) , 2008 .

[20]  Han Gi Chae,et al.  Stabilization and carbonization of gel spun polyacrylonitrile/single wall carbon nanotube composite fibers , 2007 .

[21]  Ian R. Harrison,et al.  New aspects in the oxidative stabilization of PAN-based carbon fibers: II , 1996 .

[22]  Han Gi Chae,et al.  Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization , 2011 .

[23]  Z. Bashir.  A critical review of the stabilisation of polyacrylonitrile , 1991 .

[24]  A. Oberlin,et al.  Stabilization and carbonization of pan-based carbon fibers as related to mechanical properties , 1991 .

[25]  W. Koros,et al.  Temperature dependence of gas sorption and transport properties in polymers: measurement and applications , 1992 .

[26]  J. Schurz.  Discoloration effects in acrylonitrile polymers , 1958 .

[27]  Garth L. Wilkes,et al.  Dynamic oscillatory shear properties of potentially melt processable high acrylonitrile terpolymers , 2002 .

[28]  Dan D. Edie,et al.  Model of stabilization for pan-based carbon fiber precursor bundles , 1992 .

[29]  Ahmad Fauzi Ismail,et al.  A review of heat treatment on polyacrylonitrile fiber , 2007 .