Understanding the decomposition and fire performance processes in phosphorus and nanomodified high performance epoxy resins and composites

Abstract This paper investigates the decomposition mechanism and fire performance of high performance epoxy amine resins and laminate systems, using thermogravimetry (TGA), energy dispersive spectroscopy (EDS), cone calorimetry and Fourier transform infra-red spectroscopy (FTIR). Two different, commercially-important epoxy resins, tetraglycidyl methylene dianiline (TGDDM) and diglycidyl ether of bisphenol A (DGEBA) have been cured separately with diethyl toluene diamine (DETDA) and bis(4-aminophenoxy)phenyl phosphonate (BAPP) and their relative combustion performance has been examined and discussed in terms of their decomposition profile. This paper highlights the close relationship between char yields (TGA and cone calorimetry) and thermal decomposition with the peak heat release rate, highlighting the role of the condensed phase in minimizing combustion. The lower decomposition temperatures and higher char yields of the tetra-functional epoxy (TGDDM) are therefore seen to provide superior fire performance compared to the bi-functional (DGEBA) epoxy. FTIR shows that the decomposition occurs through initial cleavage of P–O–C bonds in preference to other covalent bonds, which allows dehydration and subsequent charring and/or chain scission. TGA demonstrated that the laminated systems did not show a significant difference to the neat resin systems, with respect to initial decomposition of the network and the thermal stability of the char layer. Nanoclay addition was also found to have little effect upon degradation and fire performance.

[1]  I. Hamerton,et al.  RECENT DEVELOPMENTS IN THE CHEMISTRY OF HALOGEN-FREE FLAME RETARDANT POLYMERS , 2002 .

[2]  C. A. Wilkie,et al.  Synergy between conventional phosphorus fire retardants and organically-modified clays can lead to fire retardancy of styrenics , 2003 .

[3]  S. Bourbigot,et al.  Comprehensive study of the oxidative degradation of an epoxy resin using the degradation front model , 1996 .

[4]  J. Troitzsch Methods for the fire protection of plastics and coatings by flame retardant and intumescent systems , 1983 .

[5]  Yi-bing Cheng,et al.  Layered Silicate Nanocomposites Based on Various High-Functionality Epoxy Resins: The Influence of Cure Temperature on Morphology, Mechanical Properties, and Free Volume , 2003 .

[6]  Hsu-Chiang Kuan,et al.  Thermo-oxidative degradation of novel epoxy containing silicon and phosphorous nanocomposites , 2003 .

[7]  Ying‐Ling Liu,et al.  Preparation of silicon-/phosphorous-containing epoxy resins from the fusion process to bring a synergistic effect on improving the resins' thermal stability and flame retardancy , 2003 .

[8]  G. Camino,et al.  Halogen-free flame retardant radiation curable coatings , 2002 .

[9]  T. R. Hull,et al.  Cone calorimetry studies of polymer systems flame retarded by chemically bonded phosphorus , 2005 .

[10]  Walter J. Murphy,et al.  ADVANCES IN CHEMISTRY SERIES: Numbers 15 and 17 Demonstrate Rapidly Crowing Interest in Documentation; International Conference To Be Held in 1958 , 1956 .

[11]  Takashi Kashiwagi,et al.  PA-6 clay nanocomposite hybrid as char forming agent in intumescent formulations , 2000 .

[12]  Ying‐Ling Liu,et al.  Phosphorus-containing epoxy for flame retardance : IV. Kinetics and mechanism of thermal degradation , 1997 .

[13]  J. Verdu,et al.  Thermogravimetric study of amine cross-linked epoxies , 1984 .

[14]  S. Lomakin,et al.  New aspects of ecologically friendly polymer flame retardant systems , 1996 .

[15]  Chun-Shan Wang,et al.  Novel phosphorus-containing epoxy resins Part I. Synthesis and properties , 2001 .

[16]  Richard E. Lyon,et al.  Heat release kinetics , 2000 .

[17]  R. Delobel,et al.  Thermal oxidative degradation of an epoxy resin , 1993 .

[18]  J. Brosse,et al.  Chemical modification of epoxy resins by dialkyl(or aryl) phosphates: Evaluation of fire behavior and thermal stability , 1996 .

[19]  G. Camino,et al.  Mechanistic study of thermal behaviour and combustion performance of epoxy resins. II. TGDDM/DDS system , 1995 .

[20]  C. Lin,et al.  Synthesis and properties of phosphorus-containing advanced epoxy resins. II , 2000 .

[21]  D. Kourtides,et al.  Flame-Retardant Composition of Epoxy Resins with Phosphorus Compounds , 1984 .

[22]  G. Simon,et al.  A phosphorus‐containing diamine for flame‐retardant, high‐functionality epoxy resins. I. Synthesis, reactivity, and thermal degradation properties , 2004 .

[23]  G. Camino,et al.  Mechanistic study of thermal behaviour and combustion performance of carbon fibre-epoxy resin composites fire retarded with a phosphorus-based curing system , 1996 .

[24]  M. Shau,et al.  Synthesis, structure, and thermal properties of epoxy‐imide resin cured by phosphorylated diamine , 1995 .

[25]  Joseph G. Smith,et al.  Flame retardant aircraft epoxy resins containing phosphorus , 2005 .

[26]  Ying‐Ling Liu,et al.  Phosphorus‐containing epoxy resins for flame retardancy V: Synergistic effect of phosphorus–silicon on flame retardancy , 2000 .

[27]  Yu-Zhong Wang,et al.  Thermal oxidative degradation behaviours of flame-retardant copolyesters containing phosphorous linked pendent group/montmorillonite nanocomposites , 2005 .