Thermal and Mechanical Properties of Flame Retardant ABS Nanocomposites Containing Organo-Modified Layered Double Hydoxide

유기변성 LDH를 사용한 난연 ABS 나노복합재료의 열적 및 기계적 물성

  • Kim, Seog-Jun (Department of Nano & Chemical Engineering, Kunsan National University)
  • 김석준 (군산대 공대 신소재.나노화학공학부 나노화학공학)
  • Published : 2008.12.31


ZnAl-LDH(layered double hydroxide) modified with oleic acid(SO-ZnAl LDH) was synthesized and added to the flame retardant ABS compounds containing brominated epoxy resin(BER) and antimony trioxide(${Sb_2}{O_3}$). Flame retardant ABS compounds were manufactured by using a twin-screw co-rotating extruder and subsequently injection molded into several specimen for flame retardancy and mechanical properties. The XRD patterns of ABS nanocomposites showed no peaks. The thermal stability of ABS nanocomposites was enhanced by the addition of SO-ZnAl LDH as shown in TGA results. However, these nanocomposites showed no rating in the UL 94 vertical test at 1.6 mm thickness. Only ABS nanocomposites with additional BER more than 1.5 wt% showed UL 94 V0 rating. Notched Izod impact strength, tensile modulus, and elongation at break of flame retardant ABS nanocomposites increased with the proportion of So-ZnAl LDH whereas their melt index decreased.


  1. L. A. Utracki, M. Sepehr, and E. Boccaleri, "Synthetic, Layered Nanoparticles for Polymeric Nanocomposites", Polymers for Advanced Technologies, 18, 1 (2007)
  2. A. B. Morgan, "Flame Retarded Polymer Layered Silicate Nanocomposites: A Review of Commercial and Open Literature Systems", Polymers for Advanced Technologies, 17, 206 (2006)
  3. J. Njuguna and K. Pielochowski, "Polymer Nanocomposites for Aerospace Applications: Fabrication", Advanced Engineering Materials, 6, 193 (2004)
  4. S. S. Ray and M. Okamoto, "Polymer/layered Silicate Nanocomposites: A Review from Preparation to Processing", Prog. Polym. Sci., 28, 1539 (2003)
  5. J. Zhang, F. Zhang, L. Ren, D. G. Evans, and X. Duan, "Synthesis of Layered Double Hydroxide Anionic Clays by Carboxylate Anions", Materials Chemistry and Physics, 85, 207 (2004)
  6. K-H. Koh, T-T. Lim, and Z. Dong, "Application of Layered Double Hydroxides for Removal of Oxyanions: A Review", Water Research, 42, 1343 (2008)
  7. S. Nandal and S. Mayadevi, "Adsorption of Fluoride Ions by Zn-Al Layered Double Hydroxides", Applied Clay Science, 40, 54 (2008)
  8. C-H. Chan, J-K. Chen, and F-C. Chang, "Specific DNA Extraction through Fluid Channels with Immobilization of Layered Double Hydroxides on Polycarbonate Surface", Sensors and Actuators B, 133, 327 (2008)
  9. S. Y. Kwak, Y. J. Jeong, J. S. Park, and J. H. Choy, "Bio-LDH nanohybrid for Gene Theraphy", Solid State Ionics, 151, 229 (2002)
  10. V. Ambrogi, G. FArdella, G. Grandolini, and L. Perioli, "Intercalation Compounds of Hydrotalcitelike Anionic Clays eith Antiflammatory Agents-I. Intercalation and In Vitro Release of Ibuprofin", International Journal of Pharmaceutics, 220, 23 (2001)
  11. P. Liu, H. Wang, Z. Feng, P. Ying, and C. Li, "Direct Immobilization of Self-assembled Polyoxymetalate Catalyst in Layered Double Hydroxide for Heterogeneous Epoxidation of Olefins", Journal of Catalysis, 256, 345 (2008)
  12. M. Veronica, B. Graciela, A. Norma, and L. Miguel, "Ethanol Steam Forming Using Ni(II)- Al(III) Layered Double Hydroxides Layered Double Hydroxide as Catalyst Precursor: Kinetic Study", Chemical Engineering Journal, 138, 602 (2008)
  13. Y-J. Lin, D-Q. Li, D. G. Evans, and X. Duan, "Modulating Effect of Mg-Al-$CO_3$ Layered Double Hydroxides on The Thermal Stability of PVC Resin", Polymer Degradation and Stability, 88, 286 (2005)
  14. Z. P. Xu, S. K. Saha, P. S. Braterman, and N. D'Souza, "The Effect of Zn, Al Layered Double Hydroxide on Thermal Decomposition of Poly(vinyl chloride)", Polymer Degradation and Stability, 91, 3237 (2006)
  15. L. Zhang, Y. Lin, Z. Tuo, D. G. Evans, and D. Li, "Synthesis and UV Absorption Properties of 5-Sulfosalicylate-Intercalated Zn-Al Layered Double Hydroxide", Journal of Solid State Chemistry, 180, 1230 (2007)
  16. L. Perioli, V. Ambrogi, C. Rossi, L. LAtterini, M. Nocchetti, and U. Costantino, "Use of Anionic Clays for Photoprotection and Sunscreen Photostability: Hydrotalcites and Phenylbenzimidazole Sulfonic Acid", Journal of Physics and Chemistry of Solids, 67, 1079 (2006)
  17. M. Zhang, P. Ding, L. Du, and B. Qu, "Structural Characterization and Related Properties of EVA/ ZnAl-LDH Nanocomposites Prepared by Melt and Solution Intercalation", Materials Chemistry and Physics, 109, 206 (2008)
  18. T. Kulia, H. Acharya, S. K. Srivastava, and A. K. Bhowmick, "Effects of Vinyl Acetate Content on the Mechanical and Thermal Properties of Ethylene Vinyl Acetate/MgAl Layered Double Hydroxide Nanocomposites", Journal of Applied Polymer Science, 108, 1329 (2008)
  19. T. Kulia, H. Acharya, S. K. Srivastava, and A. K. Bhowmick, "Synthesis and Characterization of Ethylene Vinyl Acetate/Mg-Al Layered Double Hydroxide Nanocomposites", Journal of Applied Polymer Science, 104, 1845 (2007).
  20. W. D. Lee and S. S. Im. "Thermomechanical Properties and Crystallization Behavior of Layered Double Hydroxide/Poly(ethylene terephthalate) Nanocomposites Prepared by In-situ Polymerization", Journal of Polymer Science: Part B: Polymer Physics, 45, 28 (2007)
  21. C-H. Tseng, H-B. Hsueh, and C-Y. Chen, "Effect of reactive Layered Double Hydroxides on the Thermal and Mechanical Properties of LDH/Epoxy Nanocomposites", Composites Science and Technology, 67, 2350 (2007)
  22. R. Pucciariello, L. Tammaro, V. Villani, and V. Vittoria, "New Nanohybrids of Poly($\varepsilon$-caprolactone) and a Modified Mg/Al Hydrotalcite: Mechanical and Thermal Properties", Journal of Polymer Science: Part B: Polymer Physics, 45, 945 (2007)
  23. W. D. Lee, S. S. Im, H-M. Lim, and K-J. Kim, "Preparation and Properties of Layered Double Hydroxide/Poly(ethylene terephthalate) Nanocompsoites by Direct Melt Compounding", Polymer, 47, 1364 (2006)
  24. W. Chen and B. Qu, "Enhanced Thermal and Mechanical Properties of Poly(methyl acrylate)/ZnAl Layered Double Hydroxide Nanocompsites Formed by In-situ Polymerization", Polymer Degradation and Stability, 90, 162 (2006)
  25. S. Martinez-Gallegos, M. Herrero, and V. Rives, "In Situ Microwave-Assisted Polymerization of Polyethylene Terephthalate in Layered Double Hydroxides", Journal of Applied Polymer Science, 109, 1388 (2008)
  26. T-M. Wu, S-F. Hsu, Y-F. Shih, and C-S. Liao, "Thermal Degradation Kinetics of Biodegradable Poly(3-hydroxybutyrate)/Layered Double Hydroxide Nanocomposite", Journal of Polymer Science: Part B: Polymer Physics, 46, 1207 (2008)
  27. T-Y. Tsai, S-W. Lu, and F-S. Li, "Preparation and Characterization of Epoxy/Layered Double Hydroxide Nanocomposites", Journal of Physics and Chemistry of Solids, 69, 1386 (2008)
  28. F-A. He and L-M. Zhang, "New Polyethylene Nanocomposites Prepared by In-Situ Polymerization Method Using Nickel a-Diimine Catalyst Supported on Organo-Modified ZnAl Layered Double Hydroxide", Composite Science and Technology, 67, 3226 (2007)
  29. P. Ding and B. Qu, "Synthesis of Exfoliated PP/LDH Nanocomposites via Melt-Intercalation: Structure, Thermal Properties, and Photo-Oxidative Behavior in Comparison with PP/MMT Nanocomposites", Polymer Engineering and Science, 46, 1153 (2006)
  30. L-C. Du and B-J. Qu, "Preparation of LLDPE/ MgAl-LDH Exfoliation Nanocomposites with Enhanced Thermal Properties by Melt Intercalation", Chinese Journal of Chemistry, 24, 1342 (2006)
  31. L. Qiu, W. Chen, and B. Qu, "Morphology and Thermal Stabilization Mechanism of LLDPE/MMT and LLDPE/LDH Nanocomposites", Polymer, 47, 922 (2006)
  32. P. Ding and B. Qu, "Structure, Thermal Stability, and Photocrosslinking Characterization of HDPE/ LDH Nanocomposites Synthesized by Melt-Intercalation", Journal of Polymer Science: Part B: Polymer Physics, 44, 3165 (2006)
  33. P. Ding and B. Qu, "Synthesis and Characterization of Exfoliated Polystyrene/ZnAl Layered Double Hydroxide Nanocomposite via Emulsion Polymerization", Journal of Colloid and Interface Science, 291, 13 (2005)
  34. W. Chen and B. Qu, "In Sity Synthesis of Poly(methyl methacrylate)/MgAl Layered Double Hydroxide with High Transparency and Enhanced Thermal Properties", Solid State Communications, 130, 259 (2004)
  35. M. Zammarano, S. Bellayer, J. W. Gilman, M. Franceschi, F. L. Beyer, R. H. Harris, and S. Meriani, "Delamination of Organo-Modified Layered Double Hydroxides in Polyamide 6 by Melt Processing", Polymer, 47, 652 (2006)
  36. N. S. Kottegodo and W. Jones, "Preparation and Characterisation of Li-Al-glycine Layered Double Hydroxides (LDHs)-Polymer Nanocomposites", Macromol. Symp., 222, 65 (2005)
  37. B. Ramaraj and K. R. Yoon, "Thermal and Physical Properties of Ethylene-vinyl Acetate Copolymer and Layered Double Hydroxide Composite", Journal of Polymer Science, 108, 4090 (2008)
  38. C-M. Jiao, Z-Z. Wang, X-L. Chen, and Y. Hu, "Synthesis of a Magenesium/Aluminum/Iron Layered Double Hydroxide and Its Flammability Characteristics in Halogen-Free, Flame-Retardant Ethylene/ Vinyl Acetate Copolymer Composites", Journal of Polymer Science, 107, 2626 (2008)
  39. L. Du, B. Qu, and M. Zhang, "Thermal Properties and Combustion Characterization of Nylon 6/MgAl- LDH Nanocomposites via Organic Modification and Melt Intercalation", Polymer Degradation and Stability, 92, 497 (2007)
  40. F. R. Costa, U. Wagenknecht, and G. Heinrich, "LDPE/Mg-Al Layered Double Hydroxide Nanocomposite: Thermal and Flammability Properties", Polymer Degradation and Stability, 92, 1813 (2007)
  41. U. Costantino, A. Gallipoli, M. Nocchetti, G. Camino, F. Bellucci, and A, Frache, "New Nanocomposites Constituted of Polyethylene and Organically Modified ZnAl-hydrotalcites", Polymer Degradation and Stability, 90, 586 (2005)
  42. M. Zammarano, M. Franceschi, S. Bellayer, J. W. Gilman, and S. Meriani, "Praparation and Flame Resistance Properties of Revolutionary Self-Extinguishing Epoxy Nanocompsoites Based on Layered Double Hydroxides", Polymer, 46, 9314 (2005)
  43. M. C. Costache, M. J. Heidecker, E. Manias, G. Camino, A. Frache, G. Beyer, R. K. Gupta, and C. A. Wilkie, "The Influence of Carbon Nanotubes, Organically Modified Montmorillonites and Layered Double Hydroxides on Thermal Degradation and Fire Retardancy of Polyethylene, Ethylene-Vinyl Acetate Copolymer and Polystyrene", Polymer, 48, 6352 (2007)
  44. C-X. Chao, Y. Liu, D-Y. Wang, D-L. Wang, and Y-Z. Wang, "Synergistic Effect of Ammonium Polyphosphate and Layered Double Hydroxide on Flame Retardant Properties of Poly(vinyl alcohol)", Polymer Degradation and Stability, 93, 1323 (2008)
  45. G. Zhang, P. Ding, M. Zhang, and B. Qu, "Synergistic Effects of Layered Double Hydoxide with Hyperfine Magnesium Hydroxide in Halogen- Free Flame Retardant EVA/HFMH/LDH Nanocomposites", Polymer Degradation and Stability, 92, 1715 (2007)
  46. L. Ye, P. Ding, M. Zhang, and B. Qu, "Synergistic Effects of Exfoliated LDH with Some Halogen-Free Flame Retardants in LDPE/EVA/HFMH/LDH Nanocomposites", Journal of Applied Polymer Science, 107, 3694 (2008)
  47. Z. Wang, E. Han, and W. Ke, "Influence of Nano-LDHs on Char Formation and Fire-Resistant Properties of Flame-Retardant Coating", Progress in Organic Coatings, 53, 29 (2005)
  48. L. Qiu, W. Chen, and B. Qu, "Structural Characterization and Thermal Properties of Exfoliated Polystyrene/ ZnAl Layered Double Hydroxide Nanocomposites Prepared by Solution Intercalation", Polymer Degradation and Stability, 87, 433 (2005)
  49. H. A. Stretz, D. R. Paul, and P. E. Cassidy, "Poly(styrene-co-acrylonitrile)/Montmorillonite Organoclay Mixtures: A Model System for ABS Nanocomposites", Polymer, 46, 3818 (2005).
  50. H. Ma, Z. Fang, and L. Tong, "Preferential Melt Intercalation of Clay in ABS/Brominated Epoxy Resin-Antimony Oxide(BER-AO) Nanocomposites and Its Synergistic Effect on Thermal degradation and Combustion Behavior", Polymer Degradation and Stability, 91, 1972 (2006)
  51. Seogjun Kim, "Phyllite as a New Flame Retardant Synergist for ABS Resin Containing Bromine Flame Retardant", Elastomer, 41, 172 (2006)
  52. F. R. Costa, M. Abdel-Goad, U. Wagenknecht, and G. Heinrich, "Nanocomposites Based on Polyethylene and Mg-Al Layered Double Hydroxide. I. Synthesis and Characterization", Polymer, 46, 4447 (2005)
  53. F. R. Costa, B. K. Satapathy, U. Wagenknecht, R. Weidisch, and G. Heinrich, "Morphology and Fracture Behavior of Polyethylene/Mg-Al Layered Double Hydroxide", European Polymer Journal, 42, 2140 (2006)