Effect of dynamic crosslinking on phase morphology and mechanical properties of polyamide 6,12/ethylene vinyl acetate copolymer blends

Authors

DOI:

https://doi.org/10.18226/23185279.v3iss1p23

Abstract

The dynamic crosslinking of polyamide 6,12 and ethylene vinyl acetate (PA6,12/EVA) blends in the mixing chamber of a torque rheometer was investigated. EVA was selectively crosslinked within the PA6,12 phase through free radical reactions using dycumil peroxide. The degree of EVA crosslinking in the PA12,6/EVA materials was estimated based on the gel content (insoluble EVA fraction). The PA6,12/EVA phase morphology was investigated by scanning electron microscopy. The mechanical properties were investigated by determining the tensile strength and hardness. The half-life time (t1/2) for homolytic scission of the dcumil peroxide (DCP) was ~6s, and this time is longer than the dispersion time of the DCP in the blends. The addition of DCP resulted in increased torque values due to specific crosslinking in the EVA phase. For the pure EVA and its blends with PA6,12 the stabilized torque values increased proportionally with the amount of DCP in the system, due to a higher degree of crosslinking of the elastomeric phase. The gel content of the dynamically crosslinked blends increased with the amount of DCP incorporated until 4 phr. At 1 phr the gel content value was 2.6wt.%, while at 4 phr it was 17wt.%. For the polymer blend with 8 phr of DCP a lubricating effect contributed to reducing the gel content. The dynamically crosslinked blends, regardless of the amount of DCP added, showed a reduction in the mechanical properties, which is related to the morphological features of the system due to the low mechanical fragmentation during melt processing.

 

http://dx.doi.org/10.18226/23185279.v3iss1p23

Author Biography

Otávio Bianchi, Universidade de Caxias do Sul

Possui graduação em Engenharia Química;mica pela Universidade de Caxias do Sul (2007) e doutorado em Ciência dos Materiais pela Universidade Federal do Rio Grande do Sul (2011). Atualmente é professor da Universidade de Caxias do Sul no Centro de Ciências Exatas e Tecnologias e no Programa de Pós-Graduação em Engenharia e Ciência dos Materiais (PGMAT). Tem experiência na área de Engenharia de Materiais com enfase em polímeros e aplicações, atuando principalmente nos seguintes temas: Poliedros Oligoméricos Silsesquioxanos (POSS), processamento reativo, análise térmica de polímeros, nanocompósitos, propriedades viscoelásticas e cinética de reações utilizando métodos termoanalíticos.

References

M. Narathichat, C. Kummerlowe, et al., “Thermoplastic natural rubber based on polyamide-12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties,” Journal of Applied Polymer Science, vol. 121, no. 2, pp. 805–814, 2011.

F. Bondan, M. R. Soares, and O. Bianchi, “Effect of dynamic cross-linking on phase morphology and dynamic mechanical properties of polyamide 12/ethylene vinyl acetate copolymer blends,” Polymer bulletin, vol. 71, no. 1, pp. 151–166, 2014.

C. F. Antunes, A. Machado, and M. Van Duin, “Morphology development and phase inversion during dynamic vulcanisation of epdm/pp blends,” European Polymer Journal, vol. 47, no. 7, pp. 1447–1459, 2011.

T. Chatterjee, S. Wiessner, et al., “Novel thermoplastic vulcanizates (tpvs) based on silicone rubber and polyamide exploring peroxide cross-link.,” Express Polymer Letters, vol. 8, no. 4, 2014.

O. Bianchi, A. Zattera, and L. Canto, “Dynamic vulcanization of hdpe/eva blend using silane,” Journal of Elastomers and Plastics, vol. 42, no. 6, pp. 561–575, 2010.

D. R. Paul, and C. B. Bucknall, Polymer blends, Wiley, 2000.

A. Coran, and R. Patel, “Thermoplastic elastomers based on dynamically vulcanized elastomer-thermoplastic blends,” Hanser Publishers, Munich, 1996.

A. R. Bhattacharyya, A. K. Ghosh, and A. Misra, “Reactively compatibilised polymer blends: a case study on pa6/eva blend system,” Polymer, vol. 42, no. 21, pp. 9143–9154, 2001.

O. Bianchi, J. D. N. Martins, et al., “Changes in activation energy and kinetic mechanism during eva crosslinking,” Polymer Testing, vol. 30, no. 6, pp. 616–624, 2011.

O. Bianchi, R. Oliveira, et al., “Assessment of avrami, ozawa and avrami–ozawa equations for determination of eva crosslinking kinetics from dsc measurements,” Polymer Testing, vol. 27, no. 6, pp. 722–729, 2008.

A. Nesterov, and E. Lebedev, “Modification of polymers by polymeric additives,” Russian Chemical Reviews, vol. 58, no. 8, pp. 795–807, 1989.

G. Moad, “The synthesis of polyolefin graft copolymers by reactive extrusion,” Progress in Polymer Science, vol. 24, no. 1, pp. 81–142, 1999.

N. Mekhilef, and H. Verhoogt, “Phase inversion and dual-phase continuity in polymer blends: theoretical predictions and experimental results,” Polymer, vol. 37, no. 18, pp. 4069–4077, 1996.

M. Faker, M. R. Aghjeh, et al., “Rheology, morphology and mechanical properties of polyethylene/ethylene vinyl acetate copolymer (pe/eva) blends,” European Polymer Journal, vol. 44, no. 6, pp. 1834–1842, 2008.

R. Robertson, and D. Paul, “Stress–strain behavior of polyolefin blends,” Journal of Applied Polymer Science, vol. 17, no. 8, pp. 2579–2595, 1973.

K. Chatterjee, and K. Naskar, “Study on characterization and properties of nanosilica-filled thermoplastic vulcanizates,” Polymer Engineering & Science, vol. 48, no. 6, pp. 1077–1084, 2008.

J. Van Dyke, M. Gnatowski, and A. Burczyk, “Solvent resistance and mechanical properties in thermoplastic elastomer blends prepared by dynamic vulcanization,” Journal of applied polymer science, vol. 109, no. 3, pp. 1535–1546, 2008.

M. I. Kohan, et al., Nylon plastics handbook, vol. 378, Hanser Munich, 1995.

A. Zattera, O. Bianchi, et al., “Influence of composition and crosslinking on mechanical and thermal properties of recycled polyethylene/eva mixtures,” Progress in rubber, plastics and recycling technology, vol. 22, no. 2, pp. 69–87, 2006.

O. Bianchi, R. Fiorio, et al., “Crosslinking kinetics of blends of ethylene vinyl acetate and ground tire rubber,” Journal of Elastomers and Plastics, vol. 41, no. 2, pp. 175–189, 2009.

J. N. Martins, T. G. Klohn, et al., “Dynamic mechanical, thermal, and morphological study of abs/textile fiber composites,” Polymer bulletin, vol. 64, no. 5, pp. 497–510, 2010.

E. Freire, O. Bianchi, et al., “Processability of pvdf/pmma blends studied by torque rheometry,” Materials Science and Engineering: C, vol. 29, no. 2, pp. 657–661, 2009.

Z. Tadmor, and C. G. Gogos, Principles of polymer processing, John Wiley & Sons, 2013.

A. Msakni, P. Chaumont, and P. Cassagnau, “Diffusion of the dicumyl peroxide in molten polymer probed by rheology,” Rheologica acta, vol. 46, no. 7, pp. 933–943, 2007.

G. Martin, C. Barres, et al., “Morphology development in thermoplastic vulcanizates (tpv): Dispersion mechanisms of a pre-crosslinked epdm phase,” European Polymer Journal, vol. 45, no. 11, pp. 3257–3268, 2009.

M. Akiba, and A. Hashim, “Vulcanization and crosslinking in elastomers,” Progress in polymer science, vol. 22, no. 3, pp. 475–521, 1997.

W. Zhou, and S. Zhu, “Esr study of peroxide-induced cross-linking of high density polyethylene,” Macromolecules, vol. 31, no. 13, pp. 4335–4341, 1998.

D. Forsstrom, and B. Terselius, “Thermo oxidative stability of ¨polyamide 6 films i. mechanical and chemical characterisation,” Polymer degradation and stability, vol. 67, no. 1, pp. 69–78, 2000.

T. Karstens, and V. Rossbach, “Thermo-oxidative degradation of polyamide 6 and 6, 6. kinetics of the formation and inhibition of uv/vis-active chromophores,” Die Makromolekulare Chemie, vol. 190, no. 12, pp. 3033–3053, 1989.

A. J. Lovinger, and M. Williams, “Tensile properties and morphology of blends of polyethylene and polypropylene,” Journal of Applied Polymer Science, vol. 25, no. 8, pp. 1703–1713, 1980.

Published

03/15/2015

How to Cite

Bondan, F., & Bianchi, O. (2015). Effect of dynamic crosslinking on phase morphology and mechanical properties of polyamide 6,12/ethylene vinyl acetate copolymer blends. Scientia Cum Industria, 3(1), 23–28. https://doi.org/10.18226/23185279.v3iss1p23

Issue

Section

Science, Education and Engineering