Abstract
Polyamide 6 microcapsules (PAMC) loaded with 2–8 wt% of Cu, Zn, or Fe and up to 30 wt% of Al particles are synthesized via activated anionic polymerization (AAP) of ε-caprolactam in suspension performed in the presence of the respective micro- or nanosized loads. The high-molecular weight porous PAMC are with typical diameters of 10–90 µm depending on the size of the metal filler particles. The latter are entrapped in the core of PAMC as proven by microscopy methods. The melt processing of the loaded microcapsules produced PA6/metal hybrid thermoplastic composites with homogeneous distribution of the loads without any functionalization. The crystalline structure of all PAMC and molded composites is studied by thermal and microfocus X-ray diffraction methods suggesting polymorph changes during the transition from PAMC to molded plates. Mechanical tests in tension showed that transforming Al-loaded PAMC into composites produces polyamide hybrids with higher modulus and strength at break. Measuring the conductivity and dielectric properties of the composites in linear and cyclic modes showed that 30 wt% of Al can change significantly the permittivity of the hybrid composites without increasing the conductivity of the PA6 matrix.
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Carotenuto G, Nicolais L, Martorana B, Perlo P (2005) Metal-polymer nanocomposite synthesis: novel in-situ and ex-situ approaches. In: Nicolais L, Carotenuto G (eds) Metal-polymer nanocomposites. Wiley, Hoboken, p 155
Song HM, Kim YJ, Park JH (2008) Three-dimensional hierarchically organized magnetic nanoparticle polymer composites: achievement of monodispersity and enhanced tensile strength. J Phys Chem C 112:5397–5404
Liang Y, Xia X, Luo Y, Jia Z (2007) Synthesis and performances of Fe2O3/PA6 nanocomposite fiber. Mater Lett 61:3269–3272
Mallakpour S, Zeraatpisheh F (2012) Preparation and morphology distinguishing of novel ZnO ultrafine particle filled nanocomposites containing new poly(amide-imide) via ultrasonic process. J Polym Res 19:9927–9936
Laachachi A, Cochez M, Ferriol M, Lopez Cuesta JM, Leroy E (2005) Influence of TiO2 and Fe2O3 fillers on the thermal properties of polymethyl methacrylate. Mater Lett 59:36–39
Althues H, Henle J, Kaskel S (2007) Functional inorganic nanofillers for transparent polymers. Chem Soc Rev 36:1454–1465
Balazs AC, Emrick T, Russell TP (2006) Nanoparticle polymer composites: where two small worlds meet. Science 314:1107–1110
Chu J-W, Shim I-W (1993) The chemistry of ruthenium in cellulose acetate: reactions with CO, H2, O2 and H2O. J Mol Catal 78:189–199
Mathiyarasu J, Senthilkumar S, Phani KLN, Yegnaraman V (2008) PEDOT-Au nanocomposite film for electrochemical sensing. Mater Lett 62:571–573
François NJ, Allo S, Jacobo SE, Daraio ME (2007) Composites of polymeric gels and magnetic nanoparticles: preparation and drug release behavior. J Appl Polym Sci 105:647–655
Carotenuto G, Martorana B, Perlo P, Nicolais L (2003) A universal method for the synthesis of metal and metal sulfide clusters embedded in polymer matrices. J Mater Chem 13:2927–2930
Reboud V, Kehagias N, Striccoli M, Placido T, Panniello A et al (2007) Photo-luminescence enhancement in metallic nanocomposite printable polymer. J Vac Sci Technol B 25:2642–2644
Zhou W, Wang Z, Dong L, Sui X, Chen Q (2015) Dielectric properties and thermal conductivity of PVDF reinforced with three types of Zn particles. Compos Part A 79:183–191
Carotenuto G, Pepe IG, Davino D, Martorana B, Perlo P et al (2006) Transparent-ferromagnetic thermoplastic polymers for optical components. Microw Opt Technol Lett 48:2505–2508
Domènech B, Ziegler KK, Carrillo F, Muñoz M, Muraviev DN, Macanás J (2013) Development of novel catalytically active polymer-metal-nanocomposites based on activated foams and textile fibers. Nanoscale Res Lett 8:238–245
Kruenate J, Tongpool R, Panyathanmaporn T (2004) Optical and mechanical properties of polypropylene modified by metal oxides. Surf Interface Anal 36:1044–1047
Wang Z, Wang X, Zhang Z (2009) Nucleating activation and spherical crystals morphology of LLDPE/LDPE/TiO2 nano composites prepared by non-isothermal crystallization. J Dispers Sci Technol 30:1231–1236
Xu Q, Li X, Zhang S, Hao Y, Zhang Z (2013) Copper nanowire/PA6 composites prepared by in situ polymerization and its properties. J Polym Res 20:257–263
Mohamed M, El-Maghraby A, El-Latif MA, Farag H, Kalaitzidou K (2013) Fe-Ni alloy/polyamide 6 nanocomposites: effect of nanocrystalline metal particles on the mechanical and physical properties of the polymer. J Polym Res 20:137–146
Palza H (2015) Antimicrobial polymers with metal nanoparticles. Int J Mol Sci 16:2099–2116
Damm C, Münstedt H, Rösch A (2007) Long-term antimicrobial PA6/Ag-nanocomposites. J Mater Sci 42:6067–6073. doi:10.1007/s10853-006-1158-5
Xu Q, Li X, Zhang Z (2015) Preparation of copper nanoparticle-improved polyamide 6 composites by an in situ solution route with cupric oxide as the metallic copper source and investigation of their properties. New J Chem 39:3015–3020
Komeily-Nia Z, Montazer M, Latifi M (2013) Synthesis of nano copper/nylon composite using ascorbic acid and CTAB. Colloids Surf A 439:167–175
Lonjon A, Caffrey I, Carponcin D, Dantras E, Lacabanne C (2013) High electrically conductive composites of Polyamide 11 filled with silver nanowires: nanocomposites processing, mechanical and electrical analysis. J Non-Cryst Solids 376:199–204
Dencheva N, Denchev Z, Lanceros-Méndez S, Ezquerra TA (2016) One-step in situ synthesis of polyamide microcapsules with inorganic payload and their transformation into responsive thermoplastic composite materials. Macromol Mat Eng 301:119–124
Rusu Gh, Ueda K, Rusu E, Rusu M (2001) Polyamides from lactams by centrifugal molding via anionic ring-opening polymerization. Polymer 42:5669–5678
Roda J (2009) Polyamides. In: Dubois P, Coulembier O, Raquez JM (eds) Handbook of ring-opening polymerization. Wiley-VCH, Wincheim, pp 165–196
Dan F, Vasiliu-Oprea C (1998) Anionic polymerization of caprolactam in organic media—morphological aspects. Colloid Polym Sci 276:483–495
Vasiliu-Oprea C, Dan F (1997) On the relation between synthesis parameters and morphology of anionic polycaproamide obtained in organic media. II. Influence of the Na[O(CH2)2OCH3]2AlH2/aliphatic diisocyanates catalytic systems. J Appl Polym Sci 64:2575–2583
Dencheva N, Denchev Z, Pouzada AS, Sampaio AS, Rocha AM (2013) Structure–properties relationship in single polymer composites based on polyamide 6 pre- pared by in-mold anionic polymerization. J Mater Sci 48:7260–7273. doi:10.1007/s10853-013-7546-8
Fornes TD, Paul DR (2003) Crystallization behavior of nylon 6 nanocomposites. Polymer 44:3945–3961
Dencheva N, Stribeck A, Denchev Z (2016) Nanostructure development in multicomponent polymer systems and its characterization by X-ray scattering. Eur Polym J 81:447–469
Dencheva N, Nunes T, Oliveira MJ, Denchev Z (2005) Microfibrillar composites based on polyamide/polyethylene blends. 1. Structure investigations in oriented and isotropic polyamide 6. Polymer 46:887–901
Acknowledgements
This article is a result of the project TSSiPRO—NORTE-01-0145-FEDER-000015—supported by the regional operational program NORTE 2020, under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund. The authors also thank for the financial support of the Portuguese Foundation for Science and Technology (FCT) in the frames of the strategic projects LA25/2013–2014, UID/CTM/50025/2013, and UID/FIS/04650/2013. Partial financing by PTDC/EEI-SII/5582/2014 and PTDC/CTM-ENE/5387/2014 is also gratefully acknowledged. ZZD appreciates the support of PETRA III (MiNaXS beamline) of the German Synchrotron Facility DESY, Germany (Project No. I-20130095 EC). Financial support from the Basque Government Industry Department under the ELKARTEK Program is acknowledged by SLM.
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Brêda, C., Dencheva, N., Lanceros-Méndez, S. et al. Preparation and properties of metal-containing polyamide hybrid composites via reactive microencapsulation. J Mater Sci 51, 10534–10554 (2016). https://doi.org/10.1007/s10853-016-0274-0
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DOI: https://doi.org/10.1007/s10853-016-0274-0