4.7 Article

Bioinspired polydopamine-induced assembly of ultrafine Fe(OH)3 nanoparticles on halloysite toward highly efficient fire retardancy of epoxy resin via an action of interfacial catalysis

Journal

POLYMER CHEMISTRY
Volume 8, Issue 26, Pages 3926-3936

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c7py00660h

Keywords

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Funding

  1. Spanish Ministry of Economy and Competitiveness (MINECO) under a Ramon y Cajal fellowship [RYC-2012-10737]
  2. COST Action CM1302 (Smart Inorganic Polymers)

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Inspired by the core-sheath-dot structure of corncobs, halloysite nanotubes (HNT) were sequentially functionalized with a biomimetic polydopamine (PDA) nanocoating and ultrafine Fe(OH)(3) nanoparticles to prepare hierarchical HNT@PDA@Fe(OH)(3), with the aim of endowing epoxy resin (EP) with improved fire retardancy, thermal stability and mechanical properties. The target product was characterized via Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). As a result, in a study of thermal degradation a nano-composite of EP with HNT@PDA@Fe(OH)(3) generated a notably higher yield of char and exhibited a lower maximum degradation rate than its counterparts. An investigation of fire retardancy revealed that EP/5HNT@PDA@Fe(OH)(3) possessed an LOI value of 33.9% and a UL-94 vertical burning rating of V-1, which represent significant enhancements in comparison with neat EP (LOI = 24.1%, no rating). In a cone calorimeter test (CCT) at 50 kW m(-2), EP/5HNT@PDA@Fe(OH)(3) gave rise to a 41% reduction in peak heat release rate (pHRR) relative to that of EP/5HNT. A TG-FTIR test disclosed that HNT@PDA@Fe(OH)(3) notably decreased the evolution of volatiles (CO, aliphatic compounds, aromatic compounds, and carbonyl compounds), which resulted in less flammable gases. Variable-temperature FTIR, Raman spectra and SEM observations revealed that char with a more compact and continuous structure was obtained with HNT@PDA@Fe(OH)(3).In addition, the tensile strength and modulus were remarkably enhanced, accompanied by an increase in the dynamic storage modulus (E'). Finally, a probable mechanism was proposed to account for the improved fire retardancy, which involved catalytic charring behavior at the interface (determined by TG-GC-MS) and intensive protection by char.

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