Abstract

A key requirement for the exploitation of two-dimensional (2D)-crystals in the field of composites relies on their large-scale production. In this respect, liquid phase exfoliation of layered-crystals is emerging as one of the most promising approaches for the scalable production of high-quality 2D-crystals. However, the dependence of the 2D crystal flakes morphology, i.e. thickness and lateral size, on the mechanical properties of the polymer composites is not fully understood yet. Herein, we tackle this issue by designing an environmentally friendly approach, based on the exfoliation of bulk hexagonal-boron nitride (h-BN), widely used as filler in polymer composites for its high intrinsic stiffness, i.e. approaching 1 TPa, in a water/surfactant solution with controlled thickness and lateral size by using cascade ultra-centrifugation. Our approach allows us to obtain two populations of flakes with aspect ratio, i.e. lateral size over thickness, equal to 250 and 350, respectively. The h-BN flakes with tuned aspect ratio are subsequently used as filler in a polycarbonate (PC) matrix by exploiting solution blending in 1,3-dioxolane, a solvent with Hansen’s solubility parameters matching the ones of h-BN, thus enhancing the dispersion of the filler inside the matrix, as evaluated by Raman mapping. We tested the composite mechanical properties finding that flakes with higher aspect ratio show superior reinforcements in terms of both ultimate tensile strength and Young’s modulus, compared with their lower aspect ratio counterparts. As example, at 0.1 wt% of loading, the difference in reinforcement in terms of Young’s Modulus is of 56 MPa, being the increment, compared to pristine PC, of ∼22% for composites produced with higher aspect ratio fillers, whereas it is instead of only ∼17% for lower aspect ratio fillers.

Highlights

  • Liquid phase exfoliation (LPE) of layered-materials [1, 2] paved the way towards the large scale exploitation of two-dimensional (2D)-crystals in polymer composite applications [3, 4]

  • The exfoliated hexagonal-boron nitride (h-BN) flakes have been sorted by aspect ratio exploiting sedimentation-based separation (SBS) [3, 29, 40, 41] using a cascade centrifugation [42], obtaining two population of flakes with different morphology, i.e. thickness and lateral size

  • Kolliphor® P188, referred as Pluronic® F68 or Lutrol® F68 according to different suppliers, is a triblock copolymer of the family of poloxamers [54, 55] composed by a hydrophobic poly(propylene oxide) central chain, that is attracted to the h-BN basal plane through hydrophobic interactions [53], surrounded by two hydrophilic poly(ethylene oxide) chains, which stabilize the exfoliated flakes by steric hindrance [53]

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Summary

Introduction

Liquid phase exfoliation (LPE) of layered-materials [1, 2] paved the way towards the large scale exploitation of two-dimensional (2D)-crystals in polymer composite applications [3, 4]. The mechanical energy is provided by either shear [7] or ultrasounds [1] in the presence of a stabilizing solvent, peeling off individual layers from the bulk crystal counterpart, resulting in dispersions of defect-free and un-functionalized nanosheets [8] This top-down method is in principle applicable to all layered materials and it has been already used for obtaining several 2D-crystals such as graphene [7], hexagonal-boron nitride (h-BN) [1, 8], molybdenum disulfide (MoS2) [1, 8], tungsten disulfide (WS2) [1, 8], indium selenide [9], and black phosphorous [10,11,12], just to cite a few. Solvents with a surface tension matching the surface energy of the flakes [3, 5, 8], having Hansen’s solubility parameters—HSPs—(i.e. the energy from dispersion forces between molecules (δD), the energy from hydrogen bonds between molecules (δH), and the energy from dipolar intermolecular force between molecules (δP)) [13] similar to the one of the flakes are able to both exfoliate the bulk-layered materials and disperse/stabilize against re-aggregation the exfoliated flakes [1, 3, 14]

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