Understanding the Mechanical Reinforcement of Metal-Organic Framework-Polymer Composites: The Effect of Aspect Ratio

The aspect ratio (AR) of filler particles is one of the most critical determinants for the mechanical properties of particle-reinforced polymer composites. However, it has been challenging to solely study the effect of particle AR due to the difficulties of controlling AR without altering the physical and chemical properties of the particle. Herein, we synthesized PCN-222, a zirconium-based porphyrinic metal-organic framework (MOF) with preferential longitudinal growth as a series of particles with ARs increasing from 3.4 to 54. The synthetic MOF conditions allowed for the chemical properties of the particles to remain constant over the series. The particles were employed as reinforcers for poly(methyl methacrylate) (PMMA). MOF-polymer composite films were fabricated using doctor-blading techniques, which facilitated particle dispersion and alignment in the PMMA matrix, as revealed by optical microscopy and wide-angle X-ray diffraction. Mechanical measurements showed that both elastic and dynamic moduli increased with particle AR and particle concentrations but started to decrease as particle loading increased beyond 0.5 wt % (1.12 vol %). The data obtained at low particle loadings were fitted well with the Halpin-Tsai model. In contrast, the percolation model and the Cox model were unable to adequately fit the data, indicating the mechanical reinforcement in our system mainly originated from efficient load transfer between particles and the matrix in the particle orienting direction. Finally, we showed that the thermal stability of composite films increased with the addition of MOF particles because of the high thermal degradation temperature and restricted polymer chain mobility.