ABSTRACT
Molecular force transduction in tough and glassy poly(meta,meta,para-phenylene) (PmmpP) was investigated as a function of Mn using covalently incorporated mechanochromic donor-acceptor torsional springs based on an ortho-substituted diphenyldiketopyrrolopyrrole (oDPP). Blending oDPP-PmmpP probe chains with long PmmpP matrix chains allowed us to investigate molar-mass-dependent mechanochromic properties for a series of specimens having mechanically identical properties. In the strain-hardening regime, the mechanochromic response (Δλmax,em) was found to be a linear function of the acting stress and fully reversible, making oDPP-PmmpP a real-time and quantitative stress sensor. For entangled and nonentangled probe chains, distinctly different values of Δλmax,em were observed, yielding a critical molar mass of Mc ≈ 11 kg mol-1 for PmmpP. Once physical cross-linking of oDPP in the network of PmmpP was ensured, Δλmax,em was found to be independent of Mn. The resulting value of Mc is in very good agreement with results from rheology.
Subject(s)
Polymers , Molecular Weight , RheologyABSTRACT
Mechanochromic polymers are intriguing materials that allow to sense force of specimens under load. Most mechanochromic systems rely on covalent bond scission and hence are two-state systems with optically distinct "on" and "off" states where correlating force with wavelength is usually not possible. Translating force of different magnitude with gradually different wavelength of absorption or emission would open up new possibilities to map and understand force distributions in polymeric materials. Here, we present a mechanochromic donor-acceptor (DA) torsional spring that undergoes force-induced planarization during uniaxial elongation leading to red-shifted absorption and emission spectra. The DA spring is based on ortho-substituted diketopyrrolopyrrole (o-DPP). Covalent incorporation of o-DPP into a rigid yet ductile polyphenylene matrix allows to transduce sufficiently large stress to the DA spring. The mechanically induced deflection from equilibrium geometry of the DA spring is theoretically predicted, in agreement with experiments, and is fully reversible upon stress release.
ABSTRACT
Mechanochromic polymeric systems are intensively investigated for real-time stress detection applications. However, an effective stress-sensing material must respond to low deformation with a detectable color change that should be quickly reversible upon force unloading. In this work, mechanochromic nanofibers made by electrospinning are used to produce mechanochromic nanofiber/poly(dimethylsiloxane) (PDMS) composites with isotropic and anisoptropic response. Due to chain alignment of spiropyran copolymer chains within the nanofibers, only very small strains are required to yield a mechanochromic response. Composites with aligned and isotropic nanofibers show anisotropic and isotropic mechanochromic behavior, respectively. Due to the special substitution pattern of spiropyran in the copolymer, the mechanochromic response of these nanofiber/PDMS composites shows fast reversibility upon force unloading. The outstanding benefit of using highly sensitive mechanochromic nanofibers as filler in composite materials allows the detection of directional stress and strain, and it is a step forward in the development of smart, mechanically responsive materials.
