A method for the synthesis of a linear block copolymer (PNIPAM-b-PANI), containing a thermoresponsive block (poly(N-isopropylacrylamide), PNIPAM) and a Near Infrared (NIR) light-absorbing block (polyaniline, PANI), is reported. The synthetic approach involves a two-step successive polymerization reaction. First, the radical polymerization of NIPAM is done using 4-aminothiophenol as a chain transfer agent for the obtention of thermosensitive block terminated with an aniline (ANI) moiety. Second, the oxidative polymerization of ANI is initiated in ANI moiety of thermosensitive block to grow the second conductive PANI block. 1H nuclear magnetic resonance (NMR) and FT-IR spectroscopy shows the characteristics peaks of both polymeric blocks revealing the successful copolymerization process. Static Light Scattering (SLS) and UV-Visible combined measurements allowed the determination of the Mw for PNIPAM-b-PANI macromolecule: 5.5 × 105 g mol−1. The resulting copolymer is soluble in water (8.3 g L−1) and in non-aqueous solvents, such as ethanol, formic acid, acetonitrile, and others. Both polymer blocks chains show the properties of the polymer chains. The block copolymer shows a lower critical solution temperature (LCST) at the same temperature (32–34 °C) than PNIPAM, while the copolymer shows pH dependent UV-vis-NIR absorption similar to PANI. The PNIPAM block suffers a coil to globule transition upon NIR light irradiation (785 nm, 100 mW), as shown by turbidimetry and Atomic Force Microscopy (AFM), due to local heating (more than 9 °C in 12 min) induced by the NIR absorption at the PANI block. Furthermore, the electrical conductivity of PNIPAM-b-PANI thin films is demonstrated (resistivity of 5.3 × 10−4 Ω−1 cm−1), indicating that the PANI block is present in its conductive form.
Photo-thermo-mechanochemical (P-T-MCh) nanocomposites provide a mechanical and/or chemical output (MCh) in response to a photonic (P) input, with the thermal (T) flux being the coupling factor. The nanocomposite combines a photon absorbing nanomaterial with a thermosensitive hydrogel matrix. Conjugated (absorbing in the near infrared (NIR, 750–850 nm) wavelength range) polymer (polyaniline, PANI) nanostructures are dispersed in cross-linked thermosensitive (poly(N-isopropylacrylamide), PNIPAM) hydrogel matrices, giving the nanocomposite P-T-MCh properties. Since PANI is a conductive polymer, electromagnetic radiation (ER) such as radiofrequency (30 kHz) and microwaves (2.4 GHz) could also be used as an input. The alternating electromagnetic field creates eddy currents in the PANI, which produces heat through the Joule effect. A new kind of “product” nanocomposite is then produced, where ER drives the mechanochemical properties of the material through thermal coupling (electromagnetic radiation thermomechanochemical, ER-T-MCh). Both optical absorption and conductivity of PANI depend on its oxidation and protonation state. Therefore, the ER-T-MCh materials are able to react to the surroundings properties (pH, redox potential) becoming a smart (electromagnetic radiation thermomechanochemical) (sER-T-MCh) material. The volume changes of the sER-T-MCh materials are reversible since the size and shape is recovered by cooling. No noticeable damage was observed after several cycles. The mechanical properties of the composite materials can be set by changing the hydrogel matrix. Four methods of material fabrication are described.
The generation of filaments constituted by nanocomposites allows printing pieces with functional properties. A method is proposed for incorporating nanoparticles in plastic filaments (thermoplastic polyurethane, PU) by diffusion in the swollen material. The nanoparticles must be dispersed in solvents (or solvent mixtures) in which the polymer swells but does not dissolve. Nanoparticles are incorporated mainly at the surface as revealed by SEM/EDS mapping. The thermal properties (studied by DSC and TGA) of the PU are only slightly affected by the presence of NPs. Test pieces successfully are printed using the modified filaments. Incorporation of solid lubricant (MoS2) nanoparticles decreases the coefficient of friction of the printed test samples.
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