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      Multiwalled Carbon Nanotube Reinforced Bio-Based Benzoxazine/Epoxy Composites with NIR-Laser Stimulated Shape Memory Effects

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          Abstract

          Smart materials with light-actuated shape memory effects are developed from renewable resources in this work. Bio-based benzoxazine resin is prepared from vanillin, furfurylamine, and paraformaldehyde by utilizing the Mannich-like condensation. Vanillin-furfurylamine-containing benzoxazine resin (V-fa) is subsequently copolymerized with epoxidized castor oil (ECO). When the copolymer is reinforced with multiwalled carbon nanotubes (MWCNTs), the resulting composite exhibits shape memory effects. Molecular characteristics of V-fa resin, ECO, and V-fa/ECO copolymers are obtained from Fourier transform infrared (FT-IR) spectroscopy. Curing behavior of V-fa/ECO copolymers is investigated by differential scanning calorimetry. Dynamic mechanical properties of MWCNT reinforced V-fa/ECO composites are determined by dynamic mechanical analysis. Morphological details and distribution of MWCNTs within the copolymer matrix are characterized by transmission electron microscopy. Shape memory performances of MWCNT reinforced V-fa/ECO composites are studied by shape memory tests performed with a universal testing machine. After a significant deformation to a temporary shape, the composites can be recovered to the original shape by near-infrared (NIR) laser actuation. The shape recovery process can be stimulated at a specific site of the composite simply by focusing NIR laser to that site. The shape recovery time of the composites under NIR actuation is four times faster than the shape recovery process under conventional thermal activation. Furthermore, the composites possess good shape fixity and good shape recovery under NIR actuation.

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          Most cited references62

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          Fast liquid-crystal elastomer swims into the dark.

          Liquid-crystal elastomers (LCEs) are rubbers whose constituent molecules are orientationally ordered. Their salient feature is strong coupling between the orientational order and mechanical strain. For example, changing the orientational order gives rise to internal stresses, which lead to strains and change the shape of a sample. Orientational order can be affected by changes in externally applied stimuli such as light. We demonstrate here that by dissolving-rather than covalently bonding-azo dyes into an LCE sample, its mechanical deformation in response to non-uniform illumination by visible light becomes very large (more than 60 degrees bending) and is more than two orders of magnitude faster than previously reported. Rapid light-induced deformations allow LCEs to interact with their environment in new and unexpected ways. When light from above is shone on a dye-doped LCE sample floating on water, the LCE 'swims' away from the light, with an action resembling that of flatfish such as skates or rays. We analyse the propulsion mechanism in terms of momentum transfer.
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            A new opto-mechanical effect in solids.

            We propose that large, reversible shape changes in solids, of between 10%-400%, can be induced optically by photoisomerizing monodomain nematic elastomers. Empirical and molecular analysis of shape change and its relation to thermal effects is given along with a simple model of the dynamics of response. Our experiments demonstrate these effects for the first time and theory is compared qualitatively with our results.
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              Remotely actuated polymer nanocomposites--stress-recovery of carbon-nanotube-filled thermoplastic elastomers.

              Stimuli-responsive (active) materials undergo large-scale shape or property changes in response to an external stimulus such as stress, temperature, light or pH. Technological uses range from durable, shape-recovery eye-glass frames, to temperature-sensitive switches, to the generation of stress to induce mechanical motion. Here, we demonstrate that the uniform dispersion of 1-5 vol.% of carbon nanotubes in a thermoplastic elastomer yields nanocomposites that can store and subsequently release, through remote means, up to 50% more recovery stress than the pristine resin. The anisotropic nanotubes increase the rubbery modulus by a factor of 2 to 5 (for 1-5 vol.%) and improve shape fixity by enhancing strain-induced crystallization. Non-radiative decay of infrared photons absorbed by the nanotubes raises the internal temperature, melting strain-induced polymer crystallites (which act as physical crosslinks that secure the deformed shape) and remotely trigger the release of the stored strain energy. Comparable effects occur for electrically induced actuation associated with Joule heating of the matrix when a current is passed through the conductive percolative network of the nanotubes within the resin. This unique combination of properties, directly arising from the nanocomposite morphology, demonstrates new opportunities for the design and fabrication of stimuli-responsive polymers, which are otherwise not available in one material system.
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                Author and article information

                Journal
                Nanomaterials (Basel)
                Nanomaterials (Basel)
                nanomaterials
                Nanomaterials
                MDPI
                2079-4991
                14 June 2019
                June 2019
                : 9
                : 6
                : 881
                Affiliations
                [1 ]Polymer Engineering Laboratory, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, 254 Phayathai Road, Pathumwan, Bangkok 10330, Thailand; w.prasomsin@ 123456gmail.com (W.P.); ParnklangT@ 123456gmail.com (T.P.)
                [2 ]National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), 111 Thailand Science Park, Phahonyothin Road, Khlong Nueng, Khlong Luang, Phatum Thani 12120, Thailand; chaweewan@ 123456nanotec.or.th
                [3 ]Department of Chemistry, Faculty of Liberal Arts & Science, Kasetsart University, Nakhon Pathom 73140, Thailand; faassntk@ 123456ku.ac.th
                [4 ]Research Network NANOTEC-CU on Advanced Structural and Functional Nanomaterials, Chulalongkorn University, Bangkok 10330, Thailand
                Author notes
                [* ]Correspondence: sarawut.r@ 123456chula.ac.th ; Tel.: +66-2218-6862
                Author information
                https://orcid.org/0000-0001-9359-3252
                https://orcid.org/0000-0002-9531-2300
                Article
                nanomaterials-09-00881
                10.3390/nano9060881
                6631418
                31197110
                6bc7dda5-a12b-4a02-9506-8daeed949dce
                © 2019 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 23 May 2019
                : 10 June 2019
                Categories
                Article

                bio-based benzoxazine,multiwalled carbon nanotubes,shape memory polymers,nir actuation,composites,renewable materials

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