Barolo, Claudia

Bonomo, Matteo

Bordiga, Silvia

Fin, Andrea

Gastaldi, Matteo

Signorile, Matteo

Viscardi, Guido

Zanetti, Marco

English

Institutional Research Information System University of Turin

16 October 2023AperTO - Archivio Istituzionale Open Access dell'Università di TorinoOriginal Citation:Tunable gas permeability of 3D printed azobased membranesTerms of use:Open Access(Article begins on next page)Anyone can freely access the full text of works made available as "Open Access". Works made availableunder a Creative Commons license can be used according to the terms and conditions of said license. Useof all other works requires consent of the right holder (author or publisher) if not exempted from copyrightprotection by the applicable law.Availability:This is the author's manuscriptThis version is available http://hdl.handle.net/2318/1806065 since 2021-09-28T12:04:18ZMatteo Gastaldia,b, Andrea Finc, Ignazio Roppolod, Matteo Bonomoa,b, Matteo Signorilea,b, Silvia Bordigaa,b, Marco Zanettia,b, Guido Viscardia,b, Claudia Baroloa,ba Dipartimento di Chimica e Centro Interdipartimentale NIS, Università di Torino, Via Pietro Giuria 7, 10125-Torino, Italyb INSTM Reference Centre, Università degli Studi di Torino, Via G. Quarello 15A, 10135 – Turin, Italyc Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria 9, 10125-Torino, Italyd Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129-Torino, Italymatteo.gastaldi@unito.it[1] Z.X. Khoo, J.E.M. Teoh, Y. Liu, C.K. Chua, S. Yang, J. An, K.F. Leong and W.Y. Yeong Virtual and Physical Prototyping, 2015, 10, 103[2] Gillono, M.; Roppolo, I.; Frascella, F.; Scaltrito, L.; Pirri, C. F.; Chiappone, A., Applied Materials Today, 2020, 18, 100470[3] Accardo, J. V.; Kalow, J. A. Chem. Sci. 2018, 9, 5987–5993ConclusionThe different transmission (Tr) rates registered for the introduced polymer are, most likely, related to the presence of the azo groups. They can increase thetransmission rate of an almost totally gas impermeable polymeric membrane.According to the steric hindrance of the ortho functional groups, different Tr values were obtained. The only functionalized samples that seem to not follow this trendare the ones with H and Cl as ortho groups. These samples are actually under investigation.Under green laser irradiation (532 nm) a rapid and reversible increase in permeability of CO2 was observed. The same behavior can’t be registered for other gases.A possible application of these membranes is under investigation, to realize 3DP devices with different tunable gas selectivity.B) Monomer used in the formulation for the Digital Light Processing (DLP).C) Photoinitiator used to start the radical polymerization.IntroductionThree-Dimensional printing (3DP) is an innovative technique,nowadays used both in industrial and academic fields. The highversatility and user-friendliness, the progressive printers’ priceknock off and the considerable saving of raw materials are justfew advantages of these technologies. Among others, the DigitalLight Project (DLP) printer is under investigation to widen thepalette of printable formulations, producing innovative functional3D printed devices. The exploitation of new functional materials,for example temperature-, light- and pH-responsive polymers,is one of the most interesting survey field [1]. Azodyes aretypically used in the formulation to confer innovative features dueto the ability to undergo cis/trans isomerization under light (UVor laser) irradiation [2]. In this work we designed, synthetized,and characterized azo benzene methacrylated monomers(Figure 1) with different groups in ortho position respect to theazo bridge, exploiting the methacrylic functional group tocovalently connect the dye with the polymeric chains. It is wellknown in literature that the ortho position in the azodyes caninteract with the polymeric matrix [3].Synthesis and photopolymerization0 1000 2000 3000 4000 5000 6000 7000 80000100200300400500600700800CO2 Tr[cc/m2*24h)]Time (sec)Tunable gas permeability of 3D printed azobased membranesD) Schematic representation of permeometer with polymeric azo-basedmembrane. Nitrogen is used as gas carrier while the analyte gas isintroduced in the first chamber, it pass through the membrane and is ledto the detector.E) O2 and F) CO2 permeability trend for each sample according to thesteric hindrance of the ortho group. G) The transmission rate over timefor CO2 under laser irradiation. When the laser is switched on, a rapidincrease in Tr is registered, in a totally reversible and repeatable way.0500100015002000250030003500Blank H F Cl Br ICO2 Permeability 25°C0100200300400500600Blank H F Cl Br IBarrerO2 Permeability 25°CE) F)A) Schematic representation of the monomer preparation: a) NaNO2, AcOH, HCl, H2O, 0 to 5°C to rt, 4 hours. b) TEA, THF, rt, 18 hours. PermeabilityD) G)POR FESR/FSE 2014/2020The research leading to these results has receivedfunding from the European Union and the RegionePiemonte, Piattaforma Tecnologica “FabbricaIntelligente” - SMART 3D Project.

Tunable gas permeability of 3D printed azobased membranes

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Tunable gas permeability of 3D printed azobased membranes

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