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The effect of graphene and graphene oxide nanoplatelets on the gas permselectivity and ageing behaviour of poly(trimethyl silyl propyne) (PTMSP). Luca Olivieri, Simone Ligi, Maria Grazia De Angelis, Giorgio Cucca, and Alberto Pettinau Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b03251 • Publication Date (Web): 21 Oct 2015 Downloaded from http://pubs.acs.org on October 28, 2015
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Industrial & Engineering Chemistry Research
The effect of graphene and graphene oxide nanoplatelets on the gas permselectivity and ageing behaviour of poly(trimethyl silyl propyne) (PTMSP). Luca Olivieri, a,b Simone Ligi,c Maria Grazia De Angelis, a,b* Giorgio Cucca,d Alberto Pettinau d
a) Dipartimento di Ingegneria Civile, Chimica, Ambientale e dei Materiali (DICAM) Via Terracini 28 I-40131 Bologna, Italy. b) Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Via G. Giusti 9, 50121, Firenze, Italy. c) GNext, Via Massimo D’Azeglio, 40123, Bologna, Italy d) SOTACARBO, Società Tecnologie Avanzate S.p.A., Ex Miniera di Serbariu, 09013 Carbonia, Italy.
Abstract Membranes obtained by adding small amounts (1 wt%) of nanoplatelets of Graphene (G) and Graphene Oxide (GO) to poly(1-trimethylsilyl-1-propyne) (PTMSP) were fabricated with a simple route, and their gas permeability was measured at 30°C over 9 months. In most cases, variations of PTMSP permeability due to the addition of filler are limited, while the ideal selectivity CO2/He, CH4/He, CH4/N2 is slightly enhanced by addition of filler. Specific measurements indicate that the CO2 and CH4 diffusivity are more strongly affected by addition of graphene than their solubility: such behaviour indicates that the filler modifies mainly the microstructure of the polymer rather than its interactions with the gas, as it is reasonable. The most significant quantitative effect observed after filler incorporation is the reduction of PTMSP ageing, that was monitored by studying gas permeability after 9 months of ageing at room temperature and after annealing at 200°C. The reduction of ageing observed after adding graphene is more significant than that obtained with large amounts (up to 20 vol%) of other inorganic fillers, like MgO and TiO2, even though the amount of filler added in this work is small ( PHe > PN 2 , i.e. that, with the exception of Helium, the permeability increases systematically with the gas critical temperature. Such behavior indicates that the gas permeability in PTMSP-based membranes is strongly affected by the solubility value, as we mentioned before.37 The trend is not followed by Helium because such gas is much smaller than the other ones and compensates its low condensability with an extremely high diffusivity value. (a) 100000
Permeability (after 2d from casting), Barrer
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PTMSP GO-MMM IND G-MMM M60-MMM
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0.30 0.25 ABS(P/PPTMSP-1)
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0.20 0.15 GO-MMM IND G-MMM M60-MMM
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kinetic diameter (A) Figure 2: Gas permeability (a) and selectivity (b) in PTMSP, GO-MMM, IND G-MMM and M60-MMM at 30°C after 48h from casting. (c) Permeability vs. penetrant Tc, for PTMSP and MMMs at 30°C. (d) Absolute relative variation of PTMSP permeability induced by filler, vs. penetrant kinetic diameter, for various MMMs at 30°C. Note that for GO-MMM P>PPTMSP, while for M60-MMM and IND G-MMM PPPTMSP, while for M60-MMM and IND G-MMM P
