Benzene-Induced Crystallization of PPO: A Combined Thermodynamic and Vibrational Spectroscopy Study

Musto, Pellegrino; Loianno, Valerio; Scherillo, Giuseppe; Manna, Pietro La; Galizia, Michele; Guerra, Gaetano; Mensitieri, Giuseppe

doi:10.1021/acs.iecr.9b04563

Cited by 11 publications

(11 citation statements)

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“…The WAXD pattern (Figure S1a) indicates the presence of c ⊥ -oriented NC α form with a degree of orientation f c ≈ −0.3. Analogous c ⊥ -oriented α form films were obtained by using room temperature guest sorption in thicker amorphous films. ,− This c ⊥ -oriented NC α form film exhibits a density (0.99 g cm –3 ) being intermediate between those of the starting amorphous film (1.04 g cm –3 ) and of the pure α form (0.93 g cm –3 ). As shown by the photo of Figure a, these films are highly transparent, as generally found for PPO films exhibiting c ⊥ planar orientation of the crystalline chain axis. …”

Section: Resultsmentioning

confidence: 95%

“…Moreover, PPO powders, which generally can be packed in absorption systems only up to an apparent density of 0.3 g cm –3 , also present the drawback of difficult handling, as always occurs for fine particles. Much more handleable are of course self-supporting polymer films, − which, however, even for NC polymers and as generally occurs for polymer films exhibit negligible SA (<4 m 2 g –1 ).…”

Section: Introductionmentioning

confidence: 99%

“…Irrespective of their negligible SA, NC PPO films can reach very fast guest uptakes by using crystallization procedures leading to orientation of the chain axes of the NC phases being preferentially perpendicular to the film plane ( c ⊥ orientation) . For these c ⊥ -oriented NC PPO films, guest sorption kinetics are much faster than for unoriented NC films as well as than for commercial absorbent polymers (Tenax) but definitely slower than for sPS and PPO NC aerogels. , …”

Section: Introductionmentioning

confidence: 99%

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High Surface Area Nanoporous-Crystalline Polymer Films

et al. 2022

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Based on a commercially available thermoplastic polymer (poly(2,6-dimethyl-1,4-phenylene) oxide, PPO), nanoporous-crystalline (NC) polymer films with a surface area (SA) higher than 600 m2 g–1 and with exceptionally fast organic pollutant uptakes are presented. Preparation procedures require fast crystallizations of amorphous films, as induced by high uptakes of nonvolatile guest molecules (typically in the range 70–90 wt %), followed by guest exchange with a volatile guest. The high SA of these NC PPO films is associated with a nanofibrillar morphology, analogous to those observed in physically cross-linked PPO aerogels. Organic pollutant diffusivities for high-SA NC PPO films are much higher than for other high-diffusivity PPO films, like for example those exhibiting NC phases with chain axes (and hence crystalline channels) being preferentially perpendicular to the film plane. Much higher diffusivities are observed both for guest sorption from vapor phase and from diluted PPO aqueous solutions and for guest desorption. Surprisingly, kinetics of guest uptakes from high-SA NC PPO films are even faster than for NC PPO aerogels and then much faster when referred to volume of the sorbent material. Because of their extremely fast kinetics of pollutant uptakes, associated with high thermal and mechanical stability, these new high-SA NC PPO films are expected to find many applications, mainly in pollutant remediation and molecular sensors.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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High Surface Area Nanoporous-Crystalline Polymer Films

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“…One possible explanation might be the accumulation of the analyte at the interfaces [ 31 ] as a step in the diffusion process, increasing the concentration and the diffusion coefficient. [ 32 ] In fact, it has been reported that the concentration of the sorbed species is higher at the interface of a layer than at its core, increasing diffusivity; [ 33 ] a typical behavior in some amorphous polymers related to their mechanical relaxation. [ 32 ]…”

Section: Resultsmentioning

confidence: 99%

Universal Design Rules for Flory–Huggins Polymer Photonic Vapor Sensors

Megahd

Lova

Comoretto

2020

Adv Funct Materials

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Multilayered photonic sensors that rely on polymer‐solvent Flory–Huggins interactions are drawing increasing interest owing to their broad‐band selectivity, even among mixtures, without the need for chemical targeting. Moreover, these sensors provide simple colorimetric responses, and easy, quick fabrication both on laboratory and industrial scales. However, complex optical responses and slow response times are limiting their development. In this work, the behavior of different photonic sensor architectures is analyzed to speed up response time and define a strategy to simplify their spectral behavior. To this end, the effect of interfaces, materials order, and thickness on the diffusion kinetics of a single reference analyte in the multilayered sensors is studied to design the optimal structure.

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“…The assumption of a temperature-independent k ij is often a good approximation in interpreting equilibrium data for several binary gaseous systems. 11,19,40 Conversely, when lattice-fluid models are applied to condensed phases, a temperature dependence would be expected based on the temperature dependence of mean-field potentials.…”

Section: Nrhb Binary Interactionmentioning

confidence: 99%

Predictive Approach for the Solubility and Permeability of Binary Gas Mixtures in Glassy Polymers Based on an NETGP-NRHB Model

Baldanza

Loianno

Mensitieri

et al. 2022

Ind. Eng. Chem. Res.

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The NETGP-NRHB lattice-fluid model describes the sorption thermodynamics of penetrants in amorphous polymer−penetrant mixtures locked in an out-of-equilibrium "glassy" state. It accounts for the nonrandom distribution of mean-field contacts and voids and for the possible occurrence of specific interactions. In this contribution, we assess the suitability of the NETGP-NRHB model to interpret the sorption thermodynamics of binary penetrant mixtures in glassy polymers. Moreover, adopting the gradients of NETGP-NRHB penetrant chemical potentials as driving forces for their diffusive fluxes, a self-consistent framework is proposed to predict the permeability of light gas binary mixtures in glassy polymer membranes once all of the model parameters are obtained by nonlinear regression of data of the corresponding binary and pure component subsystems. This approach is validated against solubility data of CO 2 /CH 4 and CO 2 /C 2 H 4 mixtures in glassy amorphous poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(methyl methacrylate) (PMMA), respectively, and permeability data of CO 2 /CH 4 mixtures in three glassy amorphous polymer membranes (PAr, PSf, PH); all of the data are taken from the literature. In particular, solubility data are investigated up to a CH 4 partial pressure of 15 atm at a fixed CO 2 partial pressure equal to 5.1 atm for the system CO 2 /CH 4 /PPO and up to a CO 2 partial pressure of 4 atm at a fixed C 2 H 4 partial pressure equal to 2.09 atm for the system CO 2 /C 2 H 4 /PMMA. Permeability data are investigated at a fixed upstream molar concentration of the binary gas mixture equal to 0.5 by changing the total pressure up to 18 atm for the systems CO 2 /CH 4 /PAr and CO 2 /CH 4 /PSf and up to 14 atm for the system CO 2 /CH 4 /PH; the downstream total pressure is equal to 0 atm for all of the systems. All of the experimental sets of data are obtained at 35 °C. Solubility and permeability predictions for the ternary systems compare very well with all experimental literature data without additional parameters besides those required for the corresponding binary subsystems.

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Benzene-Induced Crystallization of PPO: A Combined Thermodynamic and Vibrational Spectroscopy Study

Cited by 11 publications

References 58 publications

High Surface Area Nanoporous-Crystalline Polymer Films

High Surface Area Nanoporous-Crystalline Polymer Films

Universal Design Rules for Flory–Huggins Polymer Photonic Vapor Sensors

Predictive Approach for the Solubility and Permeability of Binary Gas Mixtures in Glassy Polymers Based on an NETGP-NRHB Model

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