Plasticization of amorphous polystyrene by volatile organic compounds

Kadam, Ashish; Karbowiak, Thomas; Voilley, Andrée; Gay, Jean-Pierre; Debeaufort, Frédéric

doi:10.1007/s00289-015-1580-4

Cited by 8 publications

(7 citation statements)

References 25 publications

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“…The inset of Figure shows the predicted dynamic glass transition temperature defined by τ hop , PS = 100 s and compares it to the experimental DSC measurements . The theory curve captures well the large ∼120 K reduction of the glass transition temperature as toluene loading reaches about 30%.…”

Section: Diffusion In a Polymer–molecule Mixturementioning

confidence: 68%

“…Toluene self-diffusion constant (in unit of cm 2 /s) in a molten polystyrene matrix as a function of toluene weight fraction predicted by SCCHT (curves) and measured in experiment (symbols) at 383 and 413 K. Inset: Polystyrene glass transition temperature (in Kelvin) as a function of toluene weight fraction predicted by SCCHT (curve) and measured by DSC experiment (symbols). Dashed curves throughout the figure represent theoretical results in the no-adjustable-parameter version of the calculation discussed in the text.…”

Section: Diffusion In a Polymer–molecule Mixturementioning

confidence: 99%

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Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures

Zhang

Schweizer

2018

J. Phys. Chem. B

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The Elastically Collective Nonlinear Langevin Equation theory for one-component viscous liquids and suspensions is generalized to treat coupled slow activated relaxation and diffusion in glass-forming binary sphere mixtures of any composition, size ratio, and interparticle interactions. A trajectory-level dynamical coupling parameter concept is introduced to construct two coupled dynamic free energy functions for the smaller penetrant and larger matrix particle. A two-step dynamical picture is proposed where the first-step process involves matrix-facilitated penetrant hopping quantified in a self-consistent manner based on a temporal coincidence condition. After penetrants dynamically equilibrate, the effectively one-component matrix particle dynamics is controlled by a new dynamic free energy (second-step process). Depending on the time scales associated with the first- and second-step processes, as well as the extent of matrix-correlated facilitation, distinct physical scenarios are predicted. The theory is implemented for purely hard-core interactions, and addresses the glass transition based on variable kinetic criteria, penetrant-matrix coupled activated relaxation, self-diffusion of both species, dynamic fragility, and shear elasticity. Testable predictions are made. Motivated by the analytic ultralocal limit idea derived for pure hard sphere fluids, we identify structure-thermodynamics-dynamics relationships. As a case study for molecule-polymer thermal mixtures, the chemically matched fully miscible polystyrene-toluene system is quantitatively studied based on a predictive mapping scheme. The resulting no-adjustable-parameter results for toluene diffusivity and the mixture glass transition temperature are in good agreement with experiment. The theory provides a foundation to treat diverse dynamical problems in glass-forming mixtures, including suspensions of colloids and nanoparticles, polymer-molecule liquids, and polymer nanocomposites.

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Section: Diffusion In a Polymer–molecule Mixturementioning

confidence: 68%

Section: Diffusion In a Polymer–molecule Mixturementioning

confidence: 99%

Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures

Zhang

Schweizer

2018

J. Phys. Chem. B

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“…We can assume that the BCPs start to vitrify at the Φ p value where the glass transition temperature ( T g ) of PS chains in toluene reaches the temperature of the system (30 °C). Therefore, we used the Fox equation for PS and toluene to find the Φ p of PS that yields a T g = 30 °C as where the T g , p of neat PS (373 K) and T g , s of toluene (137.5 K) were used to calculate the weight fraction of polymer ( w p ), which yielded the volume fraction Φ p of 0.842 . The D o of toluene at 30 °C was estimated to be 10 –8 cm 2 /s from the literature .…”

Section: Resultsmentioning

confidence: 99%

Aspect Ratio-Controlled Synthesis of Uniform Colloidal Block Copolymer Ellipsoids from Evaporative Emulsions

Shin

Kim

et al. 2018

Chem. Mater.

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Block copolymers (BCPs) confined in evaporative emulsions can assemble into ellipsoidal particles when solvent evaporation is faster than polymer diffusion within the droplet. Here, we report the synthesis of monodisperse, ellipsoidal polystyrene-block-1,4-polybutadiene (PS-b-PB) BCP particles with tunable aspect ratios (ARs) ranging from 1.0 to 2.2 and particle sizes ranging from 0.1 to 5 μm by membrane emulsification and subsequent solvent evaporation. The ratio of the propagation distance (l p) of ordered BCP domains perpendicular to the particle surface to the particle size (r BCP), or l p/r BCP, was found to be a critical parameter dictating the particle shape, where l p/r BCP > 1 yielded ellipsoids. We show that the AR of colloidal BCP ellipsoids can be precisely controlled by varying particle size (i.e., membrane pore size) and BCP molecular weight, as predicted by theoretical calculations of the free energy of particle elongation including three terms: (1) the interfacial energy between the two blocks of the BCP, (2) the entropic penalty associated with stretching of the BCP chains upon elongation of the particles, and (3) the surface energy between the BCP particles and the surrounding medium. Finally, using the resulting AR-controlled and highly monodisperse colloidal ellipsoids, we systematically investigated the effects of AR on the homogeneity of colloidal coatings obtained by drop-casting the ellipsoids into films.

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“…This could cause additional emission of VOCs from GTR. It should be also pointed out that formed VOCs could act like plasticizers [41], while their interactions with polymeric matrix could affect the results of SHS-GC-MS. Furthermore, it was observed that volatile organic compounds were omitted directly to the environment after MW treatment of GTR, which also affected the total content of VOCs in studied samples.…”

Section: Resultsmentioning

confidence: 99%

Synergistic Effects of Bitumen Plasticization and Microwave Treatment on Short-Term Devulcanization of Ground Tire Rubber

et al. 2018

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Ground tire rubber (GTR) was mechano-chemically modified with road bitumen 160/220 and subsequently treated using a microwave radiation. The combined impact of bitumen 160/220 content and microwave treatment on short-term devulcanization of GTR was studied by thermal camera, wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), static headspace, and gas chromatography-mass spectrometry (SHS-GC-MS), thermogravimetric analysis combined with Fourier transform infrared spectroscopy (TGA-FTIR), oscillating disc rheometer and static mechanical properties measurements. The obtained results showed that bitumen plasticizer prevents oxidation of GTR during microwave treatment and simultaneously improves processing and thermal stability of obtained reclaimed rubber.

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Plasticization of amorphous polystyrene by volatile organic compounds

Cited by 8 publications

References 25 publications

Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures

Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures

Aspect Ratio-Controlled Synthesis of Uniform Colloidal Block Copolymer Ellipsoids from Evaporative Emulsions

Synergistic Effects of Bitumen Plasticization and Microwave Treatment on Short-Term Devulcanization of Ground Tire Rubber

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