Studies on sublimation of disperse dye out of dyed polymers. I. Rate of sublimation and amorphous transition points of poly(ethylene terephthalate)

Itô, Ichiro; Okajima, Saburo; Shibata, Fumiaki

doi:10.1002/app.1970.070140304

Cited by 14 publications

(8 citation statements)

References 24 publications

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“…et al 12 that a smaller compound can more easily achieve such a condition supports our suggestion. Some papers have reported that the diffusion of disperse dyes in polymers such as poly( ethylene terephthalate ), 12 polypropylene, 13 and polystyrene 14 is hardly dependent on the initial dye concentration, when it is below 1.5 x 10-4 molg-1 of the polymer.…”

Section: Resultssupporting

confidence: 91%

“…Some papers have reported that the diffusion of disperse dyes in polymers such as poly( ethylene terephthalate ), 12 polypropylene, 13 and polystyrene 14 is hardly dependent on the initial dye concentration, when it is below 1.5 x 10-4 molg-1 of the polymer. Since the initial probe concentration used here is .…”

Section: Resultsmentioning

confidence: 99%

“…The sublimative desorption apparatus shown in Figure 1 was used, and is similar to that used by Okajima et al 12 In this apparatus two sublimation tubes are available simultaneously. Strips measuring 1.0 cm x 4.0 cm were cut out of the film containing the spin probe, placed in a sublimation tube, preheated for 20 min, and then the tubes were evacuated to achieve a pressure less than 1 x 10-3 Torr.…”

Section: Sublimative Desorption Measurementsmentioning

confidence: 99%

“…9 In the present study, a sublimative desorption method was used to determine the translational diffusion coefficients of two nitroxide spin probes in two nylon films, for comparison with their rotational motions as investigated in our previous papers. 2 • 6 This desorption method has been widely used to investigate the progressive diffusion of dyes and their model compounds in polymer films such as poly-( ethylene terephthalate ), 12 polypropylene, 13 polystyrene, 14 and so on. Here we discuss the relationships between the activation energies for translation and rotation, taking into consideration the structures of the probe molecules and of the nylons.…”

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confidence: 99%

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Translational and Rotational Diffusion of Spin Probes in Nylon Films

Hamada

Amachi

Yonetake

et al. 1987

Polym J

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ABSTRACT:The translational diffusion of nitroxide spin probes in nylon films was investigated by means of a sublimative desorption method, and compared with their rotational diffusion as determined by an electron spin resonance (ESR) technique in our previous papers. The translational diffusion coefficients D calculated using McBain's formula were dependent on the structures of the spin probes, and on the structures of the nylons. The Arrhenius plots of D defined one distinct crossover point for each probe in the temperature range examined, which was quite consistent with that found in the Arrhenius plots of the rotational diffusion coefficients R. This suggests that the motional change of the nylon chains affects not only the translational motions of the probes but also their rotation. However, the activation energies for translational and rotational diffusion were very different; the activation energies for translation were larger below the crossover point than above it, whereas those for rotation behaved in the opposite manner. This discrepancy can perhaps be explained by the differences between the time-scales of the motions detected in the translational and rotational measurements. The results obtained here are compared with those for polyethylene, natural rubber, and polyisobutylene reported elsewhere.KEY WORDS Spin Probe / Nitroxide / Diffusion / Nylon / Molecular Motion/ The relationship between translational and rotational diffusion is of interest in the fields of membrane science and dyeing chemistry. Knowledge of this relationship should provide useful information on the mechanism of transport.We have investigated the rotational mobilities of spin probes in nylon films by means of an electron spin resonance (ESR) technique.1-6 It was found that the rotational mobilities were strongly influenced not only by the structures of the spin probes and of the nylons, but also by the molecular interactions between the probe molecules and the polymer chains. In addition, the rotational motions of the probe molecules in the "high" temperature region were interpreted by taking into account their simultaneous translational diffusion. 3 From this point of view, it is worthwhile to examine the translational diffusion of the spin probes by an independent method, for comparison with their rotational diffusion.Some papers have reported on the relationships between translational and rotational diffusion of nitroxide spin probes in polymer matrices. 7 -11 Stryukov used a method of scan-1 Permanent address:

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Sublimative Desorption Measurementsmentioning

confidence: 99%

mentioning

confidence: 99%

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Translational and Rotational Diffusion of Spin Probes in Nylon Films

Hamada

Amachi

Yonetake

et al. 1987

Polym J

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“…We constructed a polymer/solute diffusivity database by conducting a literature search for diffusivity measurements of dilute solutes (<2 wt%) in non‐dilute polymers (i.e., not hydrogels or polymer solutions) at any temperature, for any solute, and using any experimental method …”

Section: Methodsmentioning

confidence: 99%

Robust estimates of solute diffusivity in polymers for predicting patient exposure to medical device leachables

Elder

Saylor

2023

Journal of Polymer Science

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Medical devices often include polymeric components, which contain additives or contaminants that may leach into patients and pose a health risk. Previously, we proposed a mass transport model that conservatively estimates the leaching kinetics and only requires the solute's diffusion coefficient in the polymer, , to be specified. Because determining experimentally is time‐consuming, we also parameterized empirical models to estimate worst‐case values using only the solute molecular weight, . These models were based on a modest database and were limited to 19 polymers and larger solutes ( g/mol). Here, we assemble a much larger database, which enables us to construct more accurate models using a robust statistical approach, expanding the coverage to 50 device‐relevant polymers and smaller solutes ( g/mol). Then, we demonstrate several applications of these bounds, including modeling the release kinetics. Finally, we observe an interesting phenomenon, a discontinuous drop in of up to 25,000× for solutes with g/mol in glassy polymers. Using molecular simulations and cheminformatics tools, we propose a novel definition of the effective diameter of free volume channels in polymers, and we show that solutes larger than this channel size diffuse much more slowly.

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Glass Transition Temperatures of Polymers

Andrews

Grulke

1999

The Wiley Database of Polymer Properties

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VI-244 4.6. Poly(benzimidazoles) VI-245 4.7. Poly(benzothiazinophenothiazines) VI-245 4.8. Poly(benzothiazoles) VI-245 4.9. Poly(benzoxazlnes) VI-245 4.10. Poly(benzoxazoles) VI-245 4.11. Poly(carboranes) VI-245 4.12. Poly(dibenzofurans) VI-246 4.13. Poly(dioxoisoindolines) VI-246 4.14. Poly(fluoresceins) VI-247 4.15. Poly(furan tetracarboxylic acid diimides) VI-247 4.16. Poly(oxabicyclononanes) VI-247 4.17. Poly(oxadiazoles) VI-248 4.18. Poly(oxindoles) VI-248 4.19. Poly(oxoisoindolines) VI-248 4.20. Poly(phthalazines) VI-248 4.21. Poly(phthalides) VI-248 4.22. Poly(piperazines) VI-248 4.23. Poly(piperidines) VI-249 4.24. Poly(pyrazinoquinoxalines) VI-249 4.25. Poly(pyrazoles) VI-249 4.26. Poly(pyridazines) VI-249 4.27. Poly(pyridines) VI-249 4.28. Poly(pyromellitimides) VI-249 4.29. Poly(pyrrolidines) VI-250 4.30. Poly(quinones) VI-250 4.31. Poly(quinoxalines) VI-250 4.32. Poly(triazines) VI-252 4.33. Poly(triazoles) VI-252 Table 5. Copolymers VI-252 G. References VI-253 A. INTRODUCTIONAmorphous (noncrystalline) polymeric solids are either glasses or rubbers. A glassy polymer lacks long range order, and is below the temperature at which molecular motions take place on the time scale of the experiment. A rubbery polymer is above the temperature at which molecular motions take place on the time scale of the experiment. The glass transition temperature, T g , is the critical temperature that separates glassy behavior from rubbery behavior. Many amorphous solids, including polymers, organic liquids, biomaterials, some metals and alloys, and inorganic oxide glasses, exhibit glass transition temperatures. The dramatic change in the local movement of polymer chains at T g leads to large changes in a host of physical properties. These properties include density, specific heat, mechanical modulus, mechanical energy absorption, dielectric coefficients, acoustical properties, viscosity, and the rate of gas or liquid diffusion through the polymer, to name a few. Any of these properties can be used, at least in a crude manner, to determine T g . References page VI -253 Specific volume Gl assCrystal l i zati on vol ume change Li qui d

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Studies on sublimation of disperse dye out of dyed polymers. I. Rate of sublimation and amorphous transition points of poly(ethylene terephthalate)

Cited by 14 publications

References 24 publications

Translational and Rotational Diffusion of Spin Probes in Nylon Films

Translational and Rotational Diffusion of Spin Probes in Nylon Films

Robust estimates of solute diffusivity in polymers for predicting patient exposure to medical device leachables

Glass Transition Temperatures of Polymers

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