Diffusion of dye molecules in polymers above and below the glass transition temperature studied by the holographic grating technique

Coutandin, Jochen; Ehlich, Dietmar; Sillescu, H.; Wang, Chin Hsien

doi:10.1021/ma00145a050

Cited by 30 publications

(12 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The analysis of these data is divided into two parts: examination of the proposed correlation between D, (dye) and D,s( solvent), embodied in eqs. (8) and (9), followed by examination of the temperature dependence of D,. Because the solutions in which D, was measured fell in a narrow range of concentration, the concentration dependence of D, will not be examined explicitly.…”

Section: Results For T 2 Tgementioning

confidence: 99%

“…These parameters can now be used to predict D, (toluene) for the solutions in which D,(AB) and D,(AZ) have been measured, in order to examine eqs. (8) and ( 9 ) . These correlations are shown in Figure 3 and the correlation parameters are given in Table 111.…”

Section: Results For T 2 Tgementioning

confidence: 99%

“…Thus, the emphasis here is on the temperature dependence of D,. In particular, measurements of D, extend below the solution Tg, which permits examination of extensions to the basic Vrentas-Duda mode1.6~~ Recently, several FRS measurements of D, through Tg have been reported for probe dyes in bulk polymer samples, [8][9][10][11] but this article represents to our knowledge the first systematic study of D, below Tg for solutions. As with the PVA/ toluene system examined in Part I, the necessary parameters for quantitative application of the Vrentas-Duda equations are already a~a i l a b l e .~ Furthermore, because some of the solutions examined are more than 100°C below the polymer Tg, a fundamental weakness in free volume models for binary systems is exposed.…”

Section: Introductionmentioning

confidence: 92%

See 2 more Smart Citations

Probe diffusion in polystyrene/toluene solutions

Frick

Huang

Tirrell

et al. 1990

J Polym Sci B Polym Phys

View full text Add to dashboard Cite

The technique of forced Rayleigh scattering has been used to measure the tracer diffusion coefficient, Dt, for two photochromic dyes, azobenzene and Aberchrome 540, in polystyrene / toluene solutions, as a function of polymer concentration (79–90% by weight) and temperature (−15–+60°C). The dye diffusivity can be scaled quantitatively to the solvent diffusivity, permitting direct application of the Vrentas‐Duda free volume predictions for binary systems. However, the scaling factors are not in agreement with the model assumptions. The temperature and concentration dependence of Dt above the solution glass transition temperature, Tgs, is in good agreement with the model, without any freely adjustable parameters. The value of Dt at Tgs is a very strong function of concentration, increasing by a factor of 103 as the polymer concentration is reduced from 90 to 80%; this is also in quantitative agreement with the model. It is demonstrated that the temperature dependence of Dt exhibits a distinct break in the vicinity of Tgs, with both the existence and the character of the break in qualitative agreement with the extension of the Vrentas‐Duda approach to glassy solutions. However, a fundamental difficulty in the calculation of the polymer contribution to the solution free volume at temperatures well below the bulk polymer Tg is exposed.

show abstract

Section: Results For T 2 Tgementioning

confidence: 99%

Section: Results For T 2 Tgementioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

See 1 more Smart Citation

Probe diffusion in polystyrene/toluene solutions

Frick

Huang

Tirrell

et al. 1990

J Polym Sci B Polym Phys

View full text Add to dashboard Cite

show abstract

“…In this equation, E D is the activation energy of diffusion. This equation has proved to be of quite general applicability for gases and small‐molecule liquid penetrants over relatively small temperature intervals (25–70°C)32, 35–38 although some deviations have also been reported including a change of slope at the polymer glass transition temperature 21, 39…”

Section: Introductionmentioning

confidence: 99%

Diffusivity of alcohols in amorphous polystyrene

Bernardo

2012

J of Applied Polymer Sci

View full text Add to dashboard Cite

Gravimetry is used to study the diffusion of a homologous series of alcohols (C n , with n ¼ 1, 2, 3, 4, 6, 10, and 16) in amorphous polystyrene at temperatures from 35 to 145 C, that is both below and above the polymer glass transition temperature of 100 C. All the mass uptake results are well described by a simple Fickian model (for t < t 1/2 ) and are used to calculate the corresponding diffusion coefficients using the thin-film approximation. At any particular temperature, the alcohols C n with n ¼ 3, 4, and 6 possess very similar diffusivities despite the fact that the chain length doubles from C 3 to C 6 . This peculiar diffusivity behavior is explained based on the variation of the polymer-solvent chemical affinity along the homologous series. As expected, at any particular temperature, the diffusivity decreases considerably from C 6 to C 10 and from C 10 to C 16 . For each alcohol, its log(D) increases linearly with the decrease in liquid viscosity associated with an increase in temperature.

show abstract

“…This equation has proved to be of quite general applicability for gases and small molecule liquid penetrants over relatively small temperature intervals (25-70°C) [26,[28][29][30][31], although some deviations have also been reported including a change of slope at the polymer glass transition temperature [15,32].…”

Section: Introductionmentioning

confidence: 99%

Diffusivity of alkanes in polystyrene

Bernardo

2012

J Polym Res

View full text Add to dashboard Cite

Gravimetry is used to study the diffusivity of a homologous series of linear alkanes (C n , with n08, 10, 12, 14 and 16) in amorphous polystyrene at temperatures ranging from 45°C to 145°C, i.e. both below and above the polymer glass transition temperature (100°C). All the mass uptake results obtained are well described by a simple Fickian model (for t0.993, for all temperatures) with respect to the number of carbon atoms (n) in the alkyl chain, log(D) decreasing when n increases. For each liquid penetrant, over the temperature intervals considered, its log (D) also increases linearly (R 2 >0.996 for all the systems) with the decrease in the penetrant's liquid viscosity.

show abstract

Diffusion of dye molecules in polymers above and below the glass transition temperature studied by the holographic grating technique

Cited by 30 publications

References 2 publications

Probe diffusion in polystyrene/toluene solutions

Probe diffusion in polystyrene/toluene solutions

Diffusivity of alcohols in amorphous polystyrene

Diffusivity of alkanes in polystyrene

Contact Info

Product

Resources

About