IUPAC-NIST Solubility Data Series 70. Solubility of Gases in Glassy Polymers

Abstract

Solubility of gases in polymers is an important property of polymeric materials relevant to many practical applications. Sorption of small molecules in polymers is a fundamental concern in such areas as food packaging, beverage storage, and polymer processing. However, by far the main interest in the solubility of gases in polymers, and especially in glassy polymers, is related to development of novel advanced materials for gas separation membranes. This is because the concentration gradient of a dissolved gas is the driving force of membrane processes. Development of these novel separation methods resulted in a rapid accumulation, in the recent literature, of thermodynamic data related to the solubility of gases in polymers at different temperatures and pressures. Polymers can be regarded as special cases of media intermediate between liquids and solids. As a consequence, modeling of gas sorption in polymers is very difficult and presents a permanent challenge to theoreticians and experimenters. The collection and critical evaluation of solubility data for various gas-polymer systems is relevant to both practical aspects of polymer applications and to fundamental studies of polymer behavior. This volume of the IUPAC-NIST Solubility Data Series summarizes the compilations and critical evaluations of the data on solubility of gases in glassy polymers. It is implied in this edition that ''gases'' are the components that are either permanent gases ͑supercitical fluids͒ or have saturated vapor pressure more than 1 atm at ambient conditions ͑298 K͒. The polymeric components of compilations and critical evaluations are primarily high molecular mass, amorphous, linear ͑noncross-linked͒ compounds that have the glass transition temperatures above ambient temperature. The data for each gas-polymer system have been evaluated, if the results of at least three independent and reliable studies have been reported. Where the data of sufficient accuracy and reliability are available, values are recommended, and in some cases smoothing equations are given to represent variations of solubility with changes in gas pressure and temperature. Referenced works are presented in the standard IUPAC-NIST Solubility Data Series format. Depending on the gas-polymer system, reported data are given in tabular form or in the form of sorption isotherms. The data included in the volume comprise solubilities of 30 different gases in more than 80 primarily amorphous homo and copolymers. Where available, the compilation or critical evaluation sheets include enthalpies of sorption and parameters for sorption isotherms. Throughout the volume, SI conventions have been employed as the customary units in addition to the units used in original publications.

Gas solubility of carbon dioxide in poly(lactic acid) at high pressures

“…In Figure 3, the solubility results of carbon dioxide in atactic polystyrene at two temperatures, 307.5 and 337.8 K and pressures up to 5 MPa are presented and compared with literature. The results obtained are in good agreement with the literature showing an average absolute deviation (AAD) around 8% at 308 K14, 15 and 3.3% at 338 K 14, 16. The experimental data were correlated with dual‐mode sorption model with an AAD of 4.0% at 307.5 K and 3.6% at 337.8 K. The dual‐mode sorption model parameters are presented in Table 3.…”

“… Solubility of carbon dioxide in atactic polystyrene at 337.8 (▪) and 307.5 K (•) measured with QCM at high pressures and comparison with literature: Wissinger and Paulaitis14 at 308 K (▵) and 338 K (○); Paterson and Yampol'skii15 at 308 K (‐‐‐‐); Hilic et al16 at 338 K (□). The solid lines are the correlation of the dual‐mode sorption model to the experimental results.…”

Sorption of light gases in glassy poly(ethyl methacrylate)

“…, some additional data were obtained in the present work (at 160 K and P < 0.5 atm, at 175 K and P < 0.5 atm, and at 273 K and atm). The figures demonstrate the typical dependence of the solubility coefficient on pressure and temperature . Note that, in the temperature range studied, the solubility coefficients for oxygen and argon are close to each other while the solubility coefficient for nitrogen is smaller by a factor of 1.7.…”

The Effect of High Pressure Processing on the Integrity of Polymeric Packaging – Analysis and Categorization of Occurring Defects

“…In the literature, however, most papers deal with pressures below 70 MPa. In this pressure range, the solubility of molecules in polymers increases with rising partial pressure (e.g …”