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Hill, Matthew R.

Publications and source records attributed to Hill, Matthew R..

How Reproducible are Surface Areas Calculated from the BET Equation?

Abstract Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro‐ and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already‐measured raw adsorption isotherms were provided to sixty‐one labs, who were asked to calculate the corresponding BET areas. This round‐robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well‐known Rouquerol criteria and makes an unambiguous BET area assignment possible.

36 MATERIALS SCIENCE↗

Pure- and mixed-gas transport properties of a microporous Tröger's Base polymer (PIM-EA-TB)

Polymers of intrinsic microporosity (PIMs) offer tantalizing combinations of high selectivity and permeability in initial gas permeation measurements. Here, we report characterization of pure- and mixed-gas permeation properties of a thick (~80 μm) PIM consisting of Tröger's Base (TB) and Ethanoanthracene (EA) films. The effects of feed pressure and temperature on pure-gas permeabilities of CH 4 , N 2 , O 2 , H 2 , and CO 2 were investigated. The physical aging behavior of the thick film was tracked via pure-gas O 2 , N 2 , and CH 4 permeability at 35 °C. Gas permeability decreased noticeably and selectivity increased as aging time increased. Particular attention was given to mixed-gas measurements of CO 2 and CH 4 (50/50) permeabilities at 35 °C and fugacities ranging from 2 to 18 atm to explore whether the rigid, bridged, bicyclic TB and EA units could resist CO 2 -induced plasticization. These results are presented along with pure-gas CO 2 and CH 4 results for membrane samples aged at different times. PIM-EA-TB aged for ~24 h did not show signs of plasticization across the fugacity range considered. Furthermore, dual-mode competitive sorption presumably caused the CO 2 /CH 4 mixed-gas selectivity to be slightly higher than its corresponding pure-gas selectivity. However, as aging time increased, aged films underwent progressively more rapid and extensive CO 2 -induced plasticization with increasing fugacity, suggesting a systematic relationship between physical aging and plasticization in PIMs. Consequently, physical aging caused less improvement in mixed-gas CO 2 /CH 4 selectivity than it did in pure-gas selectivity, due mainly to plasticization effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗