As a subset of the metal-organic frameworks, zeolitic imidazolate frameworks (ZIFs) have potential use in practical separations as a result of flexible yet reliable control over their pore sizes along with their chemical and thermal stabilities. Among many ZIF materials, we explored the effect of thermal treatments on the ZIF-7 structure, known for its promising characteristics toward H2 separations; the pore sizes of ZIF-7 (0.29 nm) are desirable for molecular sieving, favoring H2 (0.289 nm) over CO2 (0.33 nm). Although thermogravimetric analysis indicated that ZIF-7 is thermally stabile up to ~400 °C, the structural transition of ZIF-7 to an intermediate phase (as indicated by X-ray analysis) was observed under air as guest molecules were removed. The transition was further continued at higher temperatures, eventually leading toward the zinc oxide phase. Three types of ZIF-7 with differing shapes and sizes (~100 nm spherical, ~400 nm rhombic-dodecahedral, and ~1300 nm rod-shaped) were employed to elucidate (1) thermal structural transitions while considering kinetically relevant processes and (2) discrepancies in the N2 physisorption and CO2 adsorption isotherms. The largest rod-shaped ZIF-7 particles showed a delayed thermal structural transition toward the stable zinc oxide phase. The CO2 adsorption behaviors of the three ZIF-7s, despite their identical crystal structures, suggested minute differences in the pore structures; in particular, the smaller spherical ZIF-7 particles provided reversible CO2 adsorption isotherms at ~30-75 °C, a typical temperature range of flue gases from coal-fired power plants, in contrast to the larger rhombic-dodecahedral and rod-shaped ZIF-7 particles, which exhibited hysteretic CO2 adsorption/desorption behavior.

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We compared four types of ZIF-8 with varying sizes and shapes to determine their thermal-structural stability and derive appropriate thermal activation conditions and correlation between structural characteristics and adsorption properties. Under air, the ZIF-8 phase for all the samples was converted completely into the zinc oxide phase above ∼300°C, though thermalgravimetric analysis (TGA) indicated that the original structure was stable to ∼300−350°C. Longer exposures (∼30 d) suggested that thermal activation at ∼200°C was appropriate for the removal of guest and/or solvent molecules under air without structural damage. Despite no noticeable change in X-ray diffraction (XRD) patterns after activation at 250°C under air, the resulting BET surface areas and CO 2 adsorption amounts (at 1 bar and 30°C) of ZIF-8s were reduced to ∼44−54 and ∼72−87%, respectively, as compared to those of appropriately activated ZIF-8s. It appears that after the activation at 250°C under air, some Zn and N atoms were dissociated and converted to ZnOH and NOH, respectively, causing the partial structural damage of ZIF-8s.

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Purpose:The aim of this study was to investigate the influence of short and long duration sintering on microstructure and flexural strength of zirconia.Methods: To conduct three-point bending test, Zirconia specimens are milled according to ISO 6872 guidelines(N=18, n=9 per group). Two specimens group(n=8) is sintered for 10 hours(Standard schedule) and 3 hours(Speed schedule) at the peak temperature of 1550°C with silicon carbide sintering furnace. Flexural strength of specimens are measured by instron. After coating each specimen(n=1), microstructure of specimens is observed using Scanning Electron Microscope(SEM). T-test was utilized to statistically assess the data.Results: The mean and standard deviation value of the flexural strength for standard schedule group are 578.15±57.48Mpa, that of speed schedule are 465.9±62.34Mpa. T-test showed significant differences in flexural strength between two zirconia specimen group which applied standard schedule and speed schedule respectively(p<0.05). Conclusion:The result of this study showed that the increase in sintering time led to increased grain size, and also to a positive effect on the flexural strength.

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