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Item Experimental and Modeling Study of Gas Adsorption in Metal-Organic Framework Coated on 3D Printed Plastics(2020-05) Dube, Tejesh C.; Zhang, Jing; Tovar, Andres; Wei, XiaoliangMetal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs. The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffraction (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused deposition modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pressure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.Item Extrusion-Based 3D Printing of Molecular Sieve Zeolite for Gas Adsorption Applications(AIME, 2018-10) Hawaldar, Nishant; Park, Hye-Young; Jung, Yeon-Gil; Zhang, Jing; Mechanical Engineering and Energy, School of Engineering and TechnologyExtrusion based 3D printing is one of the emerging additive manufacturing technologies used for printing range of materials from metal to ceramics. In this study, we developed a customized 3D printer based on extrusion freeform fabrication technique, such as slurry deposition, for 3D printing of different molecular sieve zeolite monoliths like 3A, 4A, 5A and 13X to evaluate their performance in gas adsorption. The physical and structural properties of 3D printed zeolite monoliths will be characterized along with the gas adsorption performance. The Brunauer–Emmett–Teller (BET) test of 3D printed samples will be performed for calculation of the surface area, which will give us the capacity of gas absorption into 3D printed zeolite. The BET surface area test showed good results for Zeolite 13X compared to available literature. The surface area calculated for 3D – printed Zeolite 13X was 767m2/g and available literature showed 498 m2/g for 3D – printed Zeolite 13X. The microhardness values of 3D – printed Zeolite samples were measured using a Vicker hardness tester. The hardness value of the 3D - printed Zeolite samples increased from 8.3 ± 2 to 12.5 ± 3 HV 0.05 for Zeolite 13X, 3.3 ± 1 to 7.3 ± 1 HV 0.05 for Zeolite 3A, 4.3 ± 2 to 7.5 ± 2 HV 0.05 for Zeolite 4A, 7.4 ± 1 to 14.0 ± 0.5 HV 0.05 for Zeolite 5A, before and after sintering process, respectively. The SEM analysis was performed for 3D printed samples before and after sintering to evaluate their structural properties. The SEM analysis reveals that all 3D – printed Zeolite samples retained their microstructure after slurry preparation and also after the sintering process. The porous nature of 3D – printed Zeolite walls was retained after the sintering process.