Experimental and Modeling Study of Gas Adsorption in Metal-Organic Framework Coated on 3D Printed Plastics

Indiana University-Purdue University Indianapolis (IUPUI)Metal-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

Optimization of Printing Parameters for 3-D Printed PLA

In this work, 3D printed part of PLA was checked for dimensional accuracy and printing parameters were optimized for getting optimal design. For doing so we selected nozzle temperature and step size as printing parameters for optimization. Design of Experiment (DOE) was done using Minitab to check optimal parameters. We concluded that increasing the nozzle temperature increases the dimensional accuracy of the printed part and decreasing the step size will increase the dimensional accuracy

Simulation of Spatters Sticking Phenomenon in Laser Powder Bed Fusion Process Using the Smoothed Particle Hydrodynamics Method

In this work, a smoothed particle hydrodynamics (SPH) method is developed to simulate the spattering phenomenon in the laser powder bed fusion (L-PBF) process. First, an experiment using the high-speed synchrotron X-ray full-field imaging is conducted to acquire in-situ images during the L-PBF process. Then, a scenario is selected from the X-ray image as a case study of the SPH model. In the case study, a particle is ejected and melted by the metal vapor, impacts with another particle, solidifies, and sticks to the other particle to form a rigid body. As a result, the trajectories of the two particles match well with the experimental observation. The evolution of velocity and temperature of the particle is extracted from the simulation for analysis. The SPH model can be a useful alternative to computational models of simulating the spattering phenomenon of L-PBF

Molecular dynamics modeling of mechanical and tribological properties of additively manufactured AlCoCrFe high entropy alloy coating on aluminum substrate

In this work, an improved molecular dynamics (MD) model is developed to simulate the nanoindentation and tribological tests of additively manufactured high entropy alloys (HEA) AlCoCrFe coated on an aluminum substrate. The model shows that in the interface region between the HEA coating and Al substrate, as the laser heating temperature increases during the HEA coating additive manufacturing process, more Al in the substrate is melted to react with other elements in the coating layer, which is qualitatively in agreement with experiment in literature. Using the simulated nanoindentation tests, the calculated Young's modulus of pure Al and Al with HEA coating is 79.93 GPa and 119.30 GPa, respectively. In both our simulations and the experimental results in the literature, the hardness of Al with the HEA coating layer is about 10 times higher than the Al hardness, indicating that HEA can significantly improve the hardness of the metallic substrate. Using the simulated tribological scratch tests, the computed wear tracks are qualitatively in agreement with experimental images in literature. Both our model and experiment show that the Al with HEA coating has a much smaller wear track than that of Al, due to less plastic deformation, confirmed by a dislocation analysis. The computed average coefficient of friction of Al is 0.62 and Al with HEA coating is 0.14. This work demonstrates that the HEA coating significantly improves the mechanical and tribology properties, which are in excellent agreement with the experiments reported in the literature

High Performance Thermal Barrier Coatings on Additively Manufactured Nickel Base Superalloy Substrates

IUPUIThermal barrier coatings (TBCs) made of low-thermal-conductivity ceramic topcoat, metallic bond coat and metallic substrate, have been extensively used in gas turbine engines for thermal protection. Recently, additive manufacturing (AM) or 3D printing techniques have emerged as promising manufacturing techniques to fabricate engine components. The motivation of the thesis is that currently, application of TBCs on AM’ed metallic substrate is still in its infancy, which hinders the realization of its full potential. The goal of this thesis is to understand the processing-structure-property relationship in thermal barrier coating deposited on AM’ed superalloys. The APS method is used to deposit 7YSZ as the topcoat and NiCrAlY as the bond coat on TruForm 718 substrates fabricated using the direct metal laser sintering (DMLS) method. For comparison, another TBC system with the same topcoat and bond coat is deposited using APS on wrought 718 substrates. For thermomechanical property characterizations, thermal cycling, thermal shock (TS) and jet engine thermal shock (JETS) tests are performed for both TBC systems to evaluate thermal durability. Microhardness and elastic modulus at each layer and respective interfaces are also evaluated for both systems. Additionally, the microstructure and elemental composition are thoroughly studied to understand the cause for better performance of one system over the other. Both TBC systems showed similar performance during the thermal cycling and JETS test but TBC systems with AM substrates showed enhanced thermal durability especially in the case of the more aggressive thermal shock test. The TBC sample with AM substrate failed after 105 thermal shock cycles whereas the one with wrought substrate endured a maximum of 85 cycles after which it suffered topcoat delamination. The AM substrates also demonstrated an overall higher microhardness and elastic modulus except for post thermal cycling condition where it slightly underperformed. This study successfully demonstrated the use of AM built substrates for an improved TBC system and validated the enhanced thermal durability and mechanical properties of such a system. A modified YSZ TBC architecture with an intermediate Ti3C2 MXene layer is proposed to improve the interfacial adhesion at the topcoat/bond coat interface to improve the thermal durability of YSZ TBC systems. First principles calculations are conducted to study the interfacial adhesion energy in the modified and conventional YSZ TBC systems. The results show enhanced adhesion at the bond coat/MXene interface. At the topcoat/MXene interface, the adhesion energy is similar to the adhesion energy between the topcoat and bond coat in a conventional YSZ TBC system. An alternative route is proposed for the fabrication of YSZ TBC on nickel base superalloy substrates by using the SPS technology. SPS offers a one-step fabrication process with faster production time and reduced production cost since all the layers of the TBC system are fabricated simultaneously. Two different TBC systems are processed using the same heating protocol. The first system is a conventional TBC system with 8YSZ topcoat, NiCoCrAlY bond coat and nickel base superalloy substrate. The second system is similar to the first but with an addition of Ti3C2 MXene layer between the topcoat and the bond coat. Based on the first principles study, addition of Ti3C2 layer enhances the adhesion strength of the topcoat/bond coat interface, an area which is highly susceptible to spallation. Further tests such as thermal cycling and thermal shock along with the evaluation of mechanical properties would be carried out for these samples in future studies to support our hypothesis

High Performance Thermal Barrier Coatings On Additively Manufactured Nickel Base Superalloy Substrates

Thermal barrier coatings (TBCs) made of low-thermal-conductivity ceramic topcoat, metallic bond coat and metallic substrate, have been extensively used in gas turbine engines for thermal protection. Recently, additive manufacturing (AM) or 3D printing techniques have emerged as promising manufacturing techniques to fabricate engine components. The motivation of the thesis is that currently, application of TBCs on AM’ed metallic substrate is still in its infancy, which hinders the realization of its full potential. The goal of this thesis is to understand the processing-structure-property relationship in thermal barrier coating deposited on AM’ed superalloys. The APS method is used to deposit 7YSZ as the topcoat and NiCrAlY as the bond coat on TruForm 718 substrates fabricated using the direct metal laser sintering (DMLS) method. For comparison, another TBC system with the same topcoat and bond coat is deposited using APS on wrought 718 substrates. For thermomechanical property characterizations, thermal cycling, thermal shock (TS) and jet engine thermal shock (JETS) tests are performed for both TBC systems to evaluate thermal durability. Microhardness and elastic modulus at each layer and respective interfaces are also evaluated for both systems. Additionally, the microstructure and elemental composition are thoroughly studied to understand the cause for better performance of one system over the other. Both TBC systems showed similar performance during the thermal cycling and JETS test but TBC systems with AM substrates showed enhanced thermal durability especially in the case of the more aggressive thermal shock test. The TBC sample with AM substrate failed after 105 thermal shock cycles whereas the one with wrought substrate endured a maximum of 85 cycles after which it suffered topcoat delamination. The AM substrates also demonstrated an overall higher microhardness and elastic modulus except for post thermal cycling condition where it slightly underperformed. This study successfully demonstrated the use of AM built substrates for an improved TBC system and validated the enhanced thermal durability and mechanical properties of such a system. A modified YSZ TBC architecture with an intermediate Ti3C2 MXene layer is proposed to improve the interfacial adhesion at the topcoat/bond coat interface to improve the thermal durability of YSZ 12 TBC systems. First principles calculations are conducted to study the interfacial adhesion energy in the modified and conventional YSZ TBC systems. The results show enhanced adhesion at the bond coat/MXene interface. At the topcoat/MXene interface, the adhesion energy is similar to the adhesion energy between the topcoat and bond coat in a conventional YSZ TBC system. An alternative route is proposed for the fabrication of YSZ TBC on nickel base superalloy substrates by using the SPS technology. SPS offers a one-step fabrication process with faster production time and reduced production cost since all the layers of the TBC system are fabricated simultaneously. Two different TBC systems are processed using the same heating protocol. The first system is a conventional TBC system with 8YSZ topcoat, NiCoCrAlY bond coat and nickel base superalloy substrate. The second system is similar to the first but with an addition of Ti3C2 MXene layer between the topcoat and the bond coat. Based on the first principles study, addition of Ti3C2 layer enhances the adhesion strength of the topcoat/bond coat interface, an area which is highly susceptible to spallation. Further tests such as thermal cycling and thermal shock along with the evaluation of mechanical properties would be carried out for these samples in future studies to support our hypothesis.</p

Gaussian Process-Based Model to Optimize Additively Manufactured Powder Microstructures From Phase Field Modeling

A persistent problem in the selective laser sintering process is to maintain the quality of additively manufactured parts, which can be attributed to the various sources of uncertainty. In this work, a two-particle phase-field microstructure model has been analyzed using a Gaussian process-based model. The sources of uncertainty as the two input parameters were surface diffusivity and interparticle distance. The response quantity of interest (QOI) was selected as the size of the neck region that develops between the two particles. Two different cases with equal and unequal-sized particles were studied. It was observed that the neck size increased with increasing surface diffusivity and decreased with increasing interparticle distance irrespective of particle size. Sensitivity analysis found that the interparticle distance has more influence on variation in neck size than that of surface diffusivity. The machine learning algorithm Gaussian process regression was used to create the surrogate model of the QOI. Bayesian optimization method was used to find optimal values of the input parameters. For equal-sized particles, optimization using Probability of Improvement provided optimal values of surface diffusivity and interparticle distance as 23.8268 and 40.0001, respectively. The Expected Improvement as an acquisition function gave optimal values of 23.9874 and 40.7428, respectively. For unequal-sized particles, optimal design values from Probability of Improvement were 23.9700 and 33.3005, respectively, while those from Expected Improvement were 23.9893 and 33.962, respectively. The optimization results from the two different acquisition functions seemed to be in good agreement

Developing Virtual Reality Module to Improve Student Learning Experience in Additive Manufacturing Curriculum

In our current additive manufacturing (AM) curriculum, the study relies on taking lectures and physical lab experiments. With the advance of virtual reality (VR) technologies in terms of both software and hardware, there is a need to advance the education with adopting advanced VR technologies. In this project, we present our latest results of developing new VR modules in AM curriculum. Specifically, the developed VR modules for fusion deposition modeling and fatigue testing will be presented. In the on-going research, students will be required to use the VR modules in comparison with the physical lab experiments. The focus will be understanding the effectiveness of VR technology on engineering curriculum

Smoothed Particle Hydrodynamics Modeling of Thermal Barrier Coating Removal Process Using Abrasive Water Jet Technique

In this work, a new smoothed particle hydrodynamics (SPH)-based model is developed to simulate the removal process of thermal barrier coatings (TBCs) using the abrasive water jet (AWJ) technique. The effects of water jet abrasive particle concentration, incident angle, and impacting time on the fracture behavior of the TBCs are investigated. The Johnson–Holmquist plasticity damage model (JH-2 model) is used for the TBC material, and abrasive particles are included in the water jet model. The results show that the simulated impact hole profiles are in good agreement with the experimental observation in the literature. Both the width and depth of the impact pit holes increase with impacting time. The deepest points in the pit hole shift gradually to the right when a 30-deg water jet incident angle is used because the water jet comes from the right side, which is more effective in removing the coatings on the right side. A higher concentration of abrasive particles increases both the width and depth, which is consistent with the experimental data. The depths of the impact pit holes increase with the water jet incident angle, while the width of the impact holes decreases with the increase in the water jet incident angle. The water jet incident angle dependence can be attributed to the vertical velocity components. The erosion rate increases with the incidence angle, which shows a good agreement with the analytical model. As the water jet incident angle increases, more vertical velocity component contributes to the kinetic energy which is responsible for the erosion process

Oxidation Behavior of NiCoCrAlY Coatings Deposited by Vacuum Plasma Spraying and High-Velocity Oxygen Fuel Processes

To reduce the formation of detrimental complex oxides, bond coatings in the thermal barrier coatings for gas turbines are typically fabricated using vacuum plasma spraying (VPS) or the high-velocity oxygen fuel (HVOF) process. Herein, VPS and HVOF processes were applied using NiCoCrAlY + HfSi-based powder to assess the oxidation behavior of the bond coatings for both coating processes. Each coated sample was subjected to 50 cyclic heat treatments at 950 °C for 23 h and cooling for 1 h at 20 °C with nitrogen gas, and the weight change during the heat treatment was measured to evaluate the oxidation behavior. After the oxidation test, the coating layer was analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The VPS coating exhibited faster weight gain than the HVOF coating because the alumina particles generated during the initial formation of the HVOF coating inhibited oxidation and diffusion. The VPS coating formed a dense and thick thermal growth oxide (TGO) layer until the middle of the oxidation test and remained stable until the end of the evaluation. However, the HVOF coating demonstrated rapid weight loss during the final 20 cycles. Alumina within the bond coat suppressed the diffusion of internal elements and prevented the Al from being supplied to the surface. The isolation of the Al accelerated the growth of spinel TGO due to the oxidation of Ni, Co, and Cr near the surface. The as-coated VPS coating showed higher hardness and lower interfacial bonding strength than the HVOF did. Diffusion induced by heat treatment after the furnace cyclic test (FCT) led to a similar internal hardness and bonding strengths in both coating layers. To improve the quality of the HVOF process, the densification of the coating layer, suppression of internal oxide formation, and formation of a dense and uniform alumina layer on the surface must be additionally implemented