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- All Subjects: Additive Manufacturing
- All Subjects: Catalysis
- Creators: Materials Science and Engineering Program
Description
The purpose of this honors project is to analyze the difference between different powder separation techniques, and their suitability for my capstone project – ‘Effect of Powder Reuse on DMLS (Direct Metal Laser Sintering) Product Integrity’. Due to the nature of my capstone project, my group needs to characterize foreign contaminants in IN 718 (Ni-based superalloy) powder with a mean diameter around 40um. In order to clearly analyze the contaminants and recycle useful IN 718 powders, powder separation is favorable since the filtered samples will be much easier to characterize rather than inspect all the powders at once under microscope. By conducting literature review, I found that powder separation is commonly used in Geology, and Chemistry department. To screen which combination of techniques could be the best for my project, I have consulted several research specialists, obtained adequate knowledge about powder separation. Accordingly, I will summarize the pros and cons of each method with regard the specific project that I am working on, and further explore the impacts of each method under economical, societal, and environmental considerations. Several powder separation techniques will be discussed in details in the following sections, including water elutriation, settling column, magnetic separation and centrifugation. In addition to these methods, sieving, water tabling and panning will be briefly introduced. After detailed comparison, I found that water elutriation is the most efficient way to purity IN718 powder for reuse purpose, and recovery rate is as high as 70%, which could result in a significant reduction in the manufacturing cost for Honeywell since currently Honeywell only use virgin powders to build parts, and 90% of the leftover powders are discarded.
ContributorsLuo, Zheyu (Author) / Adams, James (Thesis director) / Tasooji, Amaneh (Committee member) / Materials Science and Engineering Program (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Honeywell is currently extending the reach of additive manufacturing (AM) in its product line and expects to produce as much as 40% of its inventory through AM in five years. Additive manufacturing itself is expected to grow into a $3.1 billion dollar industry in the next 5 to 10 years. Reusing IN 718 powder, a nickel-based super alloy metal powder, is an ideal option to reduce costs as well as reduce waste because it can be used with additive manufacturing, but the main obstacles are lack of procedure standardization and product quality assurances from this process. The goal of the capstone project, "Effect of Powder Reuse on DMLS (Direct Metal Laser Sintering) Product Integrity," is to create a powder characterization protocol in order to determine if the IN 718 powder can be reused and what effect the IN 718 reused powder has on the mechanical properties of the products Honeywell fabricates. To provide context and impact of this capstone project, this paper serves to identify the benefits of AM for Honeywell and the cost effectiveness of reusing the powder versus using virgin powder every time. It was found that Honeywell's investment in AM is due to the cost effectiveness of AM, versatility in product design, and to ensure Honeywell remains competitive in the future. In terms of reducing expenses, reusing powder enables costs to be approximately 45% less than using virgin powder. With these key pieces of information, the motivations for this capstone project are understood to a fuller and more profound degree.
ContributorsQuigley, Elizabeth (Co-author) / Luo, Zheyu (Co-author) / Murella, Anoosha (Co-author) / Lee, Wey Lyn (Co-author) / Adams, James (Thesis director) / Tasooji, Amaneh (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Climate change is one of the biggest challenges facing today's society.Since the late 19th century, the global average temperature has been rising. In order to minimize the temperature increase of the earth, it is necessary to develop alternative energy technologies that do not depend on fossil fuels. Solar fuels are one potential energy source for the future. Solar fuel technologies use catalysts to convert low energy molecules into fuels via artificial photosynthesis. TiO2, or titania, is an important model photocatalyst for studying these reactions. It is also important to use remaining fossil fuel resources efficiently and with the lowest possible greenhouse gas emissions. Fuel cells are electrochemical devices that aim to accomplish this goal and CeO2, or ceria, is an important material used in these devices. One way to observe the atomic structure of a material is with a transmission electron microscope (TEM). A traditional transmission electron microscope employs a beam of fast electrons to form atomic resolution images of a material. While imaging gives information about the positions of the atoms in the material, spectroscopy gives information about the composition and bonding of the material. A type of spectroscopy that can be performed inside the transmission electron microscope is electron energy loss spectroscopy (EELS), which provides a fundamental understanding of the electronic structure of a material. The energy loss spectrum also contains information on the chemical bonding in the material, and theoretical calculations that model the spectra are essential to correctly interpreting this bonding information. FEFF is a software that performs EELS calculations. Calculations of the oxygen K edges of TiO2 and CeO2 were made using FEFF in order to understand the changes that occur in the spectrum when oxygen vacancies are introduced as well as the changes near a grain boundary.
ContributorsHussaini, Zahra (Author) / Crozier, Peter (Thesis director) / Rez, Peter (Committee member) / Jorissen, Kevin (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Materials Science and Engineering Program (Contributor) / Department of Physics (Contributor)
Created2013-12
Description
Additive Manufacturing and 3D printing are becoming important technologies in the manufacturing sector. The benefits of this technology include complex part geometry, short lead-times, low waste, and simple user interface. However, the technology does not come without its drawbacks: mainly the removal of support structures from the component. Traditional techniques that involve sawing and cutting can be expensive and take a long time, increasing the overall price of 3D printed metal components. This paper discusses two approaches taken for dissolvable support structures in 3D printed stainless steel (17-4 PH). For the first time in powder bed fusion components, with the help of Christopher Lefky and Dr. Owen Hildreth, dissolvable support capabilities are achieved in metal prints. The first approach, direct dissolution, involves direct corrosion of the entire part, leading to support removal. This approach is not self-terminating, and leads to changes in final component geometry. The second approach involves a post-build sensitization step, which physically alters the microstructure and chemical stability of the first 100-200 microns of the metal. The component is then etched at an electric potential that will readily corrode this sensitized surface, but not the underlying base metal. An electrolytic solution of HNO3/KCl/HCl paired with an anodic bias was used for the direct dissolution approach, resulting in a loss of about 120 microns of material from the components surface. For the self-limiting approach, surface sensitization was achieve through a post build annealing step (800 C for 6 hours, air cooled) with exposure to a sodium hexacynoferrate slurry. When the slurry decomposes in the furnace, carbon atoms diffuse into the surface and precipitate a chromium-carbide, which reduces the chemical stability of the stainless steel. Etching is demonstrated in an anodic bias of HNO3/KCl. To determine proper etching potentials, open circuit potential and cyclic voltammetry experiments were run to create Potentiodynamic Polarization Curves. Further testing of the self-terminating approach was performed on a 316 stainless steel interlocking ring structure with a complex geometry. In this case, 32.5 hours of etching at anodic potentials replaced days of mechanical sawing and cutting.
ContributorsZucker, Brian Nicholas (Co-author) / Lefky, Christopher (Co-author) / Hildreth, Owen (Co-author, Thesis director) / Hsu, Keng (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
This study analyzes mechanical properties of additively manufactured plastic materials produced in a conventional 3D printer. This topic has generally been studied in controlled scenarios, and this study aims to reflect the properties seen by consumers. Layered prints are inherently anisotropic due to the direction of the layers and associated weaknesses or stress concentrators. Thus, the ultimate strength and elastic modulus of plastic specimens produced using default settings are compared based on print orientation angle, and trends are observed. When a specimen is parallel to the build plate, it tends to have ultimate strength and elastic modulus near the published bulk values of 13.2MPa and 404-710MPa, but these values tend to decrease as the print angle increases.
ContributorsGarry, Allan Edward (Author) / Patel, Jay (Thesis director) / Mertz, Benjamin (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Mechanical and Aerospace Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
ContributorsTata, Bharath (Author) / Deng, Shuguang (Thesis director) / Muhich, Christopher (Committee member) / Chemical Engineering Program (Contributor, Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
The standard for hybrid fuel grains is Hydroxyl-terminated polybutadiene (HTPB). With the advances in additive manufacturing, the promise of 3D printed fuel grains has become a possibility. Yet, 3D printed grains do not have as good of a regression rate as the casted HTPB grains. However, with 3D printing, the core of these grains can be printed to maximize surface area in contact with the oxidizer. The goal of this research is to print hybrid rocket fuel grains with various core geometries and test them on a small-scale hybrid test stand. While the hot fires are still under testing at the time of this abstract, the manufacturing posed an interesting outcome, being more time intensive than expected, contradicting the initial hypothesis of faster manufacturing. Future endeavors will continue research into the cores of the 3D printed grains, possible multi-material made grains and creating core structures for HTPB grains from 3D printed materials.
ContributorsRust, Daniel William Yun Jin (Author) / Rajadas, John (Thesis director) / Taconi, Carolyn (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
A scheme has been developed for finding the gas and temperature profiles in an environmental transmission electron microscope (ETEM), using COMSOL Multiphysics and the finite element method (FEM). This model should permit better correlation between catalyst structure and activity, by providing a more accurate understanding of gas composition than the assumption of homogeneity typically used. While more data is needed to complete the model, current progress has identified several details about the system and its ideal modeling approach.
It is found that at the low pressures and flowrates of catalysis in ETEM, natural and forced convection are negligible forms of heat transfer. Up to 250 °C, radiation is also negligible. Gas conduction, being enhanced at low pressures, dominates.
Similarly, mass transport is dominated by diffusion, which is most accurately described by the Maxwell-Stefan model. Bulk fluid flow is highly laminar, and in fact borders the line between continuum and molecular flow. The no-slip boundary condition does not apply here, and both viscous slip and thermal creep must be considered. In the porous catalyst pellet considered in this work, Knudsen diffusion dominates, with bulk flow being best described by the Darcy-Brinkman equation.
With these physics modelled, it appears as though the gas homogeneity assumption is not completely accurate, breaking down in the porous pellet where reactions occur. While these results are not yet quantitative, this trend is likely to remain in future model iterations. It is not yet clear how significant this deviation is, though methods are proposed to minimize it if necessary.
Some model-experiment mismatch has been found which must be further explored. Experimental data shows a pressure dependence on the furnace temperature at constant power, a trend as-yet unresolvable by the model. It is proposed that this relates to the breakdown of the assumption of fluid continuity at low pressures and small dimensions, though no compelling mathematical formulation has been found. This issue may have significant ramifications on ETEM and ETEM experiment design.
It is found that at the low pressures and flowrates of catalysis in ETEM, natural and forced convection are negligible forms of heat transfer. Up to 250 °C, radiation is also negligible. Gas conduction, being enhanced at low pressures, dominates.
Similarly, mass transport is dominated by diffusion, which is most accurately described by the Maxwell-Stefan model. Bulk fluid flow is highly laminar, and in fact borders the line between continuum and molecular flow. The no-slip boundary condition does not apply here, and both viscous slip and thermal creep must be considered. In the porous catalyst pellet considered in this work, Knudsen diffusion dominates, with bulk flow being best described by the Darcy-Brinkman equation.
With these physics modelled, it appears as though the gas homogeneity assumption is not completely accurate, breaking down in the porous pellet where reactions occur. While these results are not yet quantitative, this trend is likely to remain in future model iterations. It is not yet clear how significant this deviation is, though methods are proposed to minimize it if necessary.
Some model-experiment mismatch has been found which must be further explored. Experimental data shows a pressure dependence on the furnace temperature at constant power, a trend as-yet unresolvable by the model. It is proposed that this relates to the breakdown of the assumption of fluid continuity at low pressures and small dimensions, though no compelling mathematical formulation has been found. This issue may have significant ramifications on ETEM and ETEM experiment design.
ContributorsLangdon, Jayse Tanner (Author) / Crozier, Peter (Thesis director) / Hildreth, Owen (Committee member) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
This project sought to analyze the effects of recycling Inconel 718 powder for Direct Metal Laser Sintering (DMSL) for additive manufacturing by testing low cycle fatigue tensile samples ranging from virgin to ten times recycled. Fracture generally occurs at the sample surface where persistent slip planes form and accumulate to cause a sudden fracture leading to signature markings for various phases of crack growth. Effects caused by contamination would be found in the first region of crack growth at the initiation site as the cause stress concentration. Tensile strength and fatigue life were compared to initiation site size found from fracture images obtained using scanning electron microscope imaging which found no significant deviations from the expected surface cracking and LCF region of slip plane buildups. Contamination was not found at any initiation site indicating that fracture life was not impacted by the amount of powder recycling. LCF life ranged from 60,000 to 250,000 which the majority experiencing fractures near 120,000 cyclic loadings. If defect effects were to be found than the low fatigue life sample would exhibit them however its fracture surface did not exhibit contamination but a slight increase in porosity found in the phase III cracking region. The In 718 powders were also analyzed to determine that the primary powder contaminates were brush fibers used to sweep away unused powders during processing however these were not seen in the final DMLS samples.
ContributorsLaws, Alec Ky (Author) / Tasooji, Amaneh (Thesis director) / Eylon, Daniel (Committee member) / Materials Science and Engineering Program (Contributor) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05