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250 records · Page 14

Heavily Confined PBX 9501 Experiment Report FY2020

Most accidental insults to explosives are invariably thermal in nature—either direct thermal via application of heat or indirect thermal when mechanical energy is converted to heat. The key question is whether the initial thermal insult transitions into a violent explosive response. If the ultimate violence attained is moderate, nearby personnel may be harmed or killed, but Inadvertent Nuclear Detonation (IND) will not occur. However, if the explosive ultimately transitions from deflagration to detonation (DDT) then IND becomes a concern. PBX 9501 is not an insensitive high explosive (IHE). It has been conclusively demonstrated that mechanically and thermally damaged PBX 9501 can readily DDT in heavy confinement. However, it is currently unknown whether pristine explosive—i.e. thermally and mechanically undamaged— is capable of DDT. Three experiments were conducted in order to determine whether very heavily confined pristine PBX 9501 is capable of DDT. All experiments used identical 6-inch diameter spherical charges of PBX 9501 confined in a 350 lb. hardened steel vessel with >2.5-inch thick walls. The first, primary experiment tested pristine PBX 9501 and was thermally ignited at the center of using a laser over optical fiber. Two additional baseline experiments were performed for comparison: the second test was initiated at the center using a detonator; the third test was bulk heated until self-ignition (cookoff). Velocimetry data in combination with hydrocode simulations suggest that a classical detonation wave did not develop in the pristine, thermally ignited PBX 9501. Reaction violence was approximately equivalent—in terms of ultimate energy output—as a full detonation, but the acceleration of metal fragments occurred more slowly than in a detonation-driven scenario.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Ion temperature and rotation fluctuation measurements with ultra-fast charge exchange recombination spectroscopy (UF-CHERS) in the DIII-D tokamak

An upgraded detector and several optimizations have significantly improved the Ultra-Fast Charge Exchange Recombination Spectroscopy (UF-CHERS) diagnostic sensitivity to ion temperature and parallel velocity fluctuations at turbulence relevant spatio-temporal scales. Normalized broadband ion temperature and parallel velocity fluctuations down to x̃x∼1% (x = Ti, v∥) and up to ∼450 kHz have been measured in a variety of plasmas. The multi-field nature of the CHERS technique also allows measurements of the cross-phase angles of the fluctuating fields. UF-CHERS is optimized to observe emissions from the electron exchange reaction between intrinsic C6+ and hydrogenic neutral beam injected particles near 529 nm. UF-CHERS consists of two chords separated by ∼1 cm radially, less than the turbulence correlation length in DIII-D plasmas, which enables correlated measurements to suppress incoherent electronic and photon noise. The optical components of the spectrometer include a volume-phase-holographic grating with >90% transmission between 528 and 530 nm and f/2 200-mm lenses, selected to maximize the optical efficiency and photon flux. Diffracted light from each chord is collected in eight spectral bins, each with a bandwidth of ∼0.25 nm, and detected and amplified by chilled avalanche photodiodes and custom high-gain, wide bandwidth low-noise preamplifiers to achieve the optimal signal-to-noise ratio. The resulting signals are digitized at 1 MHz, 103–104× faster than the conventional CHERS diagnostics. Spatial coverage is achieved by repositioning a motorized fiber tray between plasmas. UF-CHERS measurements will advance the understanding of turbulent ion transport and contribute to the validation of transport models and simulations.

Truong, D. D. (ORCID:0000000285732539)↗

Lignin content of Populus trichocarpa residues after CELF pretreatment and CBP fermentation

Here we present a dataset of lignin content from a woody energy crop (Populus trichocarpa) residues after a series of co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment and consolidated bioprocessing (CBP) process. The natural poplar variant GW-9947 from the Center for Bioenergy Innovation (CBI) was used. The poplar was knife milled and passed through a 1 mm sieve and CELF pretreatment was performed in a Parr autoclave reactor with 7.5 wt % solids loading, 0.5 wt% H2SO4 as catalyst at 150°C with 5, 15, 25 and 30 minutes, respectively. Tetrahydrofuran was added in a 1:1 mass ratio with water as the pretreatment solvent. The residues from CELF pretreatment were then subjected to CBP using the bacterium C. thermocellum DSM 1313. CBP fermentations were performed at 60 °C in a shaker at 50, 75, and 100 grams/L solids loadings. The Klason lignin was measured using a two-step acid hydrolysis process. In brief, the poplar samples were first hydrolyzed by 72 wt% sulfuric acid at 30 oC for an hour. The hydrolysates were then diluted to 4 wt% sulfuric acid using deionized water and subsequently autoclaved at 121 oC for 1 h. Upon the completion of the two-step hydrolysis, the resulting solution was cooled to room temperature and the precipitate was then filtered through a G8 glass fiber filter through a crucible, dried at oven for overnight, and weighed to get the Klason lignin content. The lignin data provides information about lignin content changes after CELF and C. thermocellum CBP process.

Lignin Populus trichocarpa CELF pretreatment CBP f↗

Discrete element modeling of granular hopper flow of irregular-shaped deformable particles

Many natural and engineered granular materials have relatively deformable particles. Besides particle size and shape, particle deformability is another salient factor that significantly impacts the material’s flow behavior. Here, in this work, the flow of irregular-shaped deformable particles in a wedge-shaped hopper is investigated using discrete element simulations. A bonded-sphere model is developed to simultaneously capture irregular particle shapes and particle-wise deformations (e.g., compression, deflection, and distortion). Quantitative analysis of the effects of irregular shapes and particle deformations shows that the increase in particle stiffness tends to increase initial packing porosity and decrease the flow rate in the hopper. Rigid particles tend to have clogging issues, whereas deformable particles have less chance to, indicating particle deformation reduces the critical bridging width in the hopper flow. Detailed analysis of stress fields is also conducted to provide insights into the mechanism of particle flow and clogging. Stresses and discharge rates calculated from numerical simulations are compared and show good agreement with Walker’s theory and the extended Beverloo formula. Simulations with various particle shape combinations are also performed and show that the initial packing porosity decreases with an increasing percentage of fibers while the discharge rate has a complex dependency on particle shapes.

09 BIOMASS FUELS↗

Nanoweb Surface-Mounted Metal–Organic Framework Films with Tunable Amounts of Acid Sites as Tailored Catalysts

Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. In this work, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H 2 O) 3 coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu + sites, as the nanowebs mainly consist of coordinated Cu 2+ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nano-Engineered Catalyst Supported on Ceramic Hollow Fibers for the Utilization of CO 2 in Dry Reforming to Produce Syngas

The objective of this project was to develop a novel catalytic reactor containing nano-engineered catalysts for the utilization of CO 2 (captured from coal-fired power plants and other CO 2 emitting sources) in dry methane reforming (DMR) (CO 2 + CH 4 → 2 H 2 + 2 CO) to produce synthesis gas (syngas). The technology aims to reduce CO2 emissions by developing beneficial uses for CO 2 from coal-fired power plants. It also offers an alternative to mitigate CO 2 emissions in areas where geologic storage may not be an optimal solution and/or utilization could significantly offset the costs of carbon capture and sequestration. The nano-engineered Ni-based catalyst was prepared by atomic layer deposition (ALD). The Ni particles were as small as ~2-4 nm. The nano-engineered catalyst showed CH 4 conversion >95%, H 2 /CO ratio in the range of 0.7-1.0, and CH 4 reforming rate as high as 2,500 L/h/gNi at 850 ºC and pressure of 15-25 psia. The Ni-based ALD catalyst also showed good stability in DMR reaction during a 200-h continuous operation at 850 °C. This is due to strong bonding between the nanoparticles and substrates since the Ni nanoparticles were chemically bonded to the substrate during the ALD process. The high thermal stability maintains the high dispersion of Ni nanoparticles, which can inhibit coke formation because their step edges are small enough to limit carbon nucleation and growth. Technoeconomic analysis (TEA) indicates the levelized cost of syngas (LCOS) is $172/ton with our technology, which is lower than the equivalent (molar) cost of hydrogen produced by steam methane reforming (SMR) or autothermal reforming (ATR). The major operating cost is natural gas feed and fuel, and the levelized cost is highly sensitive to the price of natural gas and relatively insensitive to the CAPEX. Revenues from syngas could have a significant impact on the net cost of electricity (COE), depending on the cost of natural gas and the selling price of syngas, estimated at $36 per MWh if the syngas were sold at $195 per ton. Following DOE NETL’s guidance, a lifecycle analysis (LCA) was conducted to compare with SMR. The functional unit for the basis of comparison was defined as 1kg carbon monoxide in the product stream. The global warming potential (GWP) of our process was found to be 40% lower than the state-of-the-art SMR process. The sensitivity analysis confirms the emissions are most sensitive to the natural gas fuel requirements to deliver heat to the process.

01 COAL, LIGNITE, AND PEAT↗

Hybrid Ceramic-CMC Vane with EBC for Future Coal Derived Syngas Fired 65% Efficient Turbine Combined Cycle

The efficiency of both simple cycle and combined cycle power generation systems scale with the peak temperature at which the gas exits the combustor to drive the turbine. In conventional systems, a substantial fraction of the total turbine core flow exiting the compressor is diverted downstream to cool metallic turbine hardware rather than power the turbine, much of which is used to cool the first-stage turbine vane. The use of coal derived syngas fuels provides an additional challenge to the lifetime of materials utilized in the turbine, as particulate byproducts created in the coal gasification process melt in the combustion gas, and can subsequently deposit and interact with the turbine hardware. The development of durable hot-section materials capable of operating at temperature well above that of single crystal superalloy airfoil/zirconia based thermal barrier coatings is critical to realizing 65% efficient coal derived syngas fired gas turbine based power systems. To enable higher turbine inlet temperatures while lowering cooling air requirements, United Technologies Research Center (UTRC), the central R&D laboratory supporting UT Pratt & Whitney, led the conceptual design of a new type of ceramic composite turbine hot section materials system. The design focused on a novel hybrid monolithic ceramic-fiber reinforced ceramic matrix composite (CMC) first stage turbine vane having an environmental barrier coating. By utilizing ceramic construction in the turbine hot-section, the core flow normally used to cool metallic components will be substantially reduced, increasing efficiency and reducing emissions. To provide the framework for future demonstration testing, UTRC partnered with University of North Dakota Energy and Environmental Research Center (UNDEERC) to provide a conceptual design for a gasified coal fed high-pressure turbine combustor system designed to mimic the conditions expected in a future 65% fuel to busbar efficient syngas fueled gas turbine based combined cycle. The UNDEERC and UTRC collaborated on characterizing dusts from coal gasifier filtration systems.

10 SYNTHETIC FUELS↗

Membrane Carbonation for 100% Efficient Delivery of Industrial CO 2 Gases

Industrial processes generate about one quarter of all greenhouse gases emissions in the US, about 80% of which is carbon dioxide (CO 2 ). Biological processes are one of the largest natural sinks for atmospheric CO 2 , but the rate of capture is limited by the low concentration in air (~0.04%). Industrial emissions have significantly higher CO 2 concentrations, ranging from 5–80% CO 2 , which can significantly increase the rate of biological CO 2 capture, including many-fold improvements for cultivating microalgae to produce food, fertilizer, and renewable fuel. However, traditional methods for delivering CO 2 to microalgae using bubbling is < 40% efficient, leading to significant residual CO 2 emissions and increased cost. This project developed the Membrane Carbonation (MC) technology to significantly improve the CO 2 delivery efficiency to microalgae from power plant flue gas, wastewater treatment plant anaerobic digesters biogas (Figure 1), and other CO 2 -containing industrial sources.

09 BIOMASS FUELS↗

Characterization and assessment of the potential toxicity/pathogenicity of fibrous glaucophane

In California, the metamorphic blueschist occurrences within the Franciscan Complex are commonly composed of glaucophane, which can be found with a fibrous habit. Fibrous glaucophane's potential toxicity/pathogenicity has never been determined and it has not been considered by the International Agency for Research on Cancer (IARC) as a potential carcinogen to date. Notwithstanding, outcrops hosting fibrous glaucophane are being excavated today in California for building/construction purposes (see for example the Calaveras Dam Replacement Project - CDRP). Dust generated by these excavation activities may expose workforces and the general population to this potential natural hazard. In this work, the potential toxicity/pathogenicity of fibrous glaucophane has been determined using the fibre potential toxicity index (FPTI). This model has been applied to a representative glaucophane-rich sample collected at San Anselmo, Marin County (CA, USA), characterized using a suite of experimental techniques to determine morphometric, crystal-chemical parameters, surface reactivity, biodurability and related parameters. Additionally, with respect to the asbestos minerals, the FPTI of fibrous glaucophane is remarkably higher than that of chrysotile, and comparable to that of tremolite, thus supporting the application of the precautionary approach when excavating fibrous glaucophane-rich blueschist rocks. Because fibrous glaucophane can be considered a potential health hazard, just like amphibole asbestos, it should be taken into consideration in the standard procedures for the identification and assessment of minerals fibres in soil and air samples.

54 ENVIRONMENTAL SCIENCES↗

Bench-scale Development of a Transformational Graphene Oxide-based Membrane Process for Post-combustion CO 2 Capture

Graphene-based materials, such as graphene and graphene oxide (GO), have been considered as next-generation membrane materials. GTI Energy and The State University of New York at Buffalo (UB) have been developing a transformational GO-based membrane process (designated as GO2) that integrates a high CO 2 /N 2 selectivity membrane (GO-1) and a high CO 2 flux membrane (GO-2) for post-combustion CO 2 capture. An innovative membrane structure, consisting of GO nanochannels intercalated by single-walled carbon nanotube (SWCNT), was developed. The membrane prepared on hollow fiber substrate showed CO 2 permeance as high as 1,300 GPU with CO 2 /N 2 selectivity >200. The membranes were successfully scaled up to effective area of 50-100 cm 2 . The 50-100 cm 2 membranes showed CO 2 /N 2 selectivity ≥200 and CO 2 permeance ≥1,000 GPU for the GO-1 type, and CO 2 /N 2 selectivity ≥20 and CO 2 permeance ≥2,500 GPU for the GO-2 type. The CO 2 capture performance of the GO-based membranes was tested using a simulated flue gas. The testing results indicate that the GO-based membranes are stable in the presence of flue gas contaminants. The GO-based membranes were then further scaled up to a surface area of 1,000 cm 2 . Good stability was achieved during an integrated testing with GO-1 and GO-2 membranes using simulated flue gas. A bench-scale system was designed, constructed, and tested at the National Carbon Capture Center (NCCC). Good stability was achieved during testing of a single-stage process with >10 shutdowns/startups at NCCC. During the integrated testing, the membranes showed good stability at 50°C and 57°C. 70-90% CO 2 removal efficiencies and ≥95% CO 2 purity were validated during the steady state operation at NCCC. Techno-economic analysis indicates the GO2 membrane-based process technology provides a reduction in both the levelized cost of electricity (LCOE) and cost of capture when compared to the reference B12B case presented in the Cost and Performance Baseline for Fossil Energy Plants Volume 1: Bituminous Coal and Natural Gas to Electricity study prepared by the National Energy Technology Laboratory (NETL), before considering any system optimization or improvement opportunities. The benefits are primarily driven by a reduction in the equipment costs of the CO 2 capture process vs. the solvent-based reference process in NETL Case B12B as well as a decrease in the base plant size.

20 FOSSIL-FUELED POWER PLANTS↗

Effects of Surface Modifications of Kraft Wood Pulp Cellulose Fibres on Improving the Mechanical Properties of Cellulose Fibre/Latex Composites

In this work, three composites with different contents (5, 10, and 15% w/w) of kraft pulp fibre were produced as reinforcing elements for natural latex matrix and the mechanical properties were evaluated. In order to improve the interfacial adhesion between the matrix and the reinforcing element, chemical modifications were carried out on the surface of the fibres using octanoyl and benzoyl chlorides as modifying agents. The extension of chemical modification of the fibres was visualized by the presence of absorption bands in the spectroscopy analyzes of the modified fibre in relation to the crude fibre (ester carbonyl 1700–1740 cm{sup −1}); in addition, the hydroxyl band was preserved, which indicates a modification of surface character. The modified fibres became more hydrophobic due to the decrease in surface energy and the change in the dispersive and polar components. An increase in the storage modulus was observed for the composites with surface-modified fibres, which agrees with the improved dispersion between the surface-modified fibres and the matrix verified by means of scanning electron microscopy images. The incorporation of fibres did not cause changes in the thermal properties of the composites.

36 MATERIALS SCIENCE↗

Advancing Enhanced Raman Spectroscopy to Detect and Measure NOW Pheromones (CPRB 2022 proposal)

Insect sex pheromones are chemical compounds that insects release to attract their partners over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts. These pheromone-based strategies can include monitoring, mating disruption, mass trapping, attract-and-kill and push-pull. There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage by this pest. Just how mating disruption works is not fully established and likely varies across products and target species. For instance, the extent to which synthetic pheromones compete with natural pheromone is not well understood, or in the case of monitoring, how efficaciously the insect follows the diffusing plumes, especially across large blocks and at plot borders. Furthermore, there may be specific conditions under which poor or impeded diffusion of synthetic pheromone diminishes the disruption effect, which could result in some males effectively locating females for reproduction. At the same time, many commercially available synthetic lures are also available, and growers have been effectively using them to track population development – although the attractive range of these lures remains unclear. That is, while pheromone lures can attract many moths, the relationship between trap capture and local populations, much less crop damage, remains unclear. Regardless of the emission source (aerosol puffers, meso emitters, lures etc.), we currently lack the ability to fully understand how these synthetic pheromone compounds diffuse away from their point-source of emission – and subsequently how this might affect the efficacy of mating disruption and/or the accuracy of monitoring efforts. Raman spectroscopy (RS) may offer a means to detect synthetic pheromone because of its analytical properties and recent technological advancements. In combination with nanostructured probes, RS has a demonstrated capability to detect volatiles at extremely low concentrations. While other methods for detecting pheromones have proven to be successful, such analytical methods like mass spectrometry (MS) gas chromatography (GC) require sampling in the fields and are not real-time. Other methods such as EAG/ EAD are also invasive (use antennas) but are of course valuable. Opto-electronic, micro and nano sensors just recently enticed interest. We fall in this latter category, proposing the use of optical spectroscopy (Raman) in a fiber aided by nanostructures to provide a chemical fingerprint without transductions and in real-time (i.e. no sampling). To date, we have been able to generate Raman signatures for the main chemicals in synthetic pheromones (a first for science, to the best of our knowledge), observe their trends at different concentrations, and also provide a clear distinction of such signatures in mixed samples via Principal Component Analysis (PCA) – all of which strengthens our conclusions on the ability of RS to detect emissions in more realistic conditions. We also established processes to enhance the detection sensitivity via preconcentration with Solid Phase Micro Extraction (SPME) fibers and Surface Enhanced Raman Spectroscopy (SERS) to increase the overall optical signals. Furthermore, we explored limitations and requirements for detecting from dispensers, lures, or live moths, including Dept. of Energy and CA State regulatory approvals. Finally, we setup some of our first “orchard in a box” experiments to measure pheromone diffusion along with developing appropriate models.

42 ENGINEERING↗

Mesoscale fractal whey protein particles derived from microscale linear-shaped protein assemblies (Part 1): Manufacturing method and particle characteristics

Whey protein isolates (WPI) are widely used in processed foods for their versatile functional properties. Modifying the structural properties of proteins by assembling them into mesoscale or microscale particles may improve their functionality and broaden their applications. This study aims to manufacture and characterize mesoscale whey protein particles (WPP) derived from WPI. Two types of WPP, WPP1 (0.05 mL/min) and WPP2 (0.25 mL/min), were prepared through a multistep approach involving liquid antisolvent (LAS) precipitation, heat treatment, and microfluidization. Liquid antisolvent precipitation was performed by injecting a 20% (wt/vol) WPI dispersion (pH 7) into an ethanol-glycerol mixture (75:25, vol/vol) under laminar flow, followed by heat treatment at 80°C for 20 min as a particle hardening step. This process produced stable fiber- and ribbon-shaped whey protein assemblies (WPA), which served as precursors to WPP. Subsequent microfluidization (150 MPa, 6 passages) reduced the size of WPA, yielding mesoscale WPP with irregular morphologies and a more uniform size distribution, as revealed by microscopy and dynamic light scattering. ζ-Potential and fluorescence labeling indicated higher surface charge and surface hydrophobicity of WPP compared with untreated WPI. The WPP showed internal mass fractal and surface fractal structures at larger length scales, analyzed using small-angle X-ray scattering. Fourier transform infrared spectroscopy demonstrated an increased fraction of intermolecular β-sheets in WPP, suggesting that hydrogen bonding contributed to their formation. Gel electrophoresis confirmed that disulfide bonds served as the primary cross-links stabilizing the WPP structure. Furthermore, turbidity measurements showed that WPP exhibited superior colloidal phase stability compared with untreated WPI and maintained high colloidal stability under both acidic and neutral pH conditions.

Antisolvent precipitation↗

Real-time well integrity monitoring in underground gas storage wells using distributed temperature and strain sensing: a field demonstration

Here, this article presents the first successful field demonstration of a combined distributed temperature and strain sensing (DTSS) system installed directly on newly replaced tubing in a 5400-ft-deep operational underground gas storage well. The DTSS system uses a single optical fiber to monitor temperature and strain in real-time, providing a cost-effective solution for long-term well integrity assessment. In this study, the strain–stress correlation of the tubing—representative of material behavior analysis—is investigated as a potential method for monitoring tubing integrity throughout its lifetime. Moreover, the DTSS system’s capability to support both continuous and discrete monitoring is evaluated by comparing future data with historical records, enabling the early detection of issues such as material fatigue, corrosion, or deformation. Overall, the work examines the effectiveness and scalability of the DTSS system for real-time monitoring of well operations and integrity in a newly replaced well.

Distributed Strain Sensing↗

Integrated TBC/EBC for SiC Fiber Reinforced SiC Matrix Composites for Next Generation Gas Turbines (Final Report)

In this ambitious project, a significant challenge preventing widespread use of ceramic matrix composites in hot section components of gas power generating turbines was addressed. Hot section components made from SiC fiber reinforced SiC matrix composites (SiC/SiC composites), have the potential to achieve a combined cycle energy efficiency of above 65%. To achieve this efficiency, the temperature of the combustion gases on the turbine component surface is expected to reach as high as ~1700ºC (3100ºF). However, SiC/SiC composites suffer from volatilization at high temperature under high velocity steam environment – typical in a turbine hot chamber. This integrated collaborative project, between two research groups at Clemson University and a team of engineers and scientists at GE Gas Power, focused on design, fabrication and evaluation of a new graded environmental barrier coating. Using the excellent compositional tailorability of polymer derived ceramics (PDCs), we developed an integrated EBC/BC that smoothly transitions from bottom SiC/SiC bond interface to hermetic sesquioxide (Y 2 O 3 ) top surface. This smooth compositional transition avoided the sharp CTE mismatch at interfaces to greatly reduce the thermal stress. The developed EBC is compatible with and bonds well with the bond coat that GE uses. The top hermetic oxide surface ensures low oxygen transportation and volatilization rates under the high velocity steam environment. The graded microstructure with increasing sesquioxide concentration also decreases the amount of Si and C elements near the top hermetic sesquioxide layer. Coatings made using a process suitable for manufacturing – atmospheric plasma spraying was demonstrated. The microstructure of coatings made using this process were fully characterized. Finally, the performance of these coatings was investigated under the most demanding conditions for this application. Specifically, high temperature, high velocity steam exposure; thermal shock test; and thermal cycling tests. The graded coatings performed exceptionally well in all these tests. Specific suggestions for future development in this area have also been identified. In addition to the excellent technical progress, this project helped initiate a robust collaboration between the research groups at Clemson and GE Gas Power. It also provided a high-quality learning and mentoring opportunity for the three post-doctoral research associates and two UG students at Clemson University who worked on this project. All proposed tasks, sub-tasks were completed, and all milestones achieved.

03 NATURAL GAS↗

Development of Additively Manufactured Complex Tools for Autoclave Cure Composites

IACMI Project 4.9, Tooling for Composites with Washout Features Produced by Additive Manufacturing, assembled a team including the industry lead, Ability Composites, NREL and Colorado State University (CSU). Ability Composites had originally expressed interest in alternate methods of producing tooling for composite parts. In follow-up discussions, it became clear that one of the bigger tooling challenges revolved around small production volume composite parts that were tooled on washout material due to the complex geometry. To build an understanding of the potential, both from a technology and a cost perspective, for replacing conventional washout tooling with 3D printed thermoplastic tooling, a number of commercially available dissolvable FDM printing materials were evaluated, leading to tooling representative of commercial articles of interest to Ability Composites. Ultimately, Ability Composites was able to directly compare autoclave processed prepreg composite parts produced on conventional washout tooling to composite parts molded on 3D printed dissolvable tooling produced at CSU. Small, laboratory test specimens were developed to investigate the structural performance of the candidate materials under autoclave processing conditions, which were nominally 121 °C (250 °F) and 345 kPa (50 psi). In addition, several internal structural configurations (infills) were evaluated under autoclave conditions using model materials. The results of these tests indicated that two materials, Stratasys ST 130 and Infinite Materials Solutions Aquasys 180 (AQ 180), were the best candidates, given the specified autoclave processing conditions. ST-130 was slightly more robust than AQ-180; however, the AQ-180 was carried forward as it was dissolvable in water, not requiring the basic solution needed to dissolve ST-130. Based on the preliminary material and 3D printed structures evaluations, larger tools with a truncated square pyramid geometry were created to produce prepreg composite test articles for 3D printed dissolvable tool evaluation under standard autoclave fabrication conditions. Two tools were manufactured using ST-130 and one tool using traditional ceramic washout tooling media. The tools were evaluated for geometric fidelity and surface roughness changes before and after carbon fiber/epoxy prepreg composites were manufactured on the tooling. The autoclave processing did not impact the geometry significantly and was completed at 121 °C and 345 kPa, indicating satisfactory tool performance. The results from surface roughness testing of both the resulting composite and the associated tooling indicated that an adequate surface resulted without the need for a surface sealing step, as was required for the conventional washout tooling. Based on results of the truncated pyramid tests as a basis, ST-130, AQ-120 and AQ-180 materials were carried forward to the tool geometry of interest to Ability Composites. These hollow rectangular bent ducts, which were complex in nature and not extractable after cure, were used to understand the impacts of tool material and thickness. One ST-130 tool was produced as a partially solid part, with an enclosed 40% dense infill region to reduce weight and material use. This was the same approach evaluated in the truncated pyramid portion of the study. This tool was to be envelope vacuum bagged and directly compared to a monolithic tool of conventional washout material. The traditional monolithic ceramic tool was manufactured by Ability composites using CNC-based subtractive methods. An additional five dissolvable polymer tools, manufactured from ST-130, AQ-120, and AQ-180, using a hollow design were 3D printed and used to produce carbon fiber/epoxy composite evaluation articles. These hollow dissolvable tools were expected to be less influenced by the autoclave conditions as the wall was solid and vacuum bagging was inside and outside the tool. This alternative geometry was also evaluated as an option in techno-economic modeling. Print times were reduced from in excess of 3 days to under 30 hours, while surface quality and and tool integrity were substantially improved in the transition from the partially solid tool to the hollow tooling concept. Ability Composites produced autoclave-cured prepreg ducts on each of these tools. The autoclave conditions utilized were more severe than those of the initial trials, reaching temperatures of 160 °C and a pressure of 414 kPa. Under these conditions, the partially solid 3D printed tool with skin and 40% dense infill crushed significantly; however, the thicker ST-130 hollow tool showed good promise, deforming only slightly. The thinner hollow tool walls were unsuccessful as were the other materials. Overall, the hollow tool manufacturing process saved significant amounts of time and material in manufacturing as compared to the solid ducts and produced composite surface quality improvements compared to the traditional washout tooling. The TEM was developed to allow direct comparisons between conventional washout tool manufacturing processes and those developed at CSU. It also allowed for two separate 3D printed tool geometries to be analyzed and compared. In this case, the square bent duct tool geometry was determined to be representative of common washout tools. This geometry was compared with a scaled-up version of it to assess differences in the two manufacturing processes based on tool size. The model was developed to make use of user input in the form of geometry details, process steps, manufacturing parameters, bulk material costs, capital equipment costs, and general costs to calculate overall labor, material, capital equipment, and energy costs per manufactured tool for the conventional and additive manufacturing processes for the two representative geometries. It was also able to estimate step-by-step process times for the manufacturing process and geometries. Based on significant input from Ability Composites and CSU from their knowledge gained from hands-on manufacturing of the 3D printed bent duct tool geometry, costs and process times were calculated for the two manufacturing processes. Results showed that the additive manufacturing techniques developed at CSU can substantially reduce the costs of tool manufacturing by reducing labor times and material usage. This is because additive manufacturing is a relatively hands-off process and allows for the tool design to be optimized to reduce material usage. The disadvantage, however, is that process times for additive manufacturing are significantly longer. The three-dimensional (3D) printing process is slow if tight tolerances are required, but the analysis did show that print times could be reduced with the hollow tool geometry. Also, further advances in additive manufacturing could expedite the process. Costs and process times for the tool washout process were calculated separately. They showed that costs are relatively insignificant when compared to the overall tool manufacturing processes, but with increases in tool size, costs for the conventional manufacturing approach are larger than for additive manufacturing. Again, the washout process for conventional tools is very hands-on, whereas for additively manufactured tools the print medium is dissolved in an automated detergent bath at the sacrifice of process time. The analysis showed that optimizing the additively manufactured tools may also reduce washout times. Overall, Project 4.9 demonstrated that commercially available dissolvable 3D printing materials exist that can be used to produce dissolvable tooling capable of surviving prepreg composites fabrication under autoclave conditions of 121 °C (250 °F) and 345 kPa (50 psi). An alternative hollow dissolvable tool design was developed which was structurally superior to the initial concept and was cost and time effective versus conventional washout tooling. The 3D printed sacrificial tool required no added surface sealing steps prior to composite part layup and cure, offering a significant advantage over the porous conventional washout tooling.

36 MATERIALS SCIENCE↗