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Conformable Hydrogen Storage Pressure Vessel

Existing commercially available hydrogen storage technologies are largely based on bulky and costly pressure vessels. These pressure vessels come in various forms, ranging from Type I steel cylinders to Type III and Type IV composite wrapped cylinders with metallic or polymer liners. In efforts to increase the pressure vessel storage density and meet DOE hydrogen storage targets, manufacturers are making incremental improvements. This approach alone is unlikely to meet DOE hydrogen storage targets and increase adoption of hydrogen fuel cell vehicles. The project team, led by the Center for Transportation and the Environment (CTE) and consisting of High Energy Coil Reservoirs, LLC (HECR) and The University of Texas at Austin's Center for Electromechanics (UT-CEM), has investigated a transformational hydrogen storage technology using high pressure modulus polymeric pressure vessels. These vessels are constructed by overwrapping an extruded thermoplastic elastomeric resin liner with high performance tensile fiber. This technology is used in commercially available compressed air storage for firefighters. The result is a lightweight, flexible, non-explosive, and non-fragmenting pressure vessel that can be shaped (prior to pressurization) to conform to specific applications. Although this project was funded to investigate the potential for this technology for vehicle applications, a potential significant cost reduction allowed with this approach may make it effective for high pressure ground storage as well. As part of Phase I of this project, the research team demonstrated a Kevlar™ over-braid that achieves a burst pressure in excess of 3.1X the operating pressure of 700 bar. The conformable vessel is able to achieve this pressure rating with reduced weight and cost when compared to Type IV vessels. The researchers also identified two potential resins to serve as the liner of the vessel. These resins have excellent hydrogen barrier properties that could enable a liner thickness of 0.06 inches or less; however, difficulties in manufacturing the core due to the extrusion manufacturing processes required testing with prototype resins as commercially available resins were not found that had the required properties. The team was able to build and test a vessel with one such blend, which outperformed the baseline Hytrel resin materials but did not meet the project hydrogen permeability rate goals.

08 HYDROGEN↗

Response Bias of Electrical Cable Coatings at FIRE Conditions (REBECCA-FIRE)

This report presents the results of a series of cable fire-retardant coating tests sponsored by the US Nuclear Regulatory Commission (NRC) Office of Nuclear Regulatory Research and performed at Sandia National Laboratories in conjunction with the National Institute of Standards and Technology (NIST). The goal of the tests was to assess the effects of three commercially available fire-retardant cable coating materials on cable thermal and electrical response behavior under fire-exposure conditions. The specific test objectives were to assess, under severe radiant heating conditions, how the coating materials impacted (1) cable thermal response and (2) electrical integrity behavior. The tests were not explicitly designed to assess the impact of the coatings on cable flammability, although some insights relative to the burning behavior of the coating materials themselves and cable ignition times were gained. NIST is currently investigating these attributes under the Cable Heat Release, Ignition, and Spread in Tray Installations During Fire (CHRISTIEFIRE) program (NUREG/CR-7010). The cables used in construction of the test articles were all seven-conductor 12AWG (American wire gage) control or power type copper conductor electrical cables. Two cable insulation types were represented, a polyethylene thermoplastic material and a cross-linked polyethylene thermoset material. Both cable types used have been tested extensively in recent NRC-sponsored experimental programs involving both circuit failure modes and effects testing and fire growth testing. The test articles included uncoated cables and cables coated with one of three fire-retardant coating materials: Carboline Intumastic 285, Flamemastic F-77, and Vimasco 3i. Test configurations included single lengths of cables, bundles of seven cables, and bundles of ten cables. The tests show that, under certain conditions, the fire-retardant coatings provide a substantial benefit relative to delays in cable heating, ignition and electrical failure times. However, as has been seen in prior test programs, the performance varied substantially among the coating products. The current tests also show that the benefit gained by the coatings was heavily dependent on the thermal mass of the coated cable system. Low thermal mass systems, such as the single lengths of coated cable, saw essentially no net benefit from application of the coatings. Intermediate mass systems, represented by the seven-cable bundles, saw some benefit from application of the coatings, but the benefit was inconsistent, and some cables in the bundles saw essentially no delay in thermal response or time to failure. For the larger thermal mass systems, represented by the ten-cable bundles, the benefit of the coatings was both more pronounced and more consistent with all coatings providing a measurable benefit.

36 MATERIALS SCIENCE↗

Design and Characterization of High Thermal Conductivity Pipes from Roll-to- Roll Processed Hybrid Copper-Polymer Strips for Waste Heat Recovery

Metal based heat exchangers targeting low temperature (<150°C) waste heat recovery (WHR) face high maintenance and material costs [1] that result in long payback periods (>1 year). Low-cost polymer pipes suffer from poor thermal conductivity (~0.2 W/m.K), and thus a low overall heat transfer coefficient. Previous reports demonstrated thermal conductivity enhancement in polymers through systematic molecular alignment [2, 3, 4], or by metal micro-particle inclusions [5]. However, these approaches suffer from scalability issues for WHR heat exchangers in terms of cost [1, 3], and thermomechanical considerations [6, 7]. In this work, we propose hybrid metal-polymer strips that are strategically designed to enhance thermal conductivity by cladding copper around polymer strips. The polymer strips with copper-clad edges are wound helically to form the pipes for a heat exchanger. Through numerical simulations, we optimize the copper-polymer strip layouts to achieve high wall thermal conductivity (k > 1 W/m.K) and also have low volume fraction of copper (<70%) for the composite pipes. In copper-polymer composite heat exchangers, the bottlenecks for heat transfer are the thermal interfacial resistances of copper-copper and copper-polymer joints. We experimentally measured interfacial resistances to be ~1x10 -5 K.m 2 /W and ~4x10 -5 K.m 2 /W for copper-copper and copper-polymer joints, respectively. Using the measured interfacial resistances, we further optimized the design of the hybrid pipes to find high thermal conductivity (> 1 W/m.K) designs. We predict up to ~20 % enhancement in overall heat transfer relative to an all polymer (k = 0.2 W/m.K) heat exchanger system. Using a cohesive zone modelling (CZM) for predicting delamination at the weld joints, we find that our hybrid pipes can have operating internal pressures > 200 psi. The optimized designs of hybrid metal-polymer pipes provide a scalable and cost- effective means for harvesting waste heat from low temperature sources. Thekdi, A., and Nimbalkar, S. Oak Ridge National Lab (2014). Shen, Sheng, et al. Nature nanotechnology 5.4 (2010). Xu, Yanfei, et al. Science advances 4.3 (2018). Smith et al. ACS nano, 9(2), (2015). Sofian, N.M., et al., Journal of Thermoplastic Composite Materials (2001). Aymonier et al. Chemistry of Materials, 15(25), (2003). Tavman, I.H., Journal of Applied Polymer Science, 62(12), (1996).

C Rajagopal, Manjunath↗

Carbon Fiber Reinforced Polyolefin Body Panels

This project addresses an automotive industry desire for a cost-effective, lightweight material for body panels that offers mass reduction compared to steel and aluminum body panels, and a cost savings compared to incumbent polymer body panels. Inexpensive polypropylene (PP) combined with <10 weight % reclaimed/recycled carbon fiber (rCF) have the potential to meet both performance and affordability targets for lightweight, paintable vertical body panels. This project supports DOE and IACMI technical goals of reducing production cost of CF composites >25% in 5 years on a path to >50% in 10 years and demonstrating technologies for >80% recyclability or reuse of fiber reinforced composites in 5 years on a path to >95% in 10 years. Alternative body panel materials must meet all fit and surface finish requirements, and match the appearance of metal body panels adjacent to them. The PP/rCF materials must maintain exterior dimensional requirements with a low co-efficient of thermal expansion, excellent paintability, and mechanical performance. Thermoplastic injection molding offers significant reduction in tooling costs as injection molding dies are typically less than half the cost of stamping dies. This project utilized rCF compounded with special formulations of PPs to produce automotive components that meet requirements for fit, finish, mechanical performance, and paintability while offering significant mass savings over incumbent metal panels. It will also offer a cost savings versus other composite solutions. Fenders were molded at the IACMI – Corktown facility using an existing fender tool. Ford Motor Company was the industry lead for this project and provided project management, testing, painting and adhesion testing, and developed the cost-model/business case. Ford engaged and aggregated cost share with Borealis who provided materials, technical support for process trials, and participated in coordination meetings. Vehicles Technology Area staff in Corktown assisted in project management, process trials, molded fenders, and benchmarked physical characteristics. Over 450 plaques were molded with two different gating systems to look at processing conditions and specimens were excised for mechanical testing. Plaques were also used for paint trials, surface analysis, and dimensional analysis. Subsequently, over 200 fenders were molded at IACMI – Corktown. These fenders were used for paint trials, surface analysis, and dimensional analysis. The PP/rCF systems met all of the requirements except for paint appearance. Additional development of paint primer and top coat is necessary to fulfill automotive OEM paint surface requirements.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

HPC4Mfg with Carbon Inc.

Continuous Liquid Interface Production (CLIP) is poised to bring additive manufacturing to multiple American manufacturing sectors owing to its unique combination of rapid print speeds and material options that resemble injection molding thermoplastics. In spite of these benefits, CLIP is still a maturing process. To improve our understanding and control of the process, this project developed a multi-physics computational model that encompasses the coupled chemical-physical processes of photopolymerization and fluid flow to predict part outcomes. A physically predictive model can enable rapid optimization of CLIP and reduce the current cycle time and waste associated with optimization by four-fold. Ultimately, this effort will help open the U.S. $400B plastic manufacturing industry to the key benefits of additive manufacturing, namely mass customization, unlimited design space, and a cost- and energy-effective path to mainstream manufacturing. In the course of the project we produced a model which coupled fluid-flow, species transport, and photochemistry to model the Carbon CLIP process. As the development proceeded, we validated the code against theory and experiments. The resulting code was transferred to Carbon, and we expect it to be a useful part of their modeling capability. Future work includes improvements to the fluid solver’s robustness and performance, along with the addition of additional physics models.

42 ENGINEERING↗

Development of a Multi-physics Model to Optimize Continuous Liquid Interface Production (CLIP) for Additive Manufacturing (Carbon3D HPC4Mfg Final Report)

Continuous Liquid Interface Production (CLIP) is poised to bring additive manufacturing to multiple American manufacturing sectors owing to its unique combination of rapid print speeds and material options that resemble injection molding thermoplastics. In spite of these benefits, CLIP is still a maturing process. To improve our understanding and control of the process, this project developed a multi-physics computational model that encompasses the coupled chemical-physical processes of photopolymerization and fluid flow to predict part outcomes. A physically predictive model can enable rapid optimization of CLIP and reduce the current cycle time and waste associated with optimization by four-fold. Ultimately, this effort will help open the U.S. $400B plastic manufacturing industry to the key benefits of additive manufacturing, namely mass customization, unlimited design space, and a cost- and energy-effective path to mainstream manufacturing. In the course of the project we produced a model which coupled fluid-flow, species transport, and photochemistry to model the Carbon CLIP process. As the development proceeded, we validated the code against theory and experiments. The resulting code was transferred to Carbon, and we expect it to be a useful part of their modeling capability. Future work includes improvements to the fluid solver’s robustness and performance, along with the addition of additional physics models.

36 MATERIALS SCIENCE↗

Closing the Loop on Automotive Carbon Fiber Prepreg Manufacturing Scrap

The project demonstrated how to “close the loop” on carbon fiber by integrating industrial carbon fiber scrap into new functional components in an automotive lightweighting application. The project serves as a validation of discontinuous recycled carbon fiber in a commercial context, while generating comprehensive material data throughout the production chain. To this end, the project exhibited increasing complexity as material evaluation progressed from benchtop to commercial scale through full-scale part production, with key material properties thoroughly characterized throughout the process. Of particular focus was the form of the fiber that was fed into compounding, as recycled fiber has historically been problematic to feed at commercial-scale. Carbon fiber is energy-intensive to manufacture, so reuse of existing fiber material can reduce costs and increase sustainability. Additionally, by integrating recovered short fiber into a thermoplastic, regrind processes can be used to provide feedstock for later generations of product. While regrind plastics are not “infinitely recyclable”, reusing the manufacturing scrap over several generations of products can greatly increase material sustainability and lower the fractional embodied energy of each successive product. As such, this project supports the IACMI technical goals of (1) 25% lower carbon fiber-reinforced polymer (CFRP) cost, (2) 50% reduction in CFRP embodied energy, and (3) 80% composite recyclability into useful products. The initial stage of the project involved down selecting surface treatment (sizing) chemistries. Sizing evaluations were performed on Vartega’s chemically recycled intermediate modulus fiber along with standard modulus dry scrap which was oversized with sizing provided by Michelman. More dramatic improvements from sizing were found on the standard rather than the intermediate modulus fibers. The strength of the chemically recycled individual fibers were evaluated by Michelman and ORNL through single fiber testing and found to be comparable to similarly evaluated virgin fibers. UDRI’s mechanical testing on injection molded test specimens identified similar mechanical properties and fiber distribution relative to benchmark specimens. Additional surface chemistry tests and visualizations were performed by the Colorado School of Mines to confirm close conformance between the benchmark and recycled-fiber specimens. As the mechanical test results exceeded the 80% threshold established as the go/no-go(GNG), the project scale was increased to use commercial-scale equipment that would both better characterize the manufacturing utility of the target product format and allow qualitative assessment of a complex commercial part. An upscaled compounding evaluation was performed with a 27 mm twin-screw compounding extruding using oversized standard modulus fibers that were formatted to improve bulk solids transfer. The project team anticipated that milestone mechanical benchmarks could be achieved given the favorable performance of the sized standard modulus material identified in the initial micro-compounding trials. While the mechanical performance did meet the milestone target for that phase of the project, mechanical properties for this standard modulus-based compound were still less than those of the Ford specification. To compare the performance, the project team oversized intermediate modulus dry fibers and compounded them with the project resin at BASF using a 40 mm compounder. Test specimen mechanical performance exceeded the targets laid out in both the project milestone and the Ford specification. A series of prototype parts were successfully molded, albeit with instances of short shot components due to the high thermal conductivity of the carbon fiber compared to glass fiber for which the prototype tool was designed for. The project demonstrated that recycled carbon fiber is a viable option in fiber reinforced compound, providing greatly increased strength and modulus for applications that require them. The “agglomerated” format that facilitated effective bulk solids transfer of recovered fiber showed promise for industrial application.

36 MATERIALS SCIENCE↗

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↗

Collective Summary of sCO2 Materials Development (Supercritical Transformational Electric Power Generation (STEP) Level 2 Milestone Report) (Parts I - II)

Polymers such as PTFE (polytetrafluorethylene or Teflon), EPDM (ethylene propylene diene monomer) rubber, FKM fluoroelastomer (Viton), Nylon 11, Nitrile butadiene (NBR) rubber, hydrogenated nitrile rubber (HNBR) and perfluoroelastomers (FF_202) are commonly employed in super critical CO 2 (sCO2) energy conversion systems. O-rings and gaskets made from these polymers face stringent performance conditions such as elevated temperatures, high pressures, pollutants, and corrosive humid environments. In FY 2019, we conducted experiments at high temperatures (100°C and 120°C) under isobaric conditions (20 MPa). Findings showed that elevated temperatures accelerated degradation of polymers in sCO2, and that certain polymer microstructures are more susceptible to degradation over others. In FY 2020, the focus was to understand the effect of sCO2 on polymers at low (10 MPa) and high pressures (40 MPa) under isothermal conditions (100°C). It was clear that the same selectivity was observed in these experiments wherein certain polymeric functionalities showed more propensity to failure over others. Fast diffusion, supported by higher pressures and long exposure times (1000 hours) at the test temperature, caused increased damage in sCO2 environments to even the most robust polymers. We also looked at polymers under compression in sCO2 at 100°C and 20 MPa pressure to imitate actual sealing performance required of these materials in sCO2 systems. Compression worsened the physical damage that resulted from chemical attack of the polymers under these test conditions. In FY 2021, the effect of cycling temperature (from 50°C to 150°C to 50°C) for polymers under a steady sCO2 pressure of 20 MPa was studied. The aim was to understand the influence of cycling temperatures of sCO2 for typical polymers under isobaric (20 MPa) conditions. Thermoplastic polymers (Nylon, and PTFE) and elastomers (EPDM, Viton, Buna N, Neoprene, FF202, and HNBR) were subjected to 20 MPa sCO2 pressure for 50 cycles and 100 cycles in separate experiments. Samples were extracted for ex-situ characterization at 50 cycles and upon the completion of 100 cycles. Each cycle constituted of 175 minutes of cycling from 50°C to 150°C. The polymer samples were examined for physical and chemical changes by Dynamic Mechanical and Thermal Analysis (DMTA), Fourier Transform Infrared (FTIR) spectroscopy, and compression set. Density and mass changes immediately after removal from test were measured for degree of swell comparisons. Optical microscopy techniques and micro computer tomography (micro CT) images were collected on select specimens. Evaluations conducted showed that exposures to super-critical CO2 environments resulted in combinations of physical and/or chemical changes. For each polymer, the dominance of cycling temperatures under sCO2 pressures, were evaluated. Attempts were made to qualitatively link the permanent sCO2 effects to polymer micro- structure, free volume, backbone substitutions, presence of polar groups, and degree of crystallinity differences. This study has established that soft polymeric materials are conducive to failure in sCO2 through mechanisms of failure that are dependent on polymer microstructure and chemistry. Polar pendant groups, large atom substitutions on the backbone are some of the factors that are influential structural factors.

36 MATERIALS SCIENCE↗

Material Characterization for Large Scale Additive Manufacturing (AM)

The objective of this project was to enable prediction of residual stresses and warpage for extrusion deposition additive manufacturing (EDAM) fabricated carbon fiber thermoplastic matrix parts with three different materials systems produced by Techmer. The materials selected include Polyphenylene sulfide reinforced with 50% by weight of carbon fiber (CF-PPS), Polyethersulfone reinforced with 25% by weight of carbon fiber (CF-PESU), Polysulfone reinforced with 25% by weight of carbon fiber (CF-PSU). ADDITIVE3D © , a physics-based simulation workflow for EDAM, provided the simulation capabilities required for this project. Simulation predictions were validated against measurements carried out during and after the printing process carried out in the CAMRI and LSAM systems . Predictions for temperature, degree of crystallinity and deformation were carried out for the three material systems and two different geometries. Predictions for temperature were correlated very well with the experimental measurements for the two geometries printed using the three-material systems. The crystallinity level was verified for CF-PPS. The predictions for part deformation were in good agreement with the experimental measurements. In the best-case, predictions were within 8% of the maximum displacement observed in the 3-direction whereas predictions were within 14% for the worst-case. The adoption of this technology in commercial large-scale EDAM production processes would dramatically reduce the costs associated with producing articles by that process. Many thousands of dollars in materials, energy, and machine time could be saved by utilizing this simulation technology to develop articles rather than iterative printings to arrive at the optimal or correct design. The avoidance of a single failed print has the possibility of saving tens of thousands of dollars involved in the cost of material, machine and operators’ time.

36 MATERIALS SCIENCE↗

Methane Pyrolysis for CO2-free H2 and Carbon Nanomaterials (Abstract)

We propose to continue to develop a new process for producing CO2-free hydrogen (H2) from inexpensive and domestically-abundant natural gas (NG), while simultaneously reducing H2’s net production cost to $1.0/kg through the sale of valuable crystalline solid carbon co-product. Producing clean hydrogen at this price is a DOE Hydrogen Energy Earthshot goal. Cost effective production of clean H2 is also of commercial relevance to project partners Southern California Gas Company (SoCalGas) and startup company C4-MCP, who aim to further develop, demonstrate at scale, and ultimately deploy the new process technology developed on this project in order to meet regulatory demands in the State of California. In the current project we have focused on i) understanding the catalyst science for thermocatalytic decomposition of methane (TCD), which resulted in the development of a patent pending bimetallic catalyst offering favorable activity, stability, and selectivity under industrially relevant process conditions, ii) developing a novel, patent pending process to enable the separation of produced carbon and catalyst, and re-synthesis of the catalyst using recycled materials, iii) performing limited characterization of the produced carbon materials, and iv) performing detailed process modeling in order to perform techno economic assessment. The additional scope proposed here will accelerate the commercial deployment of TCD for CO2-free H2 and valuable solid carbon nanotubes (CNT) co-product, by i) scaling up the production of CNT co-product using a scalable, fluidized bed reactor (25 g catalyst scale versus the 1 g catalyst scale demonstrated to-date), ii) producing at least 40 g of CNT product, produced via multiple cycles of TCD, carbon-catalyst separation, and catalyst re-synthesis, to enable the production of sufficient quantities of solid carbon so as to explore its market potential, iii) understanding the quality of the co-product CNTs, produced at larger scale, through advanced characterization, and iv) beginning to explore multiple promising high volume carbon product applications (thermoplastics, automotive composites, battery, and cement reinforcement applications).

08 HYDROGEN↗

Carbon Fiber Plasma Surface Treatment (CRADA Final Report)

This project focused on developing and applying a new surface treatment technology to carbon fiber applications. During the course of this work, two different treatment prototypes were developed and explored. Highly reactive surface chemistries were successfully applied to carbon fiber, resulting in surface oxygen content as high as 27%. Enhanced composite properties of a 45% increase in the interfacial strength and a 10% increase in tensile and flexural strength were demonstrated for thermoplastic resins. This enhancement was performed while proving that the plasma surface treatment process does not damage the fiber. Treatment times were as low as 1 min.

36 MATERIALS SCIENCE↗

Relevant Additive Manufacturing Materials for Wind Industry

The purpose of this report is to equip wind industry professionals with the relevant material testing and properties of large format extrusion-based additive manufacturing processes. Discussion on the printability and processing of different classes of materials (i.e. low temperature, high temperature, thermoplastics, elastomeric, foam, etc.) is provided as well as relevant test standards and methods. Existing results for materials and properties are detailed. A companion document titled “Additive Manufacturing Design Guidelines for Wind Industry” covers the seven families of additive manufacturing, the relevance of each family to the wind industry, and design guidelines and considerations for the most relevant processes.

17 WIND ENERGY↗

Selective Laser Sintering of Polyolefins

Polyolefins are some of the most produced and used polymers around the globe. They are semi-crystalline thermoplastic polymers known for their low production cost while still exhibiting good mechanical properties and chemical resistance. These polymers are often used in a variety of manufacturing processes, including 3D printing or additive manufacturing (AM). However, due to their semi-crystalline nature, there are often issues with using polyolefins in AM processes (for example, shrinkage leading to dimensional instabilities). One example of an AM process for which polyolefins are of interest is selective laser sintering (SLS), where printability depends on the powdered material’s morphology, flowability, and size. Due to the inherent properties of polyolefins, there are a variety of issues surrounding their use in the SLS process. This paper aims to review the basics of SLS as well the current state of SLS printing of a few polyolefins and what challenges that would need to be overcome to print with these polyolefins.

36 MATERIALS SCIENCE↗

Review of Polyurethanes

Polyurethanes are used in almost every aspect of our everyday lives and have advanced areas including construction, medicine, automotive, marine, and apparel. Rigid and flexible polyurethane foams, rubbers, thermoplastic polyurethanes and many more are in everything from our couches, car steering wheels, even the soles of our shoes. This literature review is to discuss the discovery of polyurethane chemistry, today’s uses, and advancements.

36 MATERIALS SCIENCE↗

New Sesame Equations of State for Polypropylene, Polyvinylchloride (PVC), and Nylon 66

I built new Sesame equations of state (EOS) for polypropylene (PP), polyvinylchloride (PVC), and nylon 66. PP has the same stoichiometry as polyethylene and TPX but with a density intermediate between the two. Nylon is a polyamide manufactured chiefly in the form of fibers. PP and PVC are the second- and third-most widely produced polymers in the world. All three are thermoplastics. Their monomer units are depicted in Figure 1. I discuss the theory on which the EOS are based in the following section, then compare results to thermal and shock compression data in Section III.

36 MATERIALS SCIENCE↗

LightMAT: Continous Fiber Malleable Thermoset Composites with sub-1-minute dwell times; validation of impact performance and evaluation of the efficacy of the compression forming process

Recent major advances in polymer chemistry are enabling a paradigm shift in the area of processing and re-processing/recycling of advanced composite materials. Inexpensive compression molding with short cycle times, traditionally available for thermoplastic composites only, are now possible for the thermoset resins based on polyimine chemistry. Participant will collaborate with the LightMAT consortium Labs ORNL, SNL, and PNNL to non-destructively characterize microscopic structural defects (such as voids and resin-rich areas), and perform high speed impact characterization of its malleable thermoset CFRP's. This work is critical to the validation and adoption of these materials for the automotive market and towards DOE-VTO lightweighting mission objectives.

36 MATERIALS SCIENCE↗

Predictive Models and Novel Accelerated Tests for the Reliability of Cell Metallization in Photovoltaic Modules (Final Report)

Studies of metallization corrosion m photovoltaics have mainly been limited to comparisons of modules placed in accelerated chambers to fielded modules [1]. Damp Heat accelerated tests and phenomenological equations [2] are used to assess metallization corrosion without understanding the effect of UV light and temperature and humidity cycles on encapsulant adhesion degradation. The roles of encapsulant in-and out-diffusions of moisture and encapsulant impurities are important. Furthermore, few photovoltaic metallization corrosion studies included the role of bias and leakage currents, which are crucial in the electrochemical reaction of metallization. Leakage currents can highly accelerate the corrosion mechanism and are important to include in the studies of corrosion. In our research plan, we will address the following gaps in the PV community's understanding of metallization corrosion: (1) metallization corrosion with bias, humidity, and impurities in the encapsulant or metallization; (2) humidity diffusion through fresh and degraded encapsulants; and (3) comparison of model predictions with outdoor field modules and SunPower's extensive data for its back-contact and front-contact fleets [2] along with NREL's store of >20 year old modules. Our goal is to build models and accelerated tests to predict long term degradation of metallization corrosion of photovoltaic modules in the field. Our studies will include metals used in c-Si solar cells (Cu, Ag, and Al) and commonly used encapsulants (EV A (ethylene vinyl acetate), TPO (thermoplastic olefin), and silicone).

14 SOLAR ENERGY↗