The solution processability of ionogel solid electrolytes has recently garnered attention in the Li-ion battery community as a means to address the interface and fabrication issues commonly associated with most solid electrolytes. However, the trapped ionic liquid (ILE) component has hindered the electrochemical performance. In this report we present a process to tune the properties by replacing the ILE in a silica-based ionogel after fabrication with a liquid component befitting the desired application. Electrochemical cycling under various conditions showcases gels containing different liquid components incorporated into LiFePO4 (LFP)/gel/Li cells: high power (455 W kg–1 at a 1 C discharge) systems using carbonates, low temperatures (-40 °C) using ethers, or high temperatures (100 °C) using ionic liquids. Fabrication of additive-manufactured cells utilizing the exchanged carbonate-based system is demonstrated in a planar LFP/Li4Ti5O12 (LTO) system, where a marked improvement over an ionogel is found in terms of rate capability, capacity, and cycle stability (118 vs 41 mA h g–1 at C/4). This process represents a promising route to create a separator-less cell, potentially in complex architectures, where the electrolyte properties can be facilely tuned to meet the required conditions for a wide range of battery chemistries while maintaining a uniform electrolyte access throughout cast electrodes.
The development of chemistry is reported to implement selective dual-wavelength olefin metathesis polymerization for continuous additive manufacturing (AM). A resin formulation based on dicyclopentadiene is produced using a latent olefin metathesis catalyst, various photosensitizers (PSs) and photobase generators (PBGs) to achieve efficient initiation at one wavelength (e.g., blue light) and fast catalyst decomposition and polymerization deactivation at a second (e.g., UV-light). This process enables 2D stereolithographic (SLA) printing, either using photomasks or patterned, collimated light. Importantly, the same process is readily adapted for 3D continuous AM, with printing rates of 36 mm h–1 for patterned light and up to 180 mm h–1 using un-patterned, high intensity light.
Interest in 3D printing of thermoset resins has increased significantly in recent years. One approach to additive manufacturing of thermoset resins is printing dual-cure resins with direct ink write (DIW). Dual-cure resins are multi-component resins which employ an in situ curable constituent to enable net-shape fabrication while a second constituent and cure mechanism contribute to the final mechanical properties of the printed materials. In this work, the cure kinetics, green strength, printability, and print fidelity of dual-cure epoxy/acrylate thermoset resins are investigated. Resin properties are evaluated as a function of acrylate concentration and in situ UV exposure conditions. The acrylate cure kinetics are probed using photo-differential scanning calorimetry and the impacts of resin composition and UV cure profile on the acrylate extent of conversion are presented. Continuous and pulsed UV cure profiles are shown to affect total conversion due to variances in radical efficiency at different UV intensities and acrylate concentrations. The effects of acrylate concentration on the kinetics of the epoxy thermal cure and the final mechanical properties are also investigated using dynamic mechanical analysis and three-point bend measurements. The glass transition temperature is dependent on formulation, with increasing acrylate content decreasing the Tg. However, the room temperature shear moduli, flexural moduli, strength, strain-to-failure, and toughness values are relatively independent of resin composition. The similarity of the final properties allows for greater flexibility in resin formulation and in situ cure parameters, which can enable the printing of complex parts that require high green strength. We found that the in situ UV print intensities and exposure profiles that are necessary to achieve the best print quality are not, in most cases, the conditions that maximize conversion of the acrylate network. This highlights the importance of developing optimized resin compositions which enable complete cure of the acrylate network by promoting acrylate dark cure or thermal cure.
Additive Manufacturing (AM) of porous polymeric materials, such as foams, recently became a topic of intensive research due their unique combination of low density, impressive mechanical properties, and stress dissipation capabilities. Conventional methods for fabricating foams rely on complex and stochastic processes, making it challenging to achieve precise architectural control of structured porosity. In contrast, AM provides access to a wide range of printable materials, where precise spatial control over structured porosity can be modulated during the fabrication process enabling the production of foam replacement structures (FRS). Current approaches for designing FRS are based on intuitive understanding of their properties or an extensive number of finite element method (FEM) simulations. These approaches, however, are computationally expensive and time consuming. Therefore, in this work, we present a novel methodology for determining the mechanical compression response of direct ink write (DIW) 3D printed FRS using a simple cross-sectional image. By obtaining measurement data for a relatively small number of samples, an artificial neural network (ANN) was trained, and a computer vision algorithm was used to make inferences about foam compression characteristics from a single cross-sectional image. Finally, a genetic algorithm (GA) was used to solve the inverse design problem, generating the AM printing parameters that an engineer should use to achieve a desired compression response from a DIW printed FRS. The methods developed herein present an avenue for entirely autonomous design and analysis of additively manufactured structures using artificial intelligence.
The use of self-assembling, pre-polymer materials in 3D printing is rare, due to difficulties of facilitating printing with low molecular weight species and preserving their reactivity and/or functions on the macroscale. Akin to 3D printing of small molecules, examples of extrusion-based printing of pre-polymer thermosets are uncommon, arising from their limited rheological tuneability and slow reactions kinetics. The direct ink write (DIW) 3D printing of a two-part resin, Epon 828 and Jeffamine D230, using a self-assembly approach is reported. Through the addition of self-assembling, ureidopyrimidinone-modified Jeffamine D230 and nanoclay filler, suitable viscoelastic properties are obtained, enabling 3D printing of the epoxy–amine pre-polymer resin. A significant increase in viscosity is observed, with an infinite shear rate viscosity of approximately two orders of magnitude higher than control resins, in addition to, an increase in yield strength and thixotropic behavior. Printing of simple geometries is demonstrated with parts showing excellent interlayer adhesion, unachievable using control resins.
This SAND report fulfills the final report requirement for the Born Qualified Grand Challenge LDRD. Born Qualified was funded from FY16-FY18 with a total budget of ~$13M over the 3 years of funding. Overall 70+ staff, Post Docs, and students supported this project over its lifetime. The driver for Born Qualified was using Additive Manufacturing (AM) to change the qualification paradigm for low volume, high value, high consequence, complex parts that are common in high-risk industries such as ND, defense, energy, aerospace, and medical. AM offers the opportunity to transform design, manufacturing, and qualification with its unique capabilities. AM is a disruptive technology, allowing the capability to simultaneously create part and material while tightly controlling and monitoring the manufacturing process at the voxel level, with the inherent flexibility and agility in printing layer-by-layer. AM enables the possibility of measuring critical material and part parameters during manufacturing, thus changing the way we collect data, assess performance, and accept or qualify parts. It provides an opportunity to shift from the current iterative design-build-test qualification paradigm using traditional manufacturing processes to design-by-predictivity where requirements are addressed concurrently and rapidly. The new qualification paradigm driven by AM provides the opportunity to predict performance probabilistically, to optimally control the manufacturing process, and to implement accelerated cycles of learning. Exploiting these capabilities to realize a new uncertainty quantification-driven qualification that is rapid, flexible, and practical is the focus of this effort.
This report summarizes the data analysis activities that were performed under the Born Qualified Grand Challenge Project from 2016 - 2018. It is meant to document the characterization of additively manufactured parts and processe s for this project as well as demonstrate and identify further analyses and data science that could be done relating material processes to microstructure to properties to performance.
Plumley, John B.; Cook, Adam W.; Larsen, Christopher A.; Artyushkova, Kateryna; Han, Sang M.; Peng, Thomas L.; Kemp, Richard A.
Transparent electric conductors made of indium tin oxide (ITO)-doped glass prepared by a flash lamp annealing (FLA) process were compared with ITO-doped glass prepared via a conventional rapid thermal annealing (RTA) process. Stylus surface profilometry was used to determine thicknesses, scanning electron microscopy was used to image surfaces, X-ray diffraction was used to determine film structures, X-ray photoelectron spectroscopy was used to determine oxidation states and film compositions, 4-point probe measurements were used to determine electrical conductivities, UV–Vis spectroscopy was used to determine film transparencies, and selective light filtering was used to determine which wavelengths of light are needed to anneal ITO into a visibly transparent electrically conductive thin film via an FLA process. The results showed that FLA with visible light can be used to nearly instantaneously anneal ITO to create visibly transparent and electrically conductive ITO thin films on glass. The FLA process achieved this by predominately exciting unoxidized indium, unoxidized tin, tin monoxide (SnO), and non-stoichiometric indium oxide (InOx), appropriately distributed in an electron beam physical vapor-deposited amorphous ITO thin film, to allow their oxidation and crystallization into an electrically conductive visibly transparent ITO. Though it is possible to prepare ITO-doped glass that is more transparent with an RTA process, the FLA process is significantly faster, has comparable electrical conductivity, and can strongly localize heating to areas of the as-deposited ITO thin film that are not electrically conductive and visibly transparent.
Additive manufacturing offers unprecedented opportunities to design complex structures optimized for performance envelopes inaccessible under conventional manufacturing constraints. Additive processes also promote realization of engineered materials with microstructures and properties that are impossible via traditional synthesis techniques. Enthused by these capabilities, optimization design tools have experienced a recent revival. The current capabilities of additive processes and optimization tools are summarized briefly, while an emerging opportunity is discussed to achieve a holistic design paradigm whereby computational tools are integrated with stochastic process and material awareness to enable the concurrent optimization of design topologies, material constructs and fabrication processes.
There is a rising interest in developing functional electronics using additively manufactured components. Considerations in materials selection and pathways to forming hybrid circuits and devices must demonstrate useful electronic function; must enable integration; and must complement the complex shape, low cost, high volume, and high functionality of structural but generally electronically passive additively manufactured components. This article reviews several emerging technologies being used in industry and research/development to provide integration advantages of fabricating multilayer hybrid circuits or devices. First, we review a maskless, noncontact, direct write (DW) technology that excels in the deposition of metallic colloid inks for electrical interconnects. Second, we review a complementary technology, aerosol deposition (AD), which excels in the deposition of metallic and ceramic powder as consolidated, thick conformal coatings and is additionally patternable through masking. Finally, we show examples of hybrid circuits/devices integrated beyond 2-D planes, using combinations of DW or AD processes and conventional, established processes.
The work performed in this project has demonstrated the feasibility to use hydrodynamic focusing of two fluid steams to create a novel micro printing technology for electronics and other high performance applications. Initial efforts focused solely on selective evaporation of the sheath fluid from print stream provided insight in developing a unique print head geometry allowing excess sheath fluid to be separated from the print flow stream for recycling/reuse. Fluid flow models suggest that more than 81 percent of the sheath fluid can be removed without affecting the print stream. Further development and optimization is required to demonstrate this capability in operation. Print results using two-fluid hydrodynamic focusing yielded a 30 micrometers wide by 0.5 micrometers tall line that suggests that the cross-section of the printed feature from the print head was approximately 2 micrometers in diameter. Printing results also demonstrated that complete removal of the sheath fluid is not necessary for all material systems. The two-fluid printing technology could enable printing of insulated conductors and clad optical interconnects. Further development of this concept should be pursued.
We have demonstrated a novel microfluidic technique for aqueous media, which uses super-hydrophobic materials to create microfluidic channels that are open to the atmosphere. We have demonstrated the ability to perform traditional electrokinetic operations such as ionic separations and electrophoresis using these devices. The rate of evaporation was studied and found to increase with decreasing channel size, which places a limitation on the minimum size of channel that could be used for such a device.
Recent advances in nanoparticle inks have enabled inkjet printing of metal traces and interconnects with very low (100-200°C) process temperatures. This has enabled integration of printable electronics such as antennas and radio frequency identification (RFID) tags with polyimide, teflon, PCBs, and other low temperature substrates. We discuss here printing of nanoparticle inks for three dimensional interconnects, and the apparent mechanism of nanoparticle ink conductivity development at these low process temperatures.
Biofouling, the unwanted growth of biofilms on a surface, of water-treatment membranes negatively impacts in desalination and water treatment. With biofouling there is a decrease in permeate production, degradation of permeate water quality, and an increase in energy expenditure due to increased cross-flow pressure needed. To date, a universal successful and cost-effect method for controlling biofouling has not been implemented. The overall goal of the work described in this report was to use high-performance computing to direct polymer, material, and biological research to create the next generation of water-treatment membranes. Both physical (micromixers - UV-curable epoxy traces printed on the surface of a water-treatment membrane that promote chaotic mixing) and chemical (quaternary ammonium groups) modifications of the membranes for the purpose of increasing resistance to biofouling were evaluated. Creation of low-cost, efficient water-treatment membranes helps assure the availability of fresh water for human use, a growing need in both the U. S. and the world.
We have designed and built electrostatically actuated microvalves compatible with integration into a PDMS based microfluidic system. The key innovation for electrostatic actuation was the incorporation of carbon nanotubes into the PDMS valve membrane, allowing for electrostatic charging of the PDMS layer and subsequent discharging, while still allowing for significant distention of the valveseat for low voltage control of the system. Nanoparticles were applied to semi-cured PDMS using a stamp transfer method, and then cured fully to make the valve seats. DC actuation in air of these valves yielded operational voltages as low as 15V, by using a supporting structure above the valve seat that allowed sufficient restoring forces to be applied while not enhancing actuation forces to raise the valve actuation potential. Both actuate to open and actuate to close valves have been demonstrated, and integrated into a microfluidic platform, and demonstrated fluidic control using electrostatic valves.
In order to develop the next generation of high peak intensity lasers, new grating technology providing higher damage thresholds and large apertures is required. The current assumption is that this technical innovation will be multilayer dielectric gratings, wherein the uppermost layer of a thin film mirror is etched to create the desired binary phase grating. A variant of this is explored with the upper grating layer being a lower density gelatin-based volume phase grating in either sol-gel or dichromated gelatin. One key benefit is the elimination of the etching step.
Surfactant-templated silica thin films are potentially important materials for applications such as chemical sensing. However, a serious limitation for their use in aqueous environments is their poor hydrolytic stability. One convenient method of increasing the resistance of mesoporous silica to water degradation is addition of alumina, either doped into the pore walls during material synthesis or grafted onto the pore surface of preformed mesophases. Here, we compare these two routes to Al-modified mesoporous silica with respect to their effectiveness in decreasing the solubility of thin mesoporous silicate films. Direct synthesis of templated silica films prepared with Al/Si = 1:50 was found to limit film degradation, as measured by changes in film thickness, to less than 15% at near-neutral pH over a 1 week period. In addition to suppressing film dissolution, addition of Al can also cause structural changes in silica films templated with the nonionic surfactant Brij 56 (C 16H 33(OCH 2CH 2) n∼10OH), including mesophase transformation, a decrease in accessible porosity, and an increase in structural disorder. The solubility behavior of films is also sensitive to their particular mesophase, with 3D phases (cubic, disordered) possessing less internal but more thickness stability than 2D phases (hexagonal), as determined with ellipsometric measurements. Finally, grafting of Al species onto the surface of surfactant-templated silica films also significantly increases aqueous stability, although to a lesser extent than the direct synthesis route.