Christopher M. Spadaccini

Ultralight, ultrastiff mechanical metamaterials

Microlattices make marvelous materials Framework or lattice structures can be remarkably strong despite their very low density. Using a very precise technique known as projection microstereolithography, Zheng et al. fabricated octet microlattices from polymers, metals, and ceramics. The design of the lattices meant that the individual struts making up the materials did not bend under pressure. The materials were therefore exceptionally stiff, strong, and lightweight. Science, this issue p. 1373 Ultralow-density materials that deform through tension or compression rather than bending show much higher stiffness. The mechanical properties of ordinary materials degrade substantially with reduced density because their structural elements bend under applied load. We report a class of microarchitected materials that maintain a nearly constant stiffness per unit mass density, even at ultralow density. This performance derives from a network of nearly isotropic microscale unit cells with high structural connectivity and nanoscale features, whose structural members are designed to carry loads in tension or compression. Production of these microlattices, with polymers, metals, or ceramics as constituent materials, is made possible by projection microstereolithography (an additive micromanufacturing technique) combined with nanoscale coating and postprocessing. We found that these materials exhibit ultrastiff properties across more than three orders of magnitude in density, regardless of the constituent material.

Highly compressible 3D periodic graphene aerogel microlattices

Graphene is a two-dimensional material that offers a unique combination of low density, exceptional mechanical properties, large surface area and excellent electrical conductivity. Recent progress has produced bulk 3D assemblies of graphene, such as graphene aerogels, but they possess purely stochastic porous networks, which limit their performance compared with the potential of an engineered architecture. Here we report the fabrication of periodic graphene aerogel microlattices, possessing an engineered architecture via a 3D printing technique known as direct ink writing. The 3D printed graphene aerogels are lightweight, highly conductive and exhibit supercompressibility (up to 90% compressive strain). Moreover, the Youngs moduli of the 3D printed graphene aerogels show an order of magnitude improvement over bulk graphene materials with comparable geometric density and possess large surface areas. Adapting the 3D printing technique to graphene aerogels realizes the possibility of fabricating a myriad of complex aerogel architectures for a broad range of applications.

A six-wafer combustion system for a silicon micro gas turbine engine

As part of a program to develop a micro gas turbine engine capable of producing 10-50 W of electrical power in a package less than one cubic centimeter in volume, we present the design, fabrication, packaging, and experimental test results for the 6-wafer combustion system for a silicon microengine. Comprising the main nonrotating functional components of the engine, the device described measures 2.1 cm/spl times/2.1 cm/spl times/0.38 cm and is largely fabricated by deep reactive ion etching through a total thickness of 3800 /spl mu/m. Complete with a set of fuel plenums, pressure ports, fuel injectors, igniters, fluidic interconnects, and compressor and turbine static airfoils, this structure is the first demonstration of the complete hot flow path of a multilevel micro gas turbine engine. The 0.195 cm/sup 3/ combustion chamber is shown to sustain a stable hydrogen flame over a range of operating mass flows and fuel-air mixture ratios and to produce exit gas temperatures in excess of 1600 K. It also serves as the first experimental demonstration of stable hydrocarbon microcombustion within the structural constraints of silicon. Combined with longevity tests at elevated temperatures for tens of hours, these results demonstrate the viability of a silicon-based combustion system for micro heat engine applications.

Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores

Graphene is an atomically thin, two-dimensional (2D) carbon material that offers a unique combination of low density, exceptional mechanical properties, thermal stability, large surface area, and excellent electrical conductivity. Recent progress has resulted in macro-assemblies of graphene, such as bulk graphene aerogels for a variety of applications. However, these three-dimensional (3D) graphenes exhibit physicochemical property attenuation compared to their 2D building blocks because of one-fold composition and tortuous, stochastic porous networks. These limitations can be offset by developing a graphene composite material with an engineered porous architecture. Here, we report the fabrication of 3D periodic graphene composite aerogel microlattices for supercapacitor applications, via a 3D printing technique known as direct-ink writing. The key factor in developing these novel aerogels is creating an extrudable graphene oxide-based composite ink and modifying the 3D printing method to accommodate aerogel processing. The 3D-printed graphene composite aerogel (3D-GCA) electrodes are lightweight, highly conductive, and exhibit excellent electrochemical properties. In particular, the supercapacitors using these 3D-GCA electrodes with thicknesses on the order of millimeters display exceptional capacitive retention (ca. 90% from 0.5 to 10 A·g(-1)) and power densities (>4 kW·kg(-1)) that equal or exceed those of reported devices made with electrodes 10-100 times thinner. This work provides an example of how 3D-printed materials, such as graphene aerogels, can significantly expand the design space for fabricating high-performance and fully integrable energy storage devices optimized for a broad range of applications.

Capacitive desalination with flow-through electrodes

Capacitive desalination (CD) is a promising desalination technique as, relative to reverse osmosis (RO), it requires no membrane components, can operate at low (sub-osmotic) pressures, and can potentially utilize less energy for brackish water desalination. In a typical CD cell, the feed water flows through the separator layer between two electrically charged, nanoporous carbon electrodes. This architecture results in significant performance limitations, including an inability to easily (in a single charge) desalinate moderate brackish water feeds and slow, diffusion-limited desalination. We here describe an alternative architecture, where the feed flows directly through electrodes along the primary electric field direction, which we term flow-through electrode (FTE) capacitive desalination. Using macroscopic porous electrode theory, we show that FTE CD enables significant reductions in desalination time and can desalinate higher salinity feeds per charge. We then demonstrate these benefits using a custom-built FTE CD cell containing novel hierarchical carbon aerogel monoliths as an electrode material. The pore structure of our electrodes includes both micron-scale and sub-10 nm pores, allowing our electrodes to exhibit both low flow resistance and very high specific capacitance (>100 F g−1). Our cell demonstrates feed concentration reductions of up to 70 mM NaCl per charge and a mean sorption rate of nearly 1 mg NaCl per g aerogel per min, 4 to 10 times higher than that demonstrated by the typical CD cell architecture. We also show that, as predicted by our model, our cell desalinates the feed at the cells RC timescale rather than the significantly longer diffusive timescale characteristic of typical CD cells.

High Power Density Silicon Combustion Systems for Micro Gas Turbine Engines

As part of an effort to develop a microscale gas turbine engine for power generation and micropropulsion applications, this paper presents the design, fabrication, experimental testing, and modeling of the combustion system. Two radial inflow combustor designs were examined; a single-zone arrangement and a primary and dilution-zone configuration. Both combustors were micromachined from silicon using deep reactive ion etching (DRIE) and aligned fusion wafer handing. Hydrogen-air and hydrocarbon-air combustion were stabilized in both devices, each with chamber volumes of 191 mm 3 . Exit gas temperatures as high as 1800 K and power densities in excess of 1100 MW/m 3 were achieved. For the same equivalence ratio and overall efficiency, the dual-zone combustor reached power densities nearly double that of the single-zone design. Because diagnostics in microscale devices are often highly intrusive, numerical simulations were used to gain insight into the fluid and combustion physics. Unlike large-scale combustors, the performance of the microcombustors was found to be mole severely limited by heat transfer and chemical kinetics constraints. Important design trades are identified and recommendations for microcombustor design are presented.

Multiscale metallic metamaterials.

Materials with three-dimensional micro- and nanoarchitectures exhibit many beneficial mechanical, energy conversion and optical properties. However, these three-dimensional microarchitectures are significantly limited by their scalability. Efforts have only been successful only in demonstrating overall structure sizes of hundreds of micrometres, or contain size-scale gaps of several orders of magnitude. This results in degraded mechanical properties at the macroscale. Here we demonstrate hierarchical metamaterials with disparate three-dimensional features spanning seven orders of magnitude, from nanometres to centimetres. At the macroscale they achieve high tensile elasticity (>20%) not found in their brittle-like metallic constituents, and a near-constant specific strength. Creation of these materials is enabled by a high-resolution, large-area additive manufacturing technique with scalability not achievable by two-photon polymerization or traditional stereolithography. With overall part sizes approaching tens of centimetres, these unique nanostructured metamaterials might find use in a broad array of applications.

Preliminary development of a hydrocarbon-fueled catalytic micro-combustor

Abstract This paper reports development of a hydrocarbon-fueled micro-combustion system for a micro-scale gas turbine engine for power generation and micro-propulsion applications. A three-wafer catalytic combustor was fabricated and tested. Efficiencies in excess of 40% were achieved for ethylene–air and propane–air combustion. A fabrication process for a six-wafer catalytic combustor was developed and this device was successfully constructed.

Encapsulated liquid sorbents for carbon dioxide capture

Drawbacks of current carbon dioxide capture methods include corrosivity, evaporative losses and fouling. Separating the capture solvent from infrastructure and effluent gases via microencapsulation provides possible solutions to these issues. Here we report carbon capture materials that may enable low-cost and energy-efficient capture of carbon dioxide from flue gas. Polymer microcapsules composed of liquid carbonate cores and highly permeable silicone shells are produced by microfluidic assembly. This motif couples the capacity and selectivity of liquid sorbents with high surface area to facilitate rapid and controlled carbon dioxide uptake and release over repeated cycles. While mass transport across the capsule shell is slightly lower relative to neat liquid sorbents, the surface area enhancement gained via encapsulation provides an order-of-magnitude increase in carbon dioxide absorption rates for a given sorbent mass. The microcapsules are stable under typical industrial operating conditions and may be used in supported packing and fluidized beds for large-scale carbon capture.

Design and optimization of a light-emitting diode projection micro-stereolithography three-dimensional manufacturing system

The rapid manufacture of complex three-dimensional micro-scale components has eluded researchers for decades. Several additive manufacturing options have been limited by either speed or the ability to fabricate true three-dimensional structures. Projection micro-stereolithography (PμSL) is a low cost, high throughput additive fabrication technique capable of generating three-dimensional microstructures in a bottom-up, layer by layer fashion. The PμSL system is reliable and capable of manufacturing a variety of highly complex, three-dimensional structures from micro- to meso-scales with micro-scale architecture and submicron precision. Our PμSL system utilizes a reconfigurable digital mask and a 395 nm light-emitting diode (LED) array to polymerize a liquid monomer in a layer-by-layer manufacturing process. This paper discusses the critical process parameters that influence polymerization depth and structure quality. Experimental characterization and performance of the LED-based PμSL system for fabricating highly complex three-dimensional structures for a large range of applications is presented.