Three-dimensional Printing of Complex Graphite Structures
Seyed Mohammad Sajadi, Shayan Enayat, Lívia Vásárhelyi, Alessandro Alabastri, Minghe Lou, Lucas M. Sassi, Alex Kutana, Sanjit Bhowmick, Christian Durante, Ákos … 展开作者
Seyed Mohammad Sajadi, Shayan Enayat, Lívia Vásárhelyi, Alessandro Alabastri, Minghe Lou, Lucas M. Sassi, Alex Kutana, Sanjit Bhowmick, Christian Durante, Ákos Kukovecz, Anand B. Puthirath, Zoltán Kónya, Robert Vajtai, Peter Boul, Chandra Shekhar Tiwary, Muhammad M. Rahman, Pulickel M. Ajayan
Graphite, with many industrial applications, is one of the widely sought-after allotropes of carbon. The sp2 hybridized and thermodynamically stable form of carbon forms a layered structure with strong in-plane carbon bonds and weak inter-layer van der Waals bonding. Graphite is also a high-temperature ceramic, and shaping them into complex geometries is challenging, given its limited sintering behavior even at high temperatures. Although the geometric design of the graphite structure in many of the applications could dictate its precision performance, conventional synthesis methods for formulating complex geometric graphite shapes are limited due to the intrinsic brittleness and difficulties of high-temperature processing. Here, we report the development of colloidal graphite ink from commercial graphite powders with reproducible rheological behavior that allows the fabrication of any complex architectures with tunable geometry and directionality via 3D printing at room temperature. The method is enabled via using small amounts of clay, another layered material, as an additive, allowing the proper design of the graphene ink and subsequent binding of graphite platelets during printing. Sheared layers of clay are easily able to flow, adapt, and interface with graphite layers forming strong binding between the layers and between particles that make the larger structures. The direct ink printing of complex 3D architectures of graphite without further heat treatments could lead to easy shape engineering and related applications of graphite at various length scales, including complex graphite molds or crucibles. The 3D printed complex graphitic structures exhibit excellent thermal, electrical, and mechanical properties, and the clay additive does not seem to alter these properties due to the excellent inter-layer dispersion and mixing within the graphite material.
Highly oriented pyrolytic graphite (HOPG) was scribed by pulsed laser beam to produce square patterns. Patterning of HOPG surface facilitates the detachment of graphene layers during contact printing. Direct HOPG-to-substrate and glue-assisted stamp printing of a few-layers graphene was compared. Printed graphene sheets were visualized by optical and scanning electron microscopy. The number of graphene layers was measured by atomic force microscopy. Glue-assisted stamp printing allows printing relatively large graphene sheets (40x40 microns) onto a silicon wafer, which can be important for mic…
We report the exfoliation of graphite in aqueous solutions under high shear rate [$\sim10^8s^{-1}$] turbulent flow conditions, with a 100\% exfoliation yield. The material is stabilized without centrifugation at concentrations up to 100 g/L using carboxymethylcellulose sodium salt to formulate conductive printable inks. The sheet resistance of blade coated films is below$\sim2Ω/\square$. This is a simple and scalable production route for graphene-based conductive inks for large area printing in flexible electronics.
We report on suspended single-layer graphene deposition by a transfer-printing approach based on polydimethylsiloxane stamps. The transfer printing method allows the exfoliation of graphite flakes from a bulk graphite sample and their residue-free deposition on a silicon dioxide substrate. This deposition system creates a blistered graphene surface due to strain induced by the transfer process itself. Single-layer-graphene deposition and its "blistering" on the substrate are demonstrated by a combination of Raman spectroscopy, scanning electron microscopy and atomic-force microscopy measuremen…
We demonstrate ink-jet printing as a viable method for large area fabrication of graphene devices. We produce a graphene-based ink by liquid phase exfoliation of graphite in N-Methylpyrrolidone. We use it to print thin-film transistors, with mobilities up to~95cm^2V^(-1)s(-1), as well as transparent and conductive patterns, with~80 % transmittance and~30kOhm/sq sheet resistance. This paves the way to all-printed, flexible and transparent graphene devices on arbitrary substrates
Biological living materials, such as animal bones and plant stems, are able to self-heal, regenerate, adapt and make decisions under environmental pressures. Despite recent successful efforts to imbue synthetic materials with some of these remarkable functionalities, many emerging properties of complex adaptive systems found in biology remain unexplored in engineered living materials. Here, we report on a three-dimensional printing approach that harnesses the emerging properties of fungal mycelium to create living complex materials that self-repair, regenerate and adapt to the environment whil…
The emerging new paradigm of technologies, the internet of things, entails a process of device miniaturization to combine several functional components, such as sensors, actuators, and powering elements, in a single individual on-chip platform. An essential requirement is for the devices to have a small footprint and thus to be extended over three-dimensions to present adequate performance. A suitable technique to realize devices of complex architectures and virtually any size is three-dimensional printing. So far its use has seen applications exclusively at the macroscale. Here we report the …
We report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by x-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Transport measurements of exfoliated graphene after SrO deposition show a strong dependence between the Dirac point and Sr oxidation. Subsequently, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (0…
Electrochemical 3D printing of conductors with microscale resolution holds a great promise for a wide range of applications, but the choice of suitable metals for these technologies remains limited. Most efforts so far have been focused on deposition of copper, however, other metals are also of interest, especially when tuning of mechanical, electrical, or optical properties is required for a given application. Here we address the issue of a limited materials choice in electrochemical 3D printing by extending the materials library to silver and nickel. Free-standing microscale structures are f…
Conventional 3D printings are generally time-consuming and printable metal inks are rather limited. From an alternative way, we proposed a liquid phase 3D printing for quickly making metal objects. Through introducing metal alloys whose melting point is slightly above room temperature as printing inks, several representative structures spanning from one, two and three dimension to more complex patterns were demonstrated to be quickly fabricated. Compared with the air cooling in a conventional 3D printing, the liquid-phase-manufacturing offers a much higher cooling rate and thus significantly i…
3D printing technologies are currently enabling the fabrication of objects with complex architectures and tailored properties. In such framework, the production of 3D optical structures, which are typically based on optical transparent matrices, optionally doped with active molecular compounds and nanoparticles, is still limited by the poor uniformity of the printed structures. Both bulk inhomogeneities and surface roughness of the printed structures can negatively affect the propagation of light in 3D printed optical components. Here we investigate photopolymerization-based printing processes…
Porous materials are relevant for a broad range of technologies from catalysis and filtration, to tissue engineering and lightweight structures. Controlling the porosity of these materials over multiple length scales often leads to enticing new functionalities and higher efficiency but has been limited by manufacturing challenges and the poor understanding of the properties of hierarchical structures. Here, we report an experimental platform for the design and manufacturing of hierarchical porous materials via the stereolithographic printing of stable photo-curable Pickering emulsions. In the …
We have performed ab-initio molecular dynamics simulations to elucidate the mechanism of the phase transition at high pressure from hexagonal graphite (HG) to hexagonal diamond (HD) or to cubic diamond (CD). The transition from HG to HD is found to occur swiftly in very small time of 0.2 ps, with large cooperative displacements of all the atoms. We observe that alternate layers of atoms in HG slide in opposite directions by (1/3, 1/6, 0) and (-1/3, -1/6, 0), respectively, which is about 0.7 Å along the pm[2, 1, 0] direction, while simultaneously puckering by about pm0.25 Å perpendicular to the…
Additive manufacturing at the micro- and nanoscale has seen a recent upsurge to suit the increasing demand for more elaborate structures. However, the integration and precise placement of multiple distinct materials at small scales remain a challenge. To this end, we combine here the directed capillary assembly of colloidal particles and two-photon direct laser writing (DLW) to realize a new class of multi-material microstructures. We use DLW both to fabricate 3D micro-templates to guide the capillary assembly of soft- and hard colloids, and to link well-defined arrangements of polystyrene or …
The advances in the mass scale manufacturing of microscale energy storage devices via inkjet printing rely on the development of high-quality printable ink. The earth-abundant, non-toxic carbon materials such as graphene, carbon nanotube (CNT), reduced graphene oxide (r-GO) have shown excellent electrochemical performance and thus garnered significant interest as suitable electrode material. Here we report the formulation of printable graphene aerogel ink and the fabrication of the micro-supercapacitors (μ-SCs) on flexible polyimide substrates via inkjet printing method. The advantage of using…
Creating non-equilibrium states of matter with highly unequal electron and lattice temperatures allows unsurpassed insight into the dynamic coupling between electrons and ions through time-resolved energy relaxation measurements. Recent studies on low-temperature laser-heated graphite suggest a complex energy exchange when compared to other materials. To avoid problems related to surface preparation, crystal quality and poor understanding of the energy deposition and transport mechanisms, we apply a different energy deposition mechanism, via laser-accelerated protons, to isochorically and non-…
We describe the results of atomic-level stick-slip friction measurements performed on chemically-modified graphite, using atomic force microscopy (AFM). Through detailed molecular dynamics simulations, coarse-grained simulations, and theoretical arguments, we report on complex indentation profiles during AFM scans involving local reversible exfoliation of the top layer of graphene from the underlying graphite sample and its effect on the measured friction force during retraction of the scanning tip. In particular, we report nearly constant lateral stick-slip magnitudes at decreasing loads, whi…
Methanol occupies a central role in chemical synthesis and is considered an ideal candidate for cleaner fuel storage and transportation. It can be catalyzed from water and volatile organic compounds such as carbon dioxide, thereby offering an attractive solution for reducing carbon emissions. However molecular-level experimental observations of the catalytic process are scarce, and most existing catalysts tend to rely on empirically optimized, expensive and complex nano- composite materials. This lack of molecular-level insights has precluded the development of simpler, more cost-effective alt…
We demonstrate the organometallic hexahapto complexation of chromium with graphene, graphite and carbon nanotubes. All of these extended periodic pi-electron systems exhibit some degree of reactivity toward the reagents CrCO)6 and (eta6-benzene)Cr(CO)3, and we are able to demonstrate the formation of (eta6-rene)Cr(CO)3 or (eta6-arene)2Cr, where arene = single-walled carbon nanotubes (SWNT), exfoliated graphene (XG), epitaxial graphene (EG) and highly-oriented pyrolytic graphite (HOPG). We find that the SWNTs are the least reactive presumably as a result of the effect of curvature on the format…
