Nikhil Koratkar

Enhanced Mechanical Properties of Nanocomposites at Low Graphene Content

In this study, the mechanical properties of epoxy nanocomposites with graphene platelets, single-walled carbon nanotubes, and multi-walled carbon nanotube additives were compared at a nanofiller weight fraction of 0.1 +/- 0.002%. The mechanical properties measured were the Youngs modulus, ultimate tensile strength, fracture toughness, fracture energy, and the materials resistance to fatigue crack propagation. The results indicate that graphene platelets significantly out-perform carbon nanotube additives. The Youngs modulus of the graphene nanocomposite was approximately 31% greater than the pristine epoxy as compared to approximately 3% increase for single-walled carbon nanotubes. The tensile strength of the baseline epoxy was enhanced by approximately 40% with graphene platelets compared to approximately 14% improvement for multi-walled carbon nanotubes. The mode I fracture toughness of the nanocomposite with graphene platelets showed approximately 53% increase over the epoxy compared to approximately 20% improvement for multi-walled carbon nanotubes. The fatigue resistance results also showed significantly different trends. While the fatigue suppression response of nanotube/epoxy composites degrades dramatically as the stress intensity factor amplitude is increased, the reverse effect is seen for graphene-based nanocomposites. The superiority of graphene platelets over carbon nanotubes in terms of mechanical properties enhancement may be related to their high specific surface area, enhanced nanofiller-matrix adhesion/interlocking arising from their wrinkled (rough) surface, as well as the two-dimensional (planar) geometry of graphene platelets.

Miniaturized gas ionization sensors using carbon nanotubes

Gas sensors operate by a variety of fundamentally different mechanisms. Ionization sensors work by fingerprinting the ionization characteristics of distinct gases, but they are limited by their huge, bulky architecture, high power consumption and risky high-voltage operation. Here we report the fabrication and successful testing of ionization microsensors featuring the electrical breakdown of a range of gases and gas mixtures at carbon nanotube tips. The sharp tips of nanotubes generate very high electric fields at relatively low voltages, lowering breakdown voltages several-fold in comparison to traditional electrodes, and thereby enabling compact, battery-powered and safe operation of such sensors. The sensors show good sensitivity and selectivity, and are unaffected by extraneous factors such as temperature, humidity, and gas flow. As such, the devices offer several practical advantages over previously reported nanotube sensor systems. The simple, low-cost, sensors described here could be deployed for a variety of applications, such as environmental monitoring, sensing in chemical processing plants, and gas detection for counter-terrorism.

Fracture and Fatigue in Graphene Nanocomposites

Graphene, a single-atom-thick sheet of sp-bonded carbon atoms, has generatedmuch interest due to its high specific area and novel mechanical, electrical, and thermal properties. Recent advances in the production of bulk quantities of exfoliated graphene sheets from graphite have enabled the fabrication of graphene–polymer composites. Such composites show tremendous potential for mechanical-property enhancement due to their combination of high specific surface area, strong nanofiller–matrix adhesion and the outstanding mechanical properties of the sp carbon bonding network in graphene. Graphene fillers have been successfully dispersed in poly(styrene), poly(acrylonitrile) and poly(methyl methacrylate) matrices and the responses of their Young’s modulus, ultimate tensile strength, andglass-transition temperaturehave been characterized. However, to the best of our knowledge there is no report on the fracture toughness and fatigue properties of graphene–polymer composites. Fracture toughness describes the ability of a material containing a crack to resist fracture and it is a critically important material property for design applications. Fatigue involves dynamic propagation of cracks under cyclic loading and it is one of the primary causes of catastrophic failure in structural materials. Consequently, the material’s resistance to fracture and fatigue crack propagation are of paramount importance to prevent failure. Herein we report the fracture toughness, fracture energy, and fatigue properties of an epoxy polymer reinforced with various weight fractions of functionalized graphene sheets. Remarkably, only 0.125% weight of functionalized graphene sheets was observed to increase the fracture toughness of the pristine (unfilled) epoxy by 65% and the fracture energy by 115%.Toachievecomparableenhancement,carbonnanotube (CNT) and nanoparticle epoxy composites require one to two orders of magnitude larger weight fraction of nanofillers. Under fatigue conditions, incorporation of 0.125% weight of functionalized graphene sheets drastically reduced the rate of crack propagation in the epoxy 25-fold. Fractography analysis

High Sensitivity Gas Detection Using a Macroscopic Three-Dimensional Graphene Foam Network

Nanostructures are known to be exquisitely sensitive to the chemical environment and offer ultra-high sensitivity for gas-sensing. However, the fabrication and operation of devices that use individual nanostructures for sensing is complex, expensive and suffers from poor reliability due to contamination and large variability from sample-to-sample. By contrast, conventional solid-state and conducting-polymer sensors offer excellent reliability but suffer from reduced sensitivity at room-temperature. Here we report a macro graphene foam-like three-dimensional network which combines the best of both worlds. The walls of the foam are comprised of few-layer graphene sheets resulting in high sensitivity; we demonstrate parts-per-million level detection of NH3 and NO2 in air at room-temperature. Further, the foam is a mechanically robust and flexible macro-scale network that is easy to contact (without Lithography) and can rival the durability and affordability of traditional sensors. Moreover, Joule-heating expels chemisorbed molecules from the foams surface leading to fully-reversible and low-power operation.

Toughening in Graphene Ceramic Composites

The majority of work in graphene nanocomposites has focused on polymer matrices. Here we report for the first time the use of graphene to enhance the toughness of bulk silicon nitride ceramics. Ceramics are ideally suited for high-temperature applications but suffer from poor toughness. Our approach uses graphene platelets (GPL) that are homogeneously dispersed with silicon nitride particles and densified, at ∼1650 °C, using spark plasma sintering. The sintering parameters are selected to enable the GPL to survive the harsh processing environment, as confirmed by Raman spectroscopy. We find that the ceramics fracture toughness increases by up to ∼235% (from ∼2.8 to ∼6.6 MPa·m(1/2)) at ∼1.5% GPL volume fraction. Most interestingly, novel toughening mechanisms were observed that show GPL wrapping and anchoring themselves around individual ceramic grains to resist sheet pullout. The resulting cage-like graphene structures that encapsulate the individual grains were observed to deflect propagating cracks in not just two but three dimensions.

Nanostructured Copper Interfaces for Enhanced Boiling

Phase change through boiling is used in a variety of heat-transfer and chemical reaction applications. The state of the art in nucleate boiling has focused on increasing the density of bubble nucleation using porous structures and microchannels with characteristic sizes of tens of micrometers. Traditionally, it is thought that nanoscale surfaces will not improve boiling heat transfer, since the bubble nucleation process is not expected to be enhanced by such small cavities. In the experiments reported here, we observed unexpected enhancements in boiling performance for a nanostructured copper (Cu) surface formed by the deposition of Cu nanorods on a Cu substrate. Moreover, we observed striking differences in the dynamics of bubble nucleation and release from the Cu nanorods, including smaller bubble diameters, higher bubble release frequencies, and an approximately 30-fold increase in the density of active bubble nucleation sites. It appears that the ability of the Cu surface with nanorods to generate stable nucleation of bubbles at low superheated temperatures results from a synergistic coupling effect between the nanoscale gas cavities (or nanobubbles) formed within the nanorod interstices and micrometer-scale defects (voids) that form on the film surface during nanorod deposition. For such a coupled system, the interconnected nanoscale gas cavities stabilize (or feed) bubble nucleation at the microscale defect sites. This is distinct from conventional-scale boiling surfaces, since for the nanostructured surface the bubble nucleation stability is provided by features with orders-of-magnitude smaller scales than the cavity-mouth openings.

Superhydrophobic to superhydrophilic wetting control in graphene films.

Adv. Mater. 2010, 22, 2151–2154 2010 WILEY-VCH Verlag G T IO N Superhydrophobic materials with water contact angles above 1508 are the key enabler for antisticking, anticontamination, and self-cleaning technologies. Similarly, superhydrophilic materials with water contact angles below 108 have many important applications; for example, as a wicking material in heat pipes and for enhanced boiling heat transfer. In general, the wettability of a solid surface is strongly influenced both by its chemical composition and by its geometric structure (or surface roughness). Several experimental and modeling studies have focused on exploiting surface roughness to engineer superhydrophobicity or superhydrophilicity. Both microscale roughness features (e.g., micromachined silicon pillars) as well as nanoscale features (e.g., aligned arrays of carbon nanotubes) have been investigated. However, so far the wetting properties of graphene-based coatings have not been studied in detail. Graphene is a single-atom-thick sheet of sp hybridized carbon atoms. When deposited on a planer substrate, the individual graphene sheets form an interconnected film, which increases the surface roughness of the substrate by one to two orders of magnitude. We demonstrate here that this roughness effect in conjunction with the surface chemistry of the graphene sheets can be used to dramatically alter the wettability of the substrate. If hydrophilic graphene sheets are used (for example, by sonicating the as-produced graphene in water), the substrate acquires a superhydrophilic character. Conversely if hydrophobic graphene sheets are used (by sonicating the as-produced graphene in acetone) then the roughness effect imparts superhydrophobicity to the underlying substrate. By controlling the relative proportion of acetone and water in the solvent, the contact angle of the resulting graphene film can be tailored over a wide range (from superhydrophobic to superhydrophilic). Such graphene-based coatings with controllable wetting properties provide a facile and effective means to modify the wettability of a variety of surfaces. The graphene sheets used in this study were extracted from graphite using the method developed in Reference [19,20]. In this method, partially oxygenated graphene sheets are generated by the rapid thermal expansion (>2000 8C min ) of completely oxidized graphite oxide. The protocols used to oxidize graphite to graphite oxide and then generate graphene sheets (Fig. 1a) by the thermal exfoliation of graphite oxide are provided in the Experimental section. Figure 1b illustrates a transmission electron microscopy (TEM) image of a typical graphene flake synthesized by the above method and deposited on a standard TEM grid for imaging. The flake is several micrometers in dimension; note the wrinkled (rough) surface texture of the graphene flake. Figure 1c displays a high-resolution TEM (HRTEM) image of the edge of a typical graphene flake, indicating that each flake is comprised of 3 individual graphene sheets. The electron diffraction pattern (shown in inset) confirms the signature of few-layered graphene.

Graphene-Based Chemical Sensors

Pioneering research in 2004 by Geim and Novoselov (2010 Nobel Prize winners in Physics) of the University of Manchester led to the isolation of a monolayer graphene sheet. Graphene is a single-atom-thick sheet of sp(2) hybridized carbon atoms that are packed in a hexagonal honeycomb crystalline structure. Graphene is the fundamental building block of all sp(2) carbon materials including single-walled carbon nanotubes, mutliwalled carbon nanotubes, and graphite and is therefore interesting from the fundamental standpoint as well as for practical applications. One of the most promising applications of graphene that has emerged so far is its utilization as an ultrasensitive chemical or gas sensor. In this article, we review some of the significant work performed with graphene and its derivatives for gas detection and provide a perspective on the challenges that need to be overcome to enable commercially viable graphene chemical sensor technologies.

Effect of defects on the intrinsic strength and stiffness of graphene

It is important from a fundamental standpoint and for practical applications to understand how the mechanical properties of graphene are influenced by defects. Here we report that the two-dimensional elastic modulus of graphene is maintained even at a high density of sp(3)-type defects. Moreover, the breaking strength of defective graphene is only ~14% smaller than its pristine counterpart in the sp(3)-defect regime. By contrast, we report a significant drop in the mechanical properties of graphene in the vacancy-defect regime. We also provide a mapping between the Raman spectra of defective graphene and its mechanical properties. This provides a simple, yet non-destructive methodology to identify graphene samples that are still mechanically functional. By establishing a relationship between the type and density of defects and the mechanical properties of graphene, this work provides important basic information for the rational design of composites and other systems utilizing the high modulus and strength of graphene.

Tunable Bandgap in Graphene by the Controlled Adsorption of Water Molecules

Graphene, a single-atom-thick layer of sp 2 -hybridized carbon atoms, has generated considerable excitement in the scientifi c community due to its peculiar electronic band structure, which leads to unusual phenomena such as the anomalous quantum Hall effect, [ 1,2 ] spin-resolved quantum interference, [ 3 ] ballistic electron transport, [ 4 ] and bipolar supercurrent. [ 5 ] However, pristine graphene is a semimetal with zero bandgap; the local density of states at the Fermi level is zero and conduction can only occur by the thermal excitation of electrons. [ 2 ] This lack of an electronic bandgap is the major obstacle limiting the utilization of graphene in nano-electronic and -photonic devices, [ 6,7 ] such as p–n junctions, transistors, photodiodes, and lasers. The graphene band structure is sensitive to lattice symmetry and several methods have been developed to break this symmetry and open an energy gap. These methods are based on a variety of techniques, such as defect generation, [ 8 ] doping (e.g., with potassium [ 9 ] ), applied bias, [ 10–12 ] and interaction with gases [ 13 ] (e.g., nitrogen dioxide). For instance, in reference [ 12 ] a tunable bandgap of up to 0.25 eV was achieved for electrically gated bilayer graphene by a variable external electric fi eld. Similarly, an internal electric fi eld produced by an imbalance of doped charge between two graphene layers has been shown to open a bandgap. [ 9 ] It has been demonstrated that a gap of ≈ 0.26 eV can be produced by growing graphene epitaxially on silicon carbide substrates. [ 14 ] This gap originated from the breaking of sublattice symmetry due to the graphene–substrate interaction. Patterned adsorption of atomic hydrogen onto the Moire superlattice positions of graphene [ 15 ] has resulted in a bandgap of ≈ 0.73 eV opening, while half-hydrogenated graphene [ 16 ] resulted in a bandgap of ≈ 0.43 eV. A graphene nanomesh structure [ 17 ] has also been shown to exhibit a bandgap. In this graphene structure, lateral quantum confi nement and localization effects due to