Effect of density variation and non-covalent functionalization on the compressive behavior of carbon nanotube arrays

Arrays of aligned carbon nanotubes (CNTs) have been proposed for different applications, including electrochemical energy storage and shock-absorbing materials. Understanding their mechanical response, in relation to their structural characteristics, is important for tailoring the synthesis method to the different operational conditions of the material. In this paper, we grow vertically aligned CNT arrays using a thermal chemical vapor deposition system, and we study the effects of precursor flow on the structural and mechanical properties of the CNT arrays. We show that the CNT growth process is inhomogeneous along the direction of the precursor flow, resulting in varying bulk density at different points on the growth substrate. We also study the effects of non-covalent functionalization of the CNTs after growth, using surfactant and nanoparticles, to vary the effective bulk density and structural arrangement of the arrays. We find that the stiffness and peak stress of the materials increase approximately linearly with increasing bulk density.

Experimental evidence for `carbon bonding' in the solid state from charge density analysis

The validity of the newly proposed `carbon bonding', an interaction where a carbon atom acts as an electrophilic site towards a variety of nucleophiles, has been investigated in the solid state. X-ray charge density analysis provides experimental evidence for this hitherto unexplored interaction and unravels its nature and strength.

Enhancing field emission from a carbon nanotube array by lateral control of electrodynamic force field

Fluctuation of field emission current from carbon nanotubes (CNTs) poses certain difficulties for their use in nanobiomedical X-ray devices and imaging probes. This problem arises due to deformation of the CNTs due to electrodynamic force field and electron-phonon interaction. It is of great importance to have precise control of emitted electron beams very near the CNT tips. In this paper, a new array configuration with stacked array of CNTs is analysed and it is shown that the current density distribution is greatly localised at the middle of the array, that the scatter due to electrodynamic force field is minimised and that the temperature transients are much smaller compared to those in an array with random height distribution.

Low temperature electrical transport properties of carbon matrix containing iron nanoparticles

We present a comparative study of the low temperature electrical transport properties of the carbon matrix containing iron nanoparticles and the films. The conductivity of the nanoparticles located just below the metal-insulator transition exhibits metallic behavior with a logarithmic temperature dependence over a large temperature interval. The zero-field conductivity and the negative magnetoresistance, showing a characteristic upturn at liquid helium temperature, are consistently explained by incorporating the Kondo relation and the two dimensional electron-electron interaction. The films, in contrast, exhibit a crossover of the conductivity from power-law dependence at high temperatures to an activated hopping law dependence in the low temperature region. The transition is attributed to changes in the energy dependence of the density of states near the Fermi level. The observed magnetoresistance is discussed in terms of quantum interference effect on a three-dimensional variable range hopping mechanism.

Excellent field emission from semialigned carbon nanofibers grown on cylindrical copper surface

We report the field emission from carbon nanofibers (CNFs) grown directly on cylindrical copper by a simple pyrolysis technique. The turn-on field is 0.17 V/µm and the emission current density is 0.9 mA/cm2 at 0.35 V/µm. The emission current is stable at a field of 0.35 V/µm and 6.5×10−6 Torr. The excellent field emission behavior is attributed to the sp2 phase in CNFs and the stable emission is due to the direct growth. The direct growth on cylindrical cathode is advantageous for field emission. ©2009 American Institute of Physics.

Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.

A Methanol-Tolerant Carbon-Supported Pt-Au Alloy Cathode Catalyst for Direct Methanol Fuel Cells and Its Evaluation by DFT

A Pt-Au alloy catalyst of varying compositions is prepared by codeposition of Pt and Au nanoparticles onto a carbon support to evaluate its electrocatalytic activity toward an oxygen reduction reaction (ORR) with methanol tolerance in direct methanol fuel cells. The optimum atomic weight ratio of Pt to Au in the carbon-supported Pt-Au alloy (Pt-Au/C) as established by cell polarization, linear-sweep voltammetry (LSV), and cyclic voltammetry (CV) studies is determined to be 2:1. A direct methanol fuel cell (DMFC) comprising a carbon-supported Pt-Au (2:1) alloy as the cathode catalyst delivers a peak power density of 120 mW/cm2 at 70 °C in contrast to the peak power density value of 80 mW/cm2 delivered by the DMFC with carbon-supported Pt catalyst operating under identical conditions. Density functional theory (DFT) calculations on a small model cluster reflect electron transfer from Pt to Au within the alloy to be responsible for the synergistic promotion of the oxygen-reduction reaction on a Pt-Au electrode.

Electromechanical interactions in a carbon nanotube based thin film field emitting diode

Carbon nanotubes (CNTs) have emerged as promising candidates for biomedical x-ray devices and other applications of field emission. CNTs grown/deposited in a thin film are used as cathodes for field emission. In spite of the good performance of such cathodes, the procedure to estimate the device current is not straightforward and the required insight towards design optimization is not well developed. In this paper, we report an analysis aided by a computational model and experiments by which the process of evolution and self-assembly (reorientation) of CNTs is characterized and the device current is estimated. The modeling approach involves two steps: (i) a phenomenological description of the degradation and fragmentation of CNTs and (ii) a mechanics based modeling of electromechanical interaction among CNTs during field emission. A computational scheme is developed by which the states of CNTs are updated in a time incremental manner. Finally, the device current is obtained by using the Fowler–Nordheim equation for field emission and by integrating the current density over computational cells. A detailed analysis of the results reveals the deflected shapes of the CNTs in an ensemble and the extent to which the initial state of geometry and orientation angles affect the device current. Experimental results confirm these effects.

New empirical expressions to correlate solubilities of solids in supercritical carbon dioxide

Supercritical processes are gaining importance in the last few years in the food, environmental and pharmaceutical product processing. The design of any supercritical process needs accurate experimental data on solubilities of solids in the supercritical fluids (SCFs). The empirical equations are quite successful in correlating the solubilities of solid compounds in SCF both in the presence and absence of cosolvents. In this work, existing solvate complex models are discussed and a new set of empirical equations is proposed. These equations correlate the solubilities of solids in supercritical carbon dioxide (both in the presence and absence of cosolvents) as a function of temperature, density of supercritical carbon dioxide and the mole fraction of cosolvent. The accuracy of the proposed models was evaluated by correlating 15 binary and 18 ternary systems. The proposed models provided the best overall correlations. (C) 2009 Elsevier BA/. All rights reserved.

Terahertz wave characteristics of a single-walled carbon nanotube containing a fluid flow using the nonlocal Timoshenko beam model

This paper presents the effect of nonlocal scaling parameter on the terahertz wave propagation in fluid filled single walled carbon nanotubes (SWCNTs). The SWCNT is modeled as a Timoshenko beam,including rotary inertia and transverse shear deformation by considering the nonlocal scale effects. A uniform fluid velocity of 1000 m/s is assumed. The analysis shows that, for a fluid filled SWCNT, the wavenumbers of flexural and shear waves will increase and the corresponding wave speeds will decrease as compared to an empty SWCNT. The nonlocal scale parameter introduces certain band gap region in both flexural and shear wave mode where no wave propagation occurs. This is manifested in the wavenumber plots as the region where the wavenumber tends to infinite (or wave speed tends to zero). The frequency at which this phenomenon occurs is called the ``escape frequency''. The effect of fluid density on the terahertz wave propagation in SWCNT is also studied and the analysis shows that as the fluid becomes denser, the wave speeds will decrease. The escape frequency decreases with increase in nonlocal scaling parameter, for both wave modes. We also show that the effect of fluid density and velocity are negligible on the escape frequencies of flexural and shear wave modes. (C) 2010 Elsevier B.V. All rights reserved.

Study on Young's modulus and microhardness of carbon nanotubes reinforced copper nanocomposite

Carbon nanotubes (CNTs) were discovered by Iijima in 1991 as the fourth form of carbon. Carbon nanotubes are the ultimate form of the carbon fibre because of its high Young's modulus in the order of 1 TPa, which is very useful for load transfer in nanocomposites. In the present work, CNT/Cu nanocomposites were fabricated by the powder metallurgy technique, and after extrusion of the nanocomposites, bright field transmission electron microscopic studies were carried out. From the transmission electron microscopic images obtained, a novel method of ascertaining the Young's modulus of multiwalled CNTs is worked out in the present paper, which turns out to be 0.94 TPa, which is consistent with experimental results. Furthermore, an attempt is made to investigate the microhardness of copper by reinforcing it with multiwalled CNTs. There is an increase in hardness by twofold in CNT/Cu nanocomposites as compared to pure Cu matrix. This is due to high relative density, even distribution of CNTs and proper bonding at CNT/Cu interfaces.

Studies on design, fabrication and reliability assessment of embedded passives on a high-density interconnect (HDI) organic substrate using a sequential build-up process

One of the foremost design considerations in microelectronics miniaturization is the use of embedded passives which provide practical solution. In a typical circuit, over 80 percent of the electronic components are passives such as resistors, inductors, and capacitors that could take up to almost 50 percent of the entire printed circuit board area. By integrating passive components within the substrate instead of being on the surface, embedded passives reduce the system real estate, eliminate the need for discrete and assembly, enhance electrical performance and reliability, and potentially reduce the overall cost. Moreover, it is lead free. Even with these advantages, embedded passive technology is at a relatively immature stage and more characterization and optimization are needed for practical applications leading to its commercialization.This paper presents an entire process from design and fabrication to electrical characterization and reliability test of embedded passives on multilayered microvia organic substrate. Two test vehicles focusing on resistors and capacitors have been designed and fabricated. Embedded capacitors in this study are made with polymer/ceramic nanocomposite (BaTiO3) material to take advantage of low processing temperature of polymers and relatively high dielectric constant of ceramics and the values of these capacitors range from 50 pF to 1.5 nF with capacitance per area of approximately 1.5 nF/cm(2). Limited high frequency measurement of these capacitors was performed. Furthermore, reliability assessments of thermal shock and temperature humidity tests based on JEDEC standards were carried out. Resistors used in this work have been of three types: 1) carbon ink based polymer thick film (PTF), 2) resistor foils with known sheet resistivities which are laminated to printed wiring board (PWB) during a sequential build-up (SBU) process and 3) thin-film resistor plating by electroless method. Realization of embedded resistors on conventional board-level high-loss epoxy (similar to 0.015 at 1 GHz) and proposed low-loss BCB dielectric (similar to 0.0008 at > 40 GHz) has been explored in this study. Ni-P and Ni-W-P alloys were plated using conventional electroless plating, and NiCr and NiCrAlSi foils were used for the foil transfer process. For the first time, Benzocyclobutene (BCB) has been proposed as a board level dielectric for advanced System-on-Package (SOP) module primarily due to its attractive low-loss (for RF application) and thin film (for high density wiring) properties.Although embedded passives are more reliable by eliminating solder joint interconnects, they also introduce other concerns such as cracks, delamination and component instability. More layers may be needed to accommodate the embedded passives, and various materials within the substrate may cause significant thermo -mechanical stress due to coefficient of thermal expansion (CTE) mismatch. In this work, numerical models of embedded capacitors have been developed to qualitatively examine the effects of process conditions and electrical performance due to thermo-mechanical deformations.Also, a prototype working product with the board level design including features of embedded resistors and capacitors are underway. Preliminary results of these are presented.

Terahertz Time Domain Spectroscopy to Detect Low-Frequency Vibrations of Double-Walled Carbon Nanotubes

We have measured the frequency-dependent real index of refraction and extinction coefficient (and hence the complex dielectric function) of a free-standing double-walled carbon nanotube film of thickness 200 nm by using terahertz time domain spectroscopy in the frequency range 0.1 to 2.5 THz. The real index of refraction and extinction coefficient have very high values of approximately 52 and 35, respectively, at 0.1 THz, which decrease at higher frequencies. Two low-frequency phonon modes of the carbon nanotubes at 0.45 and 0.75 THz were clearly observed for the first time in the real and imaginary parts of the complex dielectric function along with a broad resonance centred at around 1.45 THz, the latter being similar to that in single-walled carbon nanotubes assigned to electronic excitations. Our experiments bring out a possible application of double-walled carbon nanotube films as a neutral density filter in the THz range.

Mesoporous Carbon and Poly(3,4-ethylenedioxythiophene) Composite as Catalyst Support for Polymer Electrolyte Fuel Cells

In situ polymerization of 3,4-ethylenedioxythiophene with sol-gel-derived mesoporous carbon (MC) leading to a new composite and its subsequent impregnation with Pt nanoparticles for application in polymer electrolyte fuel cells (PEFCs) is reported. The composite exhibits good dispersion and utilization of platinum nanoparticles akin to other commonly used microporous carbon materials, such as carbon black. Pt-supported MC-poly(3,4-ethylenedioxythiophene) (PEDOT) composite also exhibits promising electrocatalytic activity toward oxygen reduction reaction, which is central to PEFCs. The PEFC with Pt-loaded MC-PEDOT support exhibits 75% of enhancement in its power density in relation to the PEFC with Pt-loaded pristine MC support while operating under identical conditions. It is conjectured that Pt-supported MC-PEDOT composite ameliorates PEFC performance/durability on repetitive potential cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3486172] All rights reserved.

Carbon recombination lines between 34.5 and 770 MHz toward Cassiopeia A

We present observations of low-frequency recombination lines of carbon toward Cas A near 34.5 MHz (n similar to 575) using the Gauribidanur radio telescope and near 560 MHz (n similar to 225) and 770 MHz (n similar to 205) using the NRAO 140 foot (43 m) telescope in Greenbank. We also present high angular resolution (1') observations of the C270 alpha line near 332 MHz using the Very Large Array in B-configuration. A high signal-to-noise ratio spectrum is obtained at 34.5 MHz, which clearly shows a Voigt profile with distinct Lorentzian wings, resulting from significant pressure and radiation broadening at such high quantum numbers. The emission lines detected near 332, 550, and 770 MHz, on the other hand, are narrow and essentially Doppler-broadened. The measured Lorentzian width at 34.5 MHz constrains the allowed combinations of radiation temperature, electron density, and electron temperature in the line-forming region. Radiation broadening at 34.5 MHz places a lower limit of 115 pc on the separation between Cas A and the line-forming clouds. Modeling the variation in the integrated line-to-continuum ratio with frequency indicates that the region is likely to be associated with the cold atomic hydrogen component of the interstellar medium, and the physical properties of this region are likely to be T-e = 75 K, n(e) = 0.02 cm(-3), T-R100 = 3200 K, and n(H) T-e = 10,000 cm(-3) K. Comparison of the distribution of the C270 alpha recombination line emission across Cas A with that of (CO)-C-12 and H I also supports the above conclusion.