A novel conductive humidity sensor based on field ionization from carbon nanotubes

A novel, high efficiency detector for humidity is described, in which the multiwall nanotubes grown on the silicon substrates serve as anode and ITO film glass plate as cathode are separated and insulated by a glass insulator. Application of a positive bias to the multiwall nanotubes generates high electric field sufficient to field-ionize passing gas-phase atoms especially for water vapor. By monitoring the prebreakdown current, relative humidity can be determined. The sensitivity factor (I_75.8%/I_12%) is about 229.4. The recovery time from 53.4 to 6.8% RH for the humidity sensor is about 10 s.     

Fast Constructive Recognition of a Black Box Group Isomorphic toSnorAnusing Goldbach’s Conjecture

The well-known Goldbach Conjecture (GC) states that any sufficiently large even number can be represented as a sum of two odd primes. Although not yet demonstrated, it has been checked for integers up to 10¹⁴. Using two stronger versions of the conjecture, we offer a simple and fast method for recognition of a gray box group G known to be isomorphic to S_n(or A_n) with knownn ≥  20, i.e. for construction1of an isomorphism from G toS_n (or A_n). Correctness and rigorous worst case complexity estimates rely heavily on the conjectures, and yield times of O([ρ + ν + μ ] n log²n) or O([ ρ + ν + μ ] n logn / loglog n) depending on which of the stronger versions of the GC is assumed to hold. Here,ρ is the complexity of generating a uniform random element of G, ν is the complexity of finding the order of a group element in G, and μ is the time necessary for group multiplication in G. Rigorous lower bound and probabilistic approach to the time complexity of the algorithm are discussed in the Appendix.     

Stereoelectronic interaction effects on the conformational properties of hydrogen peroxide and its analogues containing S and Se atoms: An ab initio,hybrid-DFT study and NBO analysis

Ab initio molecular orbital (MP2/6-311+G**//MP2/6-31G+G**) and hybrid-density functional theory (B3LYP/6-311+G**//MP2/6-311+G**) methods and NBO analysis were used to study the stereoelectronic interaction effects on the conformational properties of hydrogen peroxide (1), hydrogen disulfide (2) and hydrogen diselenide (3). The results showed that the Gibbs free energy difference (G_T − G_S) values at 298.15 K and 1 atm between the skew (S) and trans (T) conformations (ΔG_T–S) increase from compound 1 to compound 2 but decrease from compound 2 to compound 3. The C conformations of compounds 1–3 are less stable than their S and T conformations. Based on these results, the racemization processes of the axial symmetrical (C₂ symmetry) conformations of compounds 1–3 take place via their T conformations. Based on the optimized ground state geometries using the MP2/6-311+G** level of theory, the NBO analysis of donor–acceptor (bond–antibond) interactions revealed that the stabilization (resonance) energy associated with LP₂M2 → σ*_M3-H4 electronic delocalization for the S conformations of compounds 1–3 are 1.35, 5.94 and 4.68 kcal mol⁻¹, respectively. There is excellent agreement between the variations of the calculated ΔG_T–S and stabilization (resonance) energies associated with LP₂M2→σ*_M3-H4 electronic delocalization for the S conformations of compounds 1–3. The correlations between resonance energies, orbital integrals, dipole moments, bond orders, structural parameters and conformational behaviors of compounds 1–3 have been investigated. Test were made of complete basis set methods (CBS-QB3, CBS-4 and CBS-Q), the first two gave results essentially indistinguishable from those we used, but the CBS-Q results were in disagreement with experimental and other theoretical results.     

Fabrication and characterization of a thermal switch

The development of a thermal switch based on arrays of liquid–metal micro-droplets is presented. Prototype thermal switches are assembled from a silicon substrate on which is deposited an array of 1600 30-μm liquid–metal micro-droplets. The liquid–metal micro-droplet array makes and breaks contact with a second bare silicon substrate. A gap between the two silicon substrates is filled with either air at 760 Torr, air at of 0.5 Torr or xenon at 760 Torr. Heat transfer and thermal resistance across the thermal switches are measured for “on” (make contact) and “off” (break contact) conditions using guard-heated calorimetry. The figure of merit for a thermal switch, the ratio of “off” state thermal resistance over “on” state thermal resistance, R_off/R_on, is 129 ± 43 for a xenon-filled thermal switch that opens 100 μm and 60 ± 17 for an 0.5 Torr air-filled thermal switch that opens 25 μm. These thermal resistance ratios are shown to be markedly higher than values of R_off/R_on for a thermal switch based on contact between polished silicon surfaces. Transient temperature measurements for the liquid–metal micro-droplet switches indicate thermal switching times of less than 100 ms. Switch lifetimes are found to exceed one-million cycles.     

Evaluation of response characteristics of resistive oxygen sensors based on porous cerium oxide thick film using pressure modulation method

In order to reduce the response time of resistive oxygen sensors using porous cerium oxide thick film, it is important to ascertain the factors controlling response. Pressure modulation method (PMM) was used to find the rate-limiting step of sensor response. This useful method measures the amplitude of sensor output (H(f)) for the sine wave modulation of oxygen partial pressure at constant frequency (f). In PMM, “break” response time, which is minimum period in which the sensor responds precisely, can be measured. Three points were examined: (1) simulated calculations of PMM were carried out using a model of porous thick film in which spherical particles are connected in a three-dimensional network; (2) sensor response speed was experimentally measured using PMM; and (3) the diffusion coefficient and surface reaction coefficient were estimated by comparison between experiment and calculation. The plot of log f versus log H(f) in the high f region was found to have a slope of approximately −0.5 for both porous thick film and non-porous thin film, when the rate-limiting step was diffusion. Calculations showed the response time of porous thick film was 1/20 that of non-porous thin film when the grain diameter of the porous thick film was the same as the thickness of non-porous thin film. At 973 K, “break” response time (t_b) of the resistive oxygen sensor was found by experiment to be 109 ms. It was concluded that the response of the resistive oxygen sensor prepared in this study was strongly controlled by diffusion at 923–1023 K, since the experiment revealed that the slope of plot of log f versus log H(f) in the high f region was approximately −0.5. At 923–1023 K, the diffusion coefficient of oxygen vacancy in porous ceria (D_V) was expressed as follows: D_V (m²s⁻¹) = 5.78 × 10⁻⁴ exp(−1.94 eV/kT). At 1023 K, the surface reaction coefficient (K) was found to exceed 10⁻⁴ m/s.     

Boosting sensitivity of boron nitride nanotube (BNNT) to nitrogen dioxide by Fe encapsulation

The pristine boron nitride nanotube (BNNT) exhibits a poor chemical reactivity to some adsorbates, thus greatly limiting its application for the gas sensor. In the present work, using density functional theory (DFT) methods, we put forward a novel strategy to enhance the sensitivity of BNNT to nitrogen dioxide (NO₂) by the encapsulation of a single Fe atom inside its cavity. The results suggest that the NO₂ molecule can be only physically adsorbed on the pristine BNNT with a small adsorption energy (−0.10 eV). After the inclusion of the Fe atom inside BNNT (Fe@BNNT), the interaction of NO₂ molecules with this tube is significantly enhanced, leading to a transformation from the physisorption of on pristine BNNT to the current chemisorption. Interestingly, up to five NO₂ molecules can be adsorbed on this encapsulated BNNT along its circumference with the average adsorption energy of −0.52 eV, corresponding to a short recovery time (6 ms). Moreover, 0.38 electrons are transferred from the Fe@BNNT to the adsorbed NO₂ molecules, which is enough to induce the obvious change of its electrical conductance. Thus, we predict that the encapsulation of Fe atom inside BNNT would greatly boosts its sensitivity to NO₂ molecules, indicating its potential application as NO₂ sensors.     

Fabrication and characterization of polyaniline-based gas sensor by ultra-thin film technology

Pure polyaniline (PAN) film, polyaniline and acetic acid (AA) mixed film, as well as PAN and polystyrenesulfonic acid (PSSA) composite film with various number of layers were prepared by Langmuir–Blodgett (LB) and self-assembly (SA) techniques. These ultra-thin films were characterized by ultraviolet–visible (UV–VIS) spectroscopy and ellipsometry. It is found that the thickness of PAN-based ultra-thin films increases linearly with the increase of the number of film layers. The gas-sensitivity of these ultra-thin films with various layers to NO₂ was studied. It is found that pure polyaniline films prepared by LB technique had good sensitivity to NO₂, while SA films exhibited faster recovery property. The response time to NO₂ and the relative change of resistance of ultra-thin films increased with the increase of the number of film layers. The response time of three-layer PAN film prepared by LB technique to 20 ppm NO₂ was about 10 s, two-layer SA film was about 8 s. The mechanism of sensitivity to NO₂ of PAN-based ultra-thin films was also discussed.     

On identifying codes that are robust against edge changes

Assume that G = (V, E) is an undirected graph, and C ⊆ V. For every v ∈ V, denote I_r(G; v) = {u ∈ C: d(u,v) ≤ r}, where d(u,v) denotes the number of edges on any shortest path from u to v in G. If all the sets I_r(G; v) for v ∈ V are pairwise different, and none of them is the empty set, the code C is called r-identifying. The motivation for identifying codes comes, for instance, from finding faulty processors in multiprocessor systems or from location detection in emergency sensor networks. The underlying architecture is modelled by a graph. We study various types of identifying codes that are robust against six natural changes in the graph; known or unknown edge deletions, additions or both. Our focus is on the radius r = 1. We show that in the infinite square grid the optimal density of a 1-identifying code that is robust against one unknown edge deletion is 1/2 and the optimal density of a 1-identifying code that is robust against one unknown edge addition equals 3/4 in the infinite hexagonal mesh. Moreover, although it is shown that all six problems are in general different, we prove that in the binary hypercube there are cases where five of the six problems coincide.     

Thermodynamic study of the cerium–cadmium system

Cadmium vapor pressures were determined over Ce–Cd samples by an isopiestic method. The measurements were carried out in the temperature range from 690 to 1080 K and over a composition range of 48–85 at% Cd. From the vapor pressures thermodynamic activities of Cd were derived for all samples at their respective sample temperatures, and partial molar enthalpies of Cd were obtained from the temperature dependence of the activities. With these partial molar enthalpies the Cd activities were converted to a common temperature of 823 K. By means of a Gibbs–Duhem integration Ce activities were calculated, using a corresponding literature value for the two-phase field (CeCd₁₁+L) as integration constant. Finally integral Gibbs energies were calculated for the composition range 48–100 at% Cd with a minimum value of −37 kJ g-atom⁻¹ at 823 K in the phase CeCd. Phase boundaries of the intermetallic compounds CeCd, CeCd₂, Ce₁₃Cd₅₈, and CeCd₁₁ were estimated from the vapor pressure measurements and from SEM analyses.     

A DFT study on the physical adsorption of cyclophosphamide derivatives on the surface of fullerene C60 nanocage

The physical sorption of a series of cyclophosphamide drug derivatives with formula

where x = 2, X = F (2), Cl (3), Br (4); x = 3, X = F (5), Cl (6), Br (7) and x = 4, X = F (8), Cl (9), Br (10) on the surface of fullerene C₆₀ was studied using density functional theory (DFT) at B3LYP and B3PW91 levels. The most negative binding energies obtained using the B3LYP approach and corrected for geometrical BSSE and dispersion energies (gCP-D3-ΔE_binding) were measured for compounds 8 (among isolated drugs) and 13 (among complexes). The dipole moments of isolated drugs were obtained close to those of their complexes with C₆₀ (∼4.0–5.5 Debye) indicating their hydrophililic nature that is an appropriate property appealing for drug delivery in biological media. The adsorption of all drugs on the surface of fullerene was endergonic with all of the ΔG_adsorption > 0. The ΔH_adsorption values at B3PW91 level were only negative for complexes 14–16 indicating their exothermic adsorption nature. The HOMO–LUMO band gaps of complexes 11–19 were about 2.7 eV and are comparable with the gap in C₆₀ but are much smaller than the gaps in isolated drugs 2–10 (6.5–8.0 eV) reflecting the increase in electrical conductivities upon complexation. The QTAIM data supported the covalent character of the C–O, C–N and N–H bonds, the intermediate character of PO, P–O and P–N bonds while the electrostatic nature of PO…C(fullerene) interactions. According to the gCP-D3-ΔE_binding binding energies and ΔH_adsorption values at B3LYP level, it seems that the complexes 12 and 13 can be the most promising prodrug + carrier delivery systems.

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Gas sensing properties of ZnO thin films prepared by microcontact printing

In situ patterned zinc oxide (ZnO) thin films were prepared by precipitation of Zn(NO₃)₂/urea aqueous solution and by microcontact printing of self-assembled monolayers (SAMs) on Al/SiO₂/Si substrates. The visible precipitation of Zn(OH)₂ from the urea containing Zn(NO₃)₂ solution was enhanced by increasing the reaction temperature and the amount of urea. The optimized condition for the ZnO thin films was found to be the Zn(NO₃)₂/urea ratio of 1/8, the precipitation temperature of 80 °C, the precipitation time of 1 h and the annealing temperature of 600 °C, respectively. SAMs are formed by exposing Al/SiO₂/Si to solutions comprising of hydrophobic octadecylphosphonic acid (OPA) in tetrahydrofuran and hydrophilic 2-carboxylethylphosphonic acid (CPA) in ethanol. The ZnO thin film was then patterned with the heat treatment of Zn(OH)₂ precipitated on the surface of hydrophilic CPA. The ZnO gas sensor was exposed to different concentrations of C₃H₈ (5000 ppm), CO (250 ppm) and NO (1000 ppm) at elevated temperatures to evaluate the gas sensitivity of ZnO sensors. The optimum operating temperatures of C₃H₈, CO and NO gases showing the highest gas sensitivity were determined to be 350, 400 and 200 °C, respectively.     

Fluorescence detection of nitrogen dioxide with perylene/PMMA thin films

Thin films of polymethylmethacrylate (PMMA) doped with perylene provide selective, robust and easily prepared optical sensor films for NO₂ gas with suitable response times for materials aging applications. The materials are readily formed as 200 nm thin spin cast films on glass from chlorobenzene solution. The fluorescence emission of the films (λ_max=442 nm) is quenched upon exposure to NO₂ gas through an irreversible reaction forming non-fluorescent nitroperylene. Infrared, UV–VIS and fluorescence spectroscopies confirmed the presence of the nitro adduct in the films. In other atmospheres examined, such as air and 1000 ppm concentrations of SO₂, CO, Cl₂ and NH₃, the films exhibited no loss of fluorescence intensity over a period of days to weeks. Response curves were obtained for 1000, 100 and 10 ppm NO₂ at room temperature with equilibration times varying from hours to weeks. The response curves were fit using a numerical solution to the coupled diffusion and a nonlinear chemical reaction problem assuming that the situation is reaction limiting. The forward reaction constant fitted to experimental data was k_f∼0.06 (ppm min)⁻¹.     

Sensing characteristics of the organic vapors according to the reflectance spectrum in the porous silicon multilayer structure

We fabricated a porous silicon multilayer and investigated its reflectance spectra before, during, and after exposure to various organic vapors. During exposure of the porous silicon multilayer to isopropanol, ethanol, methanol, and acetone vapors, the reflectance peak shifted toward longer wavelengths by about 5, 12, 26, and 39 nm, respectively. The shift of the reflectance peak arises from refractive index changes induced by capillary condensation of the organic vapor in the pores of the porous silicon multilayer. In addition, we observed that the shift value of the reflectance peak increased with increasing organic solvent concentration in the organic solvent-water mixture. After removing the organic vapor, the reflectance spectrum returned completely to its original state.     

Development of wireless compressive/relaxation-stress measurement system integrated with pressure-sensitive carbon black-filled silicone rubber-based sensors

In order to detect the installation compressive stress and monitor the stress relaxation between two bending surfaces on a defensive furnishment, a wireless compressive-stress/relaxation-stress measurement system based on pressure-sensitive sensors is developed. The flexible pressure-sensitive stress sensor array is fabricated by using carbon black-filled silicone rubber-based composite. The wireless stress measurement system integrated with this sensor array is tested with compressive stress in the range from 0 MPa to 3 MPa for performance evaluation. Experimental results indicate that the fractional change in electrical resistance of the pressure-sensitive stress sensor changes linearly and reversibly with the compressive stress, and its fractional change goes up to 355% under uniaxial compression; the change rate of the electrical resistance can track the relaxation stress and give out a credible measurement in the process of stress relaxation. The relationship between input (compressive stress) and output (the fractional change in electrical resistance) of the pressure-sensitive sensor is ΔR/R₀ = σ × 1.2 MPa^?1. The wireless compressive stress measurement system can be used to achieve sensitivity of 1.33 V/MPa to the stress at stress resolution of 920.3 Pa. The newly developed wireless stress measurement system integrated with pressure-sensitive carbon black-filled silicone rubber-based sensors has advantages such as high sensitivity to stress, high stress resolution, simple circuit and low energy consumption.     

Evaluation of the absolute affinity of neuraminidase inhibitor using steered molecular dynamics simulations

The absolute free energy difference of binding (ΔG) between neuraminidase and its inhibitor was evaluated using fast pulling of ligand (FPL) method over steered molecular dynamics (SMD) simulations. The metric was computed through linear interaction approximation. Binding nature was described by free energy differences of electrostatic and van der Waals (vdW) interactions. The finding indicates that vdW metric is dominant over electrostatics in binding process. The computed values are in good agreement with experimental data with a correlation coefficient of R = 0.82 and error of σΔG_exp = 2.2 kcal/mol. The results were observed using Amber99SB-ILDN force field in comparison with CHARMM27 and GROMOS96 43a1 force fields. Obtained results may stimulate the search for an Influenza therapy.     

Computing Modular Invariants of p-groups

Let V be a finite dimensional representation of a p -group, G, over a field,k , of characteristic p. We show that there exists a choice of basis and monomial order for which the ring of invariants, k [ V ]^G, has a finite SAGBI basis. We describe two algorithms for constructing a generating set for k [ V ] G. We use these methods to analyse k [2V₃ ]^U₃where U₃is the p -Sylow subgroup ofGL₃ (F_p) and 2 V₃is the sum of two copies of the canonical representation. We give a generating set for k [2 V₃]^U₃forp =  3 and prove that the invariants fail to be Cohen–Macaulay forp >  2. We also give a minimal generating set for k [mV₂ ]^Z / pwere V₂is the two-dimensional indecomposable representation of the cyclic group Z / p.     

Giant-grain silicon (GGS) and its application to stable thin-film transistor

We developed a giant-grain silicon (GGS) by Ni-mediated crystallization of amorphous silicon (a-Si) with a silicon-nitride (SiN_x) cap layer. Ni particles were sputtered onto the SiN_x/a-Si layer and then it was annealed at around 600 °C. The Ni diffuses through a SiN_x cap and then forms NiSi₂ crystallites in a-Si, which is able to induce crystallization. The grain size can be controlled from a few to 100 μm. The grain size can be increased with increasing the cap layer thickness or by decreasing the Ni density on the SiN_x. The p-channel GGS poly-Si TFT exhibited a field-effect mobility of 101 cm²/Vs and a threshold voltage of −3.6 V and is very stable under gate or hot carrier bias-stress. These superior performances may be due to the smooth surface of GGS poly-Si and solid-phase crystallization of a-Si.     

Aviation emission inventory development and analysis

An up to date and accurate aviation emission inventory is a prerequisite for any detailed analysis of aviation emission impact on greenhouse gases and local air quality around airports. In this paper we present an aviation emission inventory using real time air traffic trajectory data. The reported inventory is in the form of a 4D database which provides resolution of 1° × 1° × 1000 ft for temporal and spatial emission analysis. The inventory is for an ongoing period of six months starting from October 2008 for Australian Airspace.In this study we show 6 months of data, with 492,936 flights (inbound, outbound and over flying). These flights used about 2515.83 kt of fuel and emitted 114.59 kt of HC, 200.95 kt of CO, 45.92 kt of NO_x, 7929.89 kt of CO₂, and 2.11 kt of SO_x. From the spatial analysis of emissions data, we found that the CO₂ concentration in some parts of Australia is much higher than other parts, especially in some major cities. The emission results also show that NO_x emission of aviation may have a significant impact on the ozone layer in the upper troposphere, but not in the stratosphere.It is expected that with the availability of this real time aviation emission database, environmental analysts and aviation experts will have an indispensable source of information for making timely decisions regarding expansion of runways, building new airports, applying route charges based on environmentally congested airways, and restructuring air traffic flow to achieve sustainable air traffic growth.