Physical properties of oleochemical carbonates

Carbonates are a class of compounds that have recently found increasing interest in commercial applications owing to their physical properties and relatively straightforward synthesis. In this work, physical and fuel properties of five straight-chain C_17–39 and three branched C_17–33 oleochemical carbonates were investigated. These properties included cetane number (CN), low-temperature properties, (kinematic) viscosity, lubricity, and surface tension. The carbonates studied had CN ranging from 47 to 107 depending on carbon chain length and branching. For the same number of carbons, the CN of carbonates were lower than those of FA alkyl esters owing to interruption of the CH₂ chain by the carbonate moiety. Kinematic viscosities at 40°C ranged from 4.9 to 22.6 mm²/s whereas m.p. ranged from +3 to below −50°C depending on the carbonate structure. High-frequency reciprocating rig testing showed the neat carbonates to have acceptable lubricity that improved as chain length increased. Finally, the carbonate's ability to influence cold-flow properties in biodiesel (methyl soyate) and lubricity in low-lubricity ultra-low sulfur diesel were examined. The carbonates studied did not significantly affect cold flow or lubricity properties at concentrations up to 10,000 ppm (1 wt%). The properties of the carbonates resemble those of fatty alkyl esters with similar trends resulting from compound structure.     

Structural and transport effects of doping perfluorosulfonic acid polymers with the heteropoly acids, H3PW12O40 or H4SiW12O40

A perfluorosulfonic acid (PFSA) polymer with pendant side chain -O(CF₂)₄SO₃H was doped with the heteropoly acids (HPAs), H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀. Infrared spectroscopy revealed a strong interaction between the HPA and the PFSA ionomer. Modes associated with the peripheral bonds of the HPA were shifted to lower wave numbers when doped into PFSA membranes. Small-angle X-ray scattering (SAXS) measurements showed the presence of large crystallites of HPA in the membrane with d spacings of ca. 10 Å, close to the lattice spacing observed in bulk HPA crystals. Under wet conditions the HPA was more dispersed and constrained the size of the sulfonic acid clusters to 20 Å at a 5 wt% HPA doping level, the same as in the vacuum treated ionomer samples. Under conditions of minimum hydration the HPA decreased the E_a for the self-diffusion of water from 27 to 15 kJ mol⁻¹. The reverse trend was seen under 100% RH conditions. Proton conductivity measurements showed improved proton conductivity of the HPA doped PFSAs at a constant dew point of 80 °C for all temperatures up to 120 °C and at all relative hummidities up to 80%. The activation energy for proton conduction generally was lower than for the undoped materials at RH ≤80%. Significantly the E_a was 1/2 that of the undoped material at RHs of 40 and 60%. A practical proton conductivity of 113 mS cm⁻¹ was observed at 100 °C and 80% RH.     

Property-composition relationships for diesel and kerosene fuels

A range of 18 diesel fuels and 21 kerosene fuels from mainly Australian petroleum and synthetic fuel sources, including coal, shale and peat, was investigated. Compositional details were defined as the weight per cent abundances of n-alkanes, branched plus cyclic saturates, single-ring aromatics, doublering aromatics and polynuclear aromatics, using both h.p.l.c. and ¹³C n.m.r. techniques. Relationships between fuel composition and a range of fuel properties were sought. Simple linear relationships between property values and compositional data were used. Explicit correlative expressions were derived using multiple linear regression analysis, with the coefficient of multiple determination, R², indicating the quality of the fit between observed and calculated property values. In most cases good correlations were achieved. For diesels the properties investigated, with R² values in parentheses, were: inverse specific gravity (0.99); ¹³C n.m.r. aromaticity (0.99); ¹H n.m.r. aromaticity (0.88); cetane index (0.97); aniline point (0.96); diesel index (0.98); and FIA-measured aromatics content (0.77). For kerosenes the properties, with R² values in parentheses, were: ¹³C n.m.r. aromaticity (0.98); ¹H n.m.r. aromaticity (0.97); smoke point (0.88); and FIA-measured aromatics content (0.94). The results are shown to be of value in assessing the potential and limitations of hydrotreating as a process for upgrading synfuels.     

OptaDOS: A tool for obtaining density of states,core-level and optical spectra from electronic structure codes

We present OptaDOS, a program for calculating core-electron and low-loss electron energy loss spectra (EELS) and optical spectra along with total-, projected- and joint-density of electronic states (DOS) from single-particle eigenenergies and dipole transition coefficients. Energy-loss spectroscopy is an important tool for probing bonding within a material. Interpreting these spectra can be aided by first principles calculations. The spectra are generated from the eigenenergies through integration over the Brillouin zone. An important feature of this code is that this integration is performed using a choice of adaptive or linear extrapolation broadening methods which we show produces higher accuracy spectra than standard fixed-width Gaussian broadening. OptaDOS  may be straightforwardly interfaced to any electronic structure code. OptaDOS  is freely available under the GNU General Public licence from http://www.optados.org.     

The role of adsorbate overlayers in thiophene hydrodesulfurization over molybdenum and rhenium single crystals

Thiophene hydrodesulfurization (HDS) has been investigated over model single crystal catalysts of molybdenum and rhenium. Thiophene HDS is a structure sensitive reaction over rhenium and a structure insensitive reaction over molybdenum. Adsorbed sulfur decreases the activity of both Re(0001) and Mo(100) surfaces while adsorbed carbon has distinctly different effects on the catalytic properties of the two metals. Carbon overlayers deactivate the Re(0001) surface but have no effect on the HDS activity of the Mo(100) surface. Radiotracer³⁵S and¹⁴C studies indicate that HDS occurs on an adsorbate overlayer on molybdenum comprised primarily of carbon. HDS over rhenium, on the other hand, occurs on the bare metal surface. This appears to be responsible for the observed differences in the influence of surface structure on HDS activity.     

Characterization of Ceramics by X-Ray and Neutron Small-Angle Scattering

This paper reviews some recent advances in small-angle X-ray and neutron scattering methods and their application to address complex issues in ceramic systems of technological importance. It is shown how small-angle scattering (SAS) can be applied to ceramic systems in order to extract statistically representative microstructure information (e.g., void volume fraction size distributions, internal surface areas, pore morphologies) that complements the information obtained from diffraction methods, X-ray microtomography, or electron microscopy. It is demonstrated how SAS studies provide insights, not obtainable by other means, on the processing–microstructure–property relationships that frequently govern technological performance.     

Automatic and Efficient Human Pose Estimation for Sign Language Videos

We present a fully automatic arm and hand tracker that detects joint positions over continuous sign language video sequences of more than an hour in length. To achieve this, we make contributions in four areas: (i) we show that the overlaid signer can be separated from the background TV broadcast using co-segmentation over all frames with a layered model; (ii) we show that joint positions (shoulders, elbows, wrists) can be predicted per-frame using a random forest regressor given only this segmentation and a colour model; (iii) we show that the random forest can be trained from an existing semi-automatic, but computationally expensive, tracker; and, (iv) introduce an evaluator to assess whether the predicted joint positions are correct for each frame. The method is applied to 20 signing footage videos with changing background, challenging imaging conditions, and for different signers. Our framework outperforms the state-of-the-art long term tracker by Buehler et al. (International Journal of Computer Vision 95:180–197, 2011), does not require the manual annotation of that work, and, after automatic initialisation, performs tracking in real-time. We also achieve superior joint localisation results to those obtained using the pose estimation method of Yang and Ramanan  (Proceedings of the IEEE conference on computer vision and pattern recognition, 2011).     

Deblurring Shaken and Partially Saturated Images

We address the problem of deblurring images degraded by camera shake blur and saturated (over-exposed) pixels. Saturated pixels violate the common assumption that the image-formation process is linear, and often cause ringing in deblurred outputs. We provide an analysis of ringing in general, and show that in order to prevent ringing, it is insufficient to simply discard saturated pixels. We show that even when saturated pixels are removed, ringing is caused by attempting to estimate the values of latent pixels that are brighter than the sensor’s maximum output. Estimating these latent pixels is likely to cause large errors, and these errors propagate across the rest of the image in the form of ringing. We propose a new deblurring algorithm that locates these error-prone bright pixels in the latent sharp image, and by decoupling them from the remainder of the latent image, greatly reduces ringing. In addition, we propose an approximate forward model for saturated images, which allows us to estimate these error-prone pixels separately without causing artefacts. Results are shown for non-blind deblurring of real photographs containing saturated regions, demonstrating improved deblurred image quality compared to previous work.     

A computationally efficient norm optimal iterative learning control approach for LTV systems

This paper proposes a computationally efficient iterative learning control (ILC) approach termed non-lifted norm optimal ILC (N-NOILC). The objective is to remove the computational complexity issues of previous 2-norm optimal ILC approaches, which are based on lifted system techniques, while retaining the iteration domain convergence properties. The computational complexity needed to implement the proposed method scales linearly with the trial length. Therefore, the approach can be implemented on controlled processes having long trial durations and high sampling rates. Robustness is accomplished by adding a penalty term on the control input in the cost function. Simulations are presented to verify and validate the features of the proposed method.