Environmental Hazard Analysis - a Variant of Preliminary Hazard Analysis for Autonomous Mobile Robots

Robot manufacturers will be required to demonstrate objectively that all reasonably foreseeable hazards have been identified in any robotic product design that is to be marketed commercially. This is problematic for autonomous mobile robots because conventional methods, which have been developed for automatic systems do not assist safety analysts in identifying non-mission interactions with environmental features that are not directly associated with the robot’s design mission, and which may comprise the majority of the required tasks of autonomous robots. In this paper we develop a new variant of preliminary hazard analysis that is explicitly aimed at identifying non-mission interactions by means of new sets of guidewords not normally found in existing variants. We develop the required features of the method and describe its application to several small trials conducted at Bristol Robotics Laboratory in the 2011–2012 period.     

The degradation of polystyrene during extrusion

An investigation was made of the magnitude and mechanism of shear degradation of a narrow distribution, high molecular weight (M_w = 670,000) polystyrene. An Instron rheometer was used to perform the extrusion at temperatures from 164° to 250°C. The change in molecular weight distribution was studied by gel permeation chromatography. The maximum shear stress employed was 5.83 kg/cm². It was found that degradation could be induced at high stress at temperatures of 50°C lower than degradation of polystyrene would occur exclusively due to thermal forces. An activation energy for the degradation, calculated at constant shear rate, was +20.2 kcal/mole. The direction and magnitude of this value are consistent with degradation induced through a mechanical reduced activation for thermal degradation.     

The flexible surface or the rigid surface?

In this paper we discuss aspects of the concept described by Somorjai as the flexible surface, and whether some surfaces can be considered to be inflexible, or rigid. We present STM results which appear to manifest both types of behaviour for surfaces, depending on their oxidation state. Copper metal surfaces can be classed as flexible, showing facile reconstruction in the presence of oxygen, whereas an oxidised Pd(110) surface shows no apparent diffusivity, even at 500 K. We go on to show data for a bulk oxide which indicates that sub-stoichiometry in the sample induces an element of flexibility in the surface, especially during reaction with oxygen. Finally, this is related to the direct observation of spillover on model catalysts of Pd nanoparticles supported on TiO₂. It must be recognised that flexibility relates to surface diffusivity and hence length- and time-scales. Surfaces which appear inflexible at short times may be flexible at long times. In relation to catalysis then, surface flexibility depends on the relationship between the time-scale of diffusive events on the surface and the catalytic turnover number.     

CONCENTRATED ACID CONVERSION OF PINE SOFTWOOD TO SUGARS. PART I: USE OF A TWIN-SCREW REACTOR FOR HYDROLYSIS PRETREATMENT

The first stage of a two-step concentrated sulfuric acid process that converts softwood sawdust to sugars has been explored. The research focuses on the ability of an in-house custom fabricated corotating twin-screw reactor (TSR) to effectively break down and solubilize crystalline cellulose into low molecular weight carbohydrates. Based on design of experiment (DOE) screening results, a four-level, two-factor experimental model building DOE was undertaken. Solid sawdust conversion to liquid, screw torque, and TSR exit pressure were measured or recorded at each experimental condition to yield percent conversion of solids, processed material viscosity, and material energy requirements. Thereafter, model quadratic equations were fitted to the experimental data and found to be statistically significant. Based on data obtained in the DOE the process was optimized to establish a base case operating condition. The acid-treated product made at base case twin-screw operating conditions showed a 38.2% conversion of dry sawdust solids to soluble liquids. The dry solids conversion reduced 73.8% of all hemicellulose and 44.4% of all cellulose to soluble monomers and oligosaccharides.     

Synthesis and properties of aminopropyl nucleic acids

Oligonucleotides that contain up to three aminopropyl nucleoside analogues have been synthesized. Dimers of aminopropyl adenine and thymidine were prepared and used as building blocks by applying phosphoramidite chemistry. Both R and S isomers of the aminopropyl nucleosides were used. This incorporation led to a reduction of thermal stability of double-stranded DNA. Furthermore, the (R)-adenine analogue, which yielded (S)-APNA, can be considered as a candidate for universal base pairing.     

The effects of oxygen diffusion on the surface photooxidation of polystyrene

This paper further illustrates the applicability of multiple internal reflectance infrared spectroscopy to the analysis of near-surface photooxidation. The results are compared with transmission infrared spectra to evaluate compositional gradients resulting from photooxidation and the influence of oxygen diffusion. The sample was a solvent-cast film of atactic, narrow distribution polystyrene, M_w of 100,000, that had been drawn to a ratio of 3.0 at 110°C by solid state coextrusion. Irradiation of these thin films, ～25μm thickness, was performed on exposure to air at 35°C for periods of up to 6 h using a mercury source emitting at 254 nm. On photooxidation, a board peak appears at 3200–3500 cm^?1, attributable to hydroperoxide formation. The most dramatic increase in the infrared spectra is found for a carbonyl band at 1730 cm^?1. It appears to result from an aromatic acid group since it is shifted to 1660 cm^?1 on immersion of the oxidized polystyrene films in aqueous ammonium hydroxide. It is confirmed that the photooxidation of polystyrene occurs preferentially at the surface and that this reaction rate is greatly reduced in the drawn polystyrene film.     

Purity of Aluminum Hydroxide Derived from Triethylaluminum

Aluminum hydroxide obtained by hydrolysis of triethylaluminum is free of uranium and thorium at detection limits of 1 to 9 parts per billion (ppb). Other impurities commonly associated with aluminum oxides are present at low levels (Fe, ∼ 1 ppm; Si, 3 to 6 ppm). When the organoaluminum is intentionally contaminated with an iron salt, purity is restored by a simple distillation.     

Excess Gibbs free energy and excess enthalpy for mixtures of benzene and 1,1,2-trichlorotrifluoroethane

The rapid measurement of static vapour pressures of binary liquid mixtures as a function of composition by a new continuous-dilution apparatus is described. These measurements, together with the computed excess Gibbs free energies, are reported for mixtures of benzene and 1,1,2-trichlorotrifluoroethane at 283.30, 287.83, 293.21, 298.21, 303.06 and 308.15 K over the full composition range, and are compared with the results of Linford and Hildebrand. The excess enthalpies were measured directly at 303.15 K using a batch calorimeter. The equimolar excess enthalpy is + 754 J mol^?1, which is close to the value, + 727 J mol^?1, calculated from the temperature dependence of the computed equimolar excess Gibbs free energies.     

Mechanical Activation of Tetracalcium Phosphate

It was found that prolonged high-energy ball-milling of Hilgenstokite (tetracalcium phosphate, TTCP) resulted in a decrease in both particle and crystallite size, leading to a mechanical activation of the compound. This mechanically activated material demonstrated a high reactivity such that, in contrast to highly crystalline TTCP, a setting reaction with water to nanocrystalline hydroxyapatite (HA) and Ca(OH)₂ could be achieved at 37°C. However, crystalline TTCP is practically unreactive at physiologic temperatures because of the formation of a thin HA layer on the particle surface preventing further reaction.     

Induction of DNA-double-strand breaks by auger electrons from 99mTc complexes with DNA-binding ligands

The potential of certain Auger electron emitting nuclides for systemic radiotherapeutic applications has recently gained much attention. In particular, the ability of several nuclides, including 111In, 125I, and 123I, to induce DNA double-strand breaks (dsb), a good indicator of cytotoxicity, has been extensively studied. However, this ability has never previously been shown experimentally for 99mTc, which, besides the well-known gamma radiation that is used for diagnostic applications, also emits an average of 1.1 conversion electrons and 4 Auger or Coster-Kronig electrons per decay. Owing to the short range of Auger electrons, the radionuclide needs to be located very close to the DNA for dsb to occur. We synthesized two cationic 99mTcI-tricarbonyl complexes with pendant DNA binders, pyrene and anthraquinone. The X-ray crystal structures of the two complexes could be elucidated. Linear dichroism and UV/Vis spectroscopy revealed that the complex with pyrene intercalates DNA with a stability constant, K, of 1.1 x 10(6) M(-1), while the analogous complex with anthraquinone interacts with DNA in a groove-binding mode and has an affinity value of K=8.9 x 10(4) M(-1). We showed with phiX174 double-stranded DNA that the corresponding 99mTc complexes induce a significant amount of dsb, whereas non-DNA-binding [TcO4]- and nonradioactive Re compounds did not. These results indicate that the Auger electron emitter 99mTc can induce dsb in DNA when decaying in its direct vicinity and this implies potential for systemic radiotherapy with 99mTc complexes.