Gold nanoparticles on ceria: importance of O vacancies in the activation of gold

Synchrotron-based techniques (high-resolution photoemission, in-situ X-ray absorption spectroscopy, and time-resolved X-ray diffraction) have been used to study the destruction of SO₂ and the water-gas shift (WGS, CO + H₂O → H₂ + CO₂) reaction on a series of gold/ceria systems. The adsorption and chemistry of SO₂ was investigated on Au/CeO₂(111) and AuO _x /CeO₂ surfaces. The heat of adsorption of the molecule on Au nanoparticles supported on stoichiometric CeO₂(111) was 4–7 kcal/mol larger than on Au(111). However, there was negligible dissociation of SO₂ on the Au/CeO₂(111) surfaces. The full decomposition of SO₂ was observed only after introducing O vacancies in the ceria support. AuO _x /CeO₂ surfaces were found to be much less chemically active than Au/CeO₂(111) or Au/CeO_2−x (111) surfaces. In a separate set of experiments, in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to monitor the behavior of nanostructured {Au + AuO _x }–CeO₂ catalysts under the WGS reaction. At temperatures above 250 °C, a complete AuO _x → Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO₂(111) single crystal corroborate that cationic Au^δ+ species cannot be the key sites responsible for the WGS activity at high temperatures. The active sites in {Au + AuO _x }/ceria catalysts should involve pure gold nanoparticles in contact with O vacancies of the oxide.     

Second-law efficiency analysis of a coal gasification process

The present paper summarizes a comprehensive Second-Law analysis of the SYNTHANE process of coal gasification⁽¹⁾, based on the available-energy concept as applied to design conditions and data. The analysis yields an overall process efficiency of 46%. For every 100 MJ of useful energy supplied with coal, 51 MJ are consumed during the various unit operations while effluents carry 3 MJ. Unit 30, Steam and Power Production, consumes nearly 20 MJ; Unit 15, Gasification, used up nearly 16 MJ; Units 12 and 14, Coal Preparation and Feeding, about 5 MJ; Units 16 and 17, Raw Gas Quenching and Shift Conversion, 4 MJ; Unit 32, Oxygen Plant, approximately 2 MJ; other miscellaneous units contribute a combined available-energy destruction of 4 MJ. The Second-Law analysis unveils the inefficiencies present in the process and their sources, thus pinpointing the opportunities for improvement in the SYNTHANE process.     

Preparation of silica by acid dissolution of sepiolite and study of its reinforcing effect in elastomers

The preparation of amorphous silica by acid treatment of a natural magnesium silicate and its use as reinforcing filler for NR and SBR compounds are studied. Limited to the treatment with nitric acid, the rate constants at different temperatures and acid concentrations and the activation energy are calculated, as a function of percentage of extracted magnesium. The resulting material is basically an amorphous silica (92.5% SiO₂), as shown by X-ray analysis, that keeps the fibrous morphology of the original mineral. According to a preliminary technological study the resulting silica is a suitable reinforcing filler for general purpose rubbers; a comparison between the experimental results and those obtained with a commercial fine particle precipitated silica was made. Using a SBR compound the effect of silane coupling agents on the new silica was studied.     

Formation of phase structure and crystallization behavior in blends containing polystyrene–polyethylene block copolymers

The microphase separation structure in the molten state and the structure formation in crystallization from such ordered melt were investigated for the blends of polystyrene–polyethylene block copolymers (SE) with polystyrene homopolymer (PS) and polyethylene homopolymer (PE) and for the blends consisting of two kinds of SE with different copolymer compositions from each other, using synchrotron small-angle X-ray scattering techniques (SAXS). The copolymer compositions of SE block copolymers employed were 0.34, 0.58 and 0.73 wt. fraction of PE, and their melt morphologies were cylindrical, lamellar and lamellar, respectively. Macrophase separation or the morphology change in the melt occurred depending on the molecular weight and the blend composition, as reported so far. In crystallization from such macrophase-separated and microphase-separated melts, the melt morphology was completely kept for all the blends. Crystallization behavior was also investigated for the blends. The crystallization within the spherical and cylindrical domains surrounded by glassy PS was not observed for SE/PS blends. In the crystallization from the macrophase-separated melt, two exothermal peaks were observed in the DSC measurements, while a single peak was observed for other blends. For the blends with PS, the degree of crystallinity was depressed and the apparent activation energy of crystallization was high, compared to those for the corresponding neat SE. For SE/PE and SE/SE blends, those were changed depending on the blend composition.     

The dynamic contact area of elastomers at different velocities

The friction in tribo-systems that contain viscoelastic materials, such as elastomers, is relevant for a large number of applications. Examples include tyres, hoses, transmission and conveyor belts. To quantify the friction in these applications, one must first understand the contact behaviour of such viscoelastic materials, both in static and in dynamic situations. This work discusses an experimental study into the change of the contact area with the sliding velocity and relates the change in contact area with the mechanical properties of the elastomer. The results show that for a tribo-system containing an elastomer, there is a threshold velocity, above which the size of the contact area significantly reduces.     

Characterization of PA-12 specimens fabricated by projection sintering at various sintering parameters

Large area projection sintering (LAPS) promises to be a new method in the field of additive manufacturing. Developed in the Mechanical Engineering Department, University of South Florida, LAPS uses long exposure times over a broad area of powder to fuse into dense, reproducible materials. In contrast, LS, a common powder-based additive manufacturing, uses a focused beam of light scanned quickly over the material. Local regions of concentrated high-energy bursts of light lead to higher peak temperatures and differing cooling dynamics and overall crystallinity. The mechanical properties of laser sintered specimens suffer because of uneven particle fusion. LAPS offers the capacity to fine-tune fusion properties through enhanced thermodynamic control of the heating and cooling profiles for sintering. Further research is required to identify the relationship between LAPS build settings and part properties to enable the fabrication of custom parts with desired properties. This study examines the influence of LAPS sintering parameters on chemical structures, crystallinity, mechanical, and thermal properties of polyamide-12 specimens using powder X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering, scanning electron microscopy, and microhardness testing. It was observed that higher crystallinity was imparted to specimens that were sintered for a shorter time and vice versa.     

Effect of heat treatment on the efficiency of Mg anodes

Commercial magnesium anodes were evaluated using ASTM G 97-89 for a standard test along with a technique of electrochemical impedance. Several heat treatments were performed, and the anodic efficiency was determined, showing an incremental increase of 10 to 12 % of the efficiency demonstrated by the nontreated commercial anodes (as-cast condition). The increase in efficiency was related to the microstructural characteristics. The appearance of second phase particles influenced the form of the corrosion process.     

Boosting text segmentation via progressive classification

A novel approach for reconciling tuples stored as free text into an existing attribute schema is proposed. The basic idea is to subject the available text to progressive classification, i.e., a multi-stage classification scheme where, at each intermediate stage, a classifier is learnt that analyzes the textual fragments not reconciled at the end of the previous steps. Classification is accomplished by an ad hoc exploitation of traditional association mining algorithms, and is supported by a data transformation scheme which takes advantage of domain-specific dictionaries/ontologies. A key feature is the capability of progressively enriching the available ontology with the results of the previous stages of classification, thus significantly improving the overall classification accuracy. An extensive experimental evaluation shows the effectiveness of our approach.     

A bio-inspired predictive sensory-motor coordination scheme for robot reaching and preshaping

This paper presents a sensory-motor coordination scheme for a robot hand-arm-head system that provides the robot with the capability to reach an object while pre-shaping the fingers to the required grasp configuration and while predicting the tactile image that will be perceived after grasping. A model for sensory-motor coordination derived from studies in humans inspired the development of this scheme. A peculiar feature of this model is the prediction of the tactile image. The implementation of the proposed scheme is based on a neuro-fuzzy module that, after a learning phase, starting from visual data, calculates the position and orientation of the hand for reaching, selects the best-suited hand configuration, and predicts the tactile feedback. The implementation of the scheme on a humanoid robot allowed experimental validation of its effectiveness in robotics and provided perspectives on applications of sensory predictions in robot motor control.