Probing the thermal decomposition process of layered double hydroxides through in situ <Superscript>57</Superscript>Fe Mössbauer and in situ X-ray diffraction experiments

The thermal decomposition properties of Mg–Fe hydrotalcites were studied through in situ ⁵⁷Fe Mössbauer spectroscopy and in situ X-ray diffraction. Abrupt changes in the quadrupolar splitting measured in the Mössbauer spectra revealed a phase transition from the starting lamellar structure to a new crystalline arrangement. By analyzing the Mössbauer parameters we show that the material is highly disordered in the 300–400 °C temperature range. This hypothesis is confirmed by the X-ray results whose diffractograms indicated the collapse of the lamellar structure and the formation of a solid solution.     

Potential for integration of electrophoretic deposition into electronic device manufacture; demonstrations using silver/palladium

A silver palladium (Ag/Pd) alloy powder is used as an example material to illustrate potential applications of electrophoretic deposition (EPD) in electronics manufacturing, in particular the forming of multilayer devices. The dispersion and deposition of the Ag/Pd powder in acetic acid is characterized. It is found that deposition can be explained by the direct action of electrostatic force on individual particles. Depositions of this Ag/Pd powder are then used to demonstrate: forming of a continuous layer on a rigid substrate; forming of continuous layers in laminated and sintered BaTiO₃ multilayers; and incorporation of patterned depositions into a multilayer by either overcasting the patterned deposition with a particulate slip to form a multicomponent tape, or direct lamination of the patterned deposition to a low temperature co-fired ceramic (LTCC) tape. It is shown that electrically conducting layers can be formed at an average thickness of only two times the diameter of the starting powder. Continuous conductor lines thirty times the average diameter of the starting powder were formed.     

Atmospheric corrosion of reference metals in Antarctic sites

This paper presents the results obtained at three Antarctic test sites participating in the “Ibero-American Map of Atmospheric Corrosiveness” (MICAT), a project on atmospheric corrosion carried out during the period 1988–1994 at some 70 sites distributed across 12 countries of the Latin-American region, Spain and Portugal. The three Antarctic sites are located near the coastline.The singular climatic characteristics of Antarctic regions are related with the purity of the air, the absence of rainfall and the formation of ice on the metallic surface during an important part of the exposure time. However, electrochemical activity is possible below ice layers. This situation affects the structure and morphology of corrosion product films and the resulting corrosion rates of metallic surfaces.     

Modeling and Analysis of a Long Thin Conducting Stripline

A long thin conducting stripline embedded in a dielectric and centered between two large conducting plates, i.e., the stripline environment, is considered. The stripline is modeled as infinitely long, infinitely thin, and perfectly conducting by first considering a stripline of finite length, thickness, and conductivity in a dielectric layer. Starting from Maxwell's equations and assuming that the current on the stripline is a propagating wave in length direction, asymptotic expressions for the fields inside and in the neighbourhood of the stripline are deduced. These expressions are used to model the stripline in the stripline environment, which leads to a boundary-value problem for the electric potential. This problem is solved by two different approaches, leading to integral equations for the current and for an auxiliary function describing the electric potential. A relation between the current and the auxiliary function is deduced, which is used to obtain asymptotic expressions for current and impedance. Results are compared with a numerical solution of the integral equation for the current and with results in literature.     

Strategies to improve the performance of very low bit rate speech coders and application to a variable rate 1.2 kb/s codec

This paper presents several strategies to improve the performance of very low bit rate speech coders and describes a speech codec that incorporates these strategies and operates at an average bit rate of 1.2 kb/s. The encoding algorithm is based on several improvements in a mixed multiband excitation (MMBE) linear predictive coding (LPC) structure. A switched-predictive vector quantiser technique that outperforms previously reported schemes is adopted to encode the LSF parameters. Spectral and sound specific low rate models are used in order to achieve high quality speech at low rates. An MMBE approach with three sub-bands is employed to encode voiced frames, while fricatives and stops modelling and synthesis techniques are used for unvoiced frames. This strategy is shown to provide good quality synthesised speech, at a bit rate of only 0.4 kb/s for unvoiced frames. To reduce coding noise and improve decoded speech, spectral envelope restoration combined with noise reduction (SERNR) postfilter is used. The contributions of the techniques described in this paper are separately assessed and then combined in the design of a low bit rate codec that is evaluated against the North American Mixed Excitation Linear Prediction (MELP) coder. The performance assessment is carried out in terms of the spectral distortion of LSF quantisation, mean opinion score (MOS), A/B comparison tests and the ITU-T P.862 perceptual evaluation of speech quality (PESQ) standard. Assessment results show that the improved methods for LSF quantisation, sound specific modelling and synthesis and the new postfiltering approach can significantly outperform previously reported techniques. Further results also indicate that a system combining the proposed improvements and operating at 1.2 kb/s, is comparable (slightly outperforming) a MELP coder operating at 2.4 kb/s. For tandem connection situations, the proposed system is clearly superior to the MELP coder.     

Dynamic vulcanisation of EPDM/PE-based thermoplastic vulcanisates studied along the extruder axis

Simple blending and dynamic vulcanisation of EPDM/PE blends using the resol/SnCl₂ system was studied in an extruder using a series of sampling devices. The melting of the PE pellets occurs just in front of and in the first kneading zone. Upon complete melting of the PE phase, the EPDM/PE blends reach very quickly their final morphology. Crosslinking of the EPDM phase to high levels occurs already when the PE phase is not yet fully molten. The higher the EPDM content, the higher the viscous dissipation, the higher the melt temperature and, consequently, the higher the crosslinking rate. For the EPDM/PE (50/50; w/w) TPV a transition from continuous via co-continuous to fully dispersed EPDM is observed, which is driven by crosslinking. Although the degree of crosslinking of the EPDM rubber is very high, this does not prevent phase inversion of the blend. The EPDM/PE interface is rather blurred, because PE crystalline lamellae are growing into the EPDM domains, probably because of the high compatibility between PE and EPDM (60 wt% of ethene). This study shows that dynamic vulcanisation in extruders proceeds quite differently from that in batch kneaders, where melting, mixing and crosslinking are separated in time. In extruders mass and heat transport, melting of the thermoplastic, morphology development (including dispersion and phase inversion), distribution and dissolution of (crosslinking) chemicals and crosslinking of the rubber do not occur as independent phenomena, but mutually and/or continuously interact.     

Integration of prior knowledge of measurement noise in kernel density classification

Samples can be measured with different precisions and reliabilities in different experiments, or even within the same experiment. These varying levels of measurement noise may deteriorate the performance of a pattern recognition system, if not treated with care. Here we seek to investigate the benefit of incorporating prior knowledge about measurement noise into system construction. We propose a kernel density classifier which integrates such prior knowledge. Instead of using an identical kernel for each sample, we transform the prior knowledge into a distinct kernel for each sample. The integration procedure is straightforward and easy to interpret. In addition, we show how to estimate the diverse measurement noise levels in a real world dataset. Compared to the basic methods, the new kernel density classifier can give a significantly better classification performance. As expected, this improvement is more obvious for small sample size datasets and large number of features.     

Life cycle of hydroprocessing catalysts and total catalyst management

Hydroprocessing catalysts based on Ni, Co, Mo and W are used in various refinery processing applications where several deactivation mechanisms become of importance (coke formation, active phase sintering, metals deposition, poisoning) in the catalyst's life cycle. The life cycle of commercial hydroprocessing catalysts is very complex and includes the catalyst production, sulfidation, use, oxidative regeneration followed by re-sulfidation and reuse or, if reuse is not possible, recycling or disposal. To understand the changes in catalyst properties taking place during a life cycle, the catalyst quality in the different stages can be best monitored by using advanced analytical techniques. The catalyst's life cycle is further complicated by numerous technical, environmental and organizational issues involved. In principle, different companies can be involved in each of the life cycle steps. Leading catalyst manufacturers, together with specialized firms, offer refineries a total catalyst management concept, starting with the purchase of the fresh catalyst and ending with its final recycling or disposal. Total catalyst management includes a broad range of services, ensuring optimal timing during the change-out process, reliable, smooth and safe operations, minimal downtime and maximum catalyst and unit performance.     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.