Alterations in the complex refractive index of copper oxide thin films as sensing effect for hydrogen sulfide monitoring

Throughout the last three decades cuprous (Cu₂O) and cupric oxide (CuO) have been subject of extensive investigations of their material properties. This research was mainly driven by potential applicability as a photovoltaic or doping material. However, CuO/Cu₂O layers show a specific reaction towards hydrogen sulfide (H₂S), making it a good candidate as highly selective gas sensor material. On this account thin film samples of CuO and Cu₂O have been investigated with regard to their specific surface interactions with H₂S gas. Changes in morphology, chemical composition, and alterations in the complex refractive index have been thoroughly examined in order to understand possible sensing effects. Raman spectroscopy was used for verifying the films composition after heat treatment. Transmission and reflection characteristics in the extended UV/Vis regime (350–1,100 nm) of initially prepared samples and after exposure to well-defined doses of H₂S were recorded. A distinct increase in transmissivity was observed for Cu₂O films in the wavelength region λ = 550–900 nm. An initial conditioning effect was observed from consecutive measurements. Absorptivity characteristics and optical band gaps were derived, showing an absorptivity shift of CuO thin films after exposure towards H₂S. A specific optical read-out based on total internal reflection was set-up, offering a transient monitoring of the materials surface interactions with the gas phase. Changes in the response, in terms of intensity variations, were reproducibly shown for low concentrations of 5 ppm of H₂S.     

Electrical Conductivity of Epitaxial SrTiO3 Thin Films as a Function of Oxygen Partial Pressure and Temperature

SrTiO₃ (100) epitaxial films with thicknesses of 3, 1 μm, and 250 nm were prepared on MgO (100) substrates by pulsed-laser deposition. The electrical conductivities of the thin films were systematically investigated as a function of temperature and ambient oxygen partial pressure. This was made possible by using a specially designed measurement setup, allowing the reliable determination of resistances of up to 25 GΩ in the temperature range of 600°–1000°C under continuously adjustable oxygen partial pressures ranging from 10⁻²⁰ to 1 bar. The capabilities of the measurement setup were tested thoroughly by measuring a SrTiO₃ single crystal. The well-known characteristics, e.g., the decline of the conductivity with a slope of –1/4 under reducing conditions and the opposite +1/4 behavior in oxidizing atmospheres, are found in the log(σ)–log( p O₂) profiles of the epitaxial films. However, the p -type conductivity decreases, and the n -type conductivity increases with decreasing film thickness. This phenomenon is attributed to the charge carrier redistribution in the surface space charge layers. Owing to the high surface-to-volume ratio, the space charge layers play an important role in thin films.     

Measurement of Crack Tip Toughness in Alumina as a Function of Grain Size

Crack profile measurements near the crack tip in the SEM were used to measure crack tip toughness of alumina as a function of grain size (average grain size 0.9–16 μm). For comparative tests, two crack configurations were included in the present study: straight cracks (CT specimen) loaded with an in situ device; and radial indentation cracks. The measured crack tip toughness values were independent of crack geometry, and no grain size dependence could be discerned. A mean crack tip toughness of 2.3 MPam^1/2 was evaluated. The crack tip toughness determined from crack profile measurements is significantly lower than the toughness evaluated with conventional indentation techniques (e.g., indentation strength bending).     

BOOTSTRAPPING STATIONARY AUTOREGRESSIVE MOVING-AVERAGE MODELS

Abstract. In this paper we develop an asymptotic theory for application of the bootstrap to stationary stochastic processes of autoregressive moving-average (ARMA) type, with known order ( p, q ). We give a proof of the asymptotic validity of the bootstrap proposal applied to M estimators for the unknown parameter vector of the process. For this purpose we derive an asymptotic expansion for M estimators in ARMA models and construct an estimate for the unknown distribution function of the residuals which in principle are not observable. A small simulation study is also included.     

Lewis Acid Induced Additions to Unsaturated Fatty Compounds

Unsaturated fatty compounds such as oleic acid, which are of interest as renewable raw materials, can be functionalized at the C,C-double bond by Lewis acid induced addition reactions. The products are branched and highly functionalized fatty compounds which may have interesting properties. SnCl₄-induced additions of nitriles to methyl oleate and ethyl 10-undecenoate give the corresponding esters of the N-acylamino fatty acids. Alkylaluminium halide induced ene additions of formaldehyde to unsaturated fatty compounds yield primary homoallylic alcohols. β,γ-Unsaturated ketones are obtained in ethylaluminium dichloride induced Friedel-Crafts acylations of unsaturated fatty compounds with acyl chlorides and cyclic anhydrides.     

Mechanism of potassium loss by desorption from an iron oxide catalyst for the styrene process

Several types of experiments have been done with molecular beam and mass spectrometric methods to characterize the desorption processes of potassium from a commercial styrene (potassium promoted iron oxide) catalyst. The loss of potassium as desorption of K is found to be mainly thermal, with an activation energy close to 1.0 eV (97 kJ/mole), which probably is associated with release of K from the initially bound positions in the bulk. The directly measured rate of loss as K appears too small to account for the experimentally observed total rate of loss. A new loss mechanism as electronically excited but not easily field ionizable potassium atoms is detected with an activation barrier of 1.7 eV (164 kJ/mole). Excited states may be important for the total loss both through direct emission of excited K atoms, and since excited states may give rise to cluster formation at the surface and more rapid loss as clusters K_n.     

Validity of the Acti4 software using ActiGraph GT3X+accelerometer for recording of arm and upper body inclination in simulated work tasks

The validity of inclinometer measurements by ActiGraph GT3X+ (AG) accelerometer, when analysed with the Acti4 customised software, was examined by comparison of inclinometer measurements with a reference system (TrakStar) in a protocol with standardised arm movements and simulated working tasks. The sensors were placed at the upper arm (distal to the deltoid insertion) and at the spine (level of T1-T2) on eight participants. Root mean square errors (RMSEs) values of inclination between the two systems were low for the slow- and medium-speed standardised arm movements and in simulated working tasks. Fast arm movements caused the inclination estimated by the AG to deviate from the reference measurements (RMSE values up to ～10°). Furthermore, it was found that AG positioned at the upper arm provided inclination data without bias compared to the reference system. These findings indicate that the AG provides valid estimates of arm and upper body inclination in working participants.     

Ice-mould freeze casting of porous ceramic components

Porous, hollow ceramic components were produced by freeze casting technique. For this purpose aqueous slurries with high solid contents were prepared which were stable against freezing down to at least −5 °C. Ice cores were made by coating steel components with freezing water which were subsequently dip-coated with the ceramic suspensions. After freeze drying which removes both, the ice core and the frozen suspension liquid, and sintering, ceramic components with a high amount of open porosity including steel parts could be achieved. As an example hydroxyapatite was used for showing the opportunities of the freeze casting technology among others for applications in the field of bone replacement. The influence of the solid content of the hydroxyapatite slurries on the ice crystal growth has been investigated by means of compact hydroxyapatite bodies which were prepared by freeze casting using ice moulds with cylindrical cavities.     

Membrane properties of microporous structures prepared from polyethylene/polymethacrylate IPN

Polyethylene/polymethacrylate interpenetrating polymer networks (PE/PMA IPN) form a matrix–particle or a co‐continuous morphology that can be adjusted by the composition and synthesis conditions. Based on the fact that PMA degrades whereas PE crosslinks when they are exposed to energetic irradiation, we developed a new approach to create a porous structure by electron beam irradiation. IPN systems that differ in the methacrylate components and composition were studied. One system contains poly(butyl methacrylate‐co‐methyl methacrylate) (BMA‐co‐MMA) and the other contains poly(dodecyl methacrylate‐co‐ethyl methacrylate) (DMA‐co‐EMA) as the PMA phase. After electron beam irradiation followed by extraction with xylene, both IPN systems have a porous structure that is permeable to water. However, the structure and size of the pores depend on the PMA components and the synthesis conditions. PMAs with long aliphatic side chains degrade less than PMAs containing only short aliphatic pendant groups. Therefore, the PE/BMA‐co‐MMA IPN forms bigger pores than PE/DMA‐co‐EMA, resulting in a higher water flux. The molecular cutoffs of the IPN are characteristic for microfiltration or ultrafiltration.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1976–1982, 2003     

Bounds on the sample complexity for private learning and private data release

Learning is a task that generalizes many of the analyses that are applied to collections of data, in particular, to collections of sensitive individual information. Hence, it is natural to ask what can be learned while preserving individual privacy. Kasiviswanathan et al. (in SIAM J. Comput., 40(3):793–826, 2011) initiated such a discussion. They formalized the notion of private learning, as a combination of PAC learning and differential privacy, and investigated what concept classes can be learned privately. Somewhat surprisingly, they showed that for finite, discrete domains (ignoring time complexity), every PAC learning task could be performed privately with polynomially many labeled examples; in many natural cases this could even be done in polynomial time. While these results seem to equate non-private and private learning, there is still a significant gap: the sample complexity of (non-private) PAC learning is crisply characterized in terms of the VC-dimension of the concept class, whereas this relationship is lost in the constructions of private learners, which exhibit, generally, a higher sample complexity. Looking into this gap, we examine several private learning tasks and give tight bounds on their sample complexity. In particular, we show strong separations between sample complexities of proper and improper private learners (such separation does not exist for non-private learners), and between sample complexities of efficient and inefficient proper private learners. Our results show that VC-dimension is not the right measure for characterizing the sample complexity of proper private learning. We also examine the task of private data release (as initiated by Blum et al. in STOC, pp. 609–618, 2008), and give new lower bounds on the sample complexity. Our results show that the logarithmic dependence on size of the instance space is essential for private data release.