Back-to-Basics tutorial: X-ray diffraction of thin films

Electrocaloric (EC) refrigeration, is accepted as an auspicious method to develop eco-friendly cooling devices. Here, the investigations on the EC response and energy storage performance of heterovalent-doped Ba(Sn, Ti)O₃ relaxor ferroelectrics are carried out. Doping of aliovalent Mn or Nb elements into Ti site would regulate both the EC and energy storage behaviors. An enhanced EC temperature change up to 1.31 K, and a maximal recoverable energy storage density of 0.24 J cm^??3 with the efficiency as high as 87.11?%, can be observed under 70 kV cm^??1 in 0.5?% acceptor-doped Ba(Sn, Ti)O₃ ceramics. It is found that the local internal stress, the local charge fluctuation, and the oxygen deficiencies would benefit the electrical behaviors of this system. These results would shed light on the effect of the heterovalent substitution on the electrical properties of lead-free BaTiO₃ system and provide a novel and simple route to further improve the EC response and energy storage performance.

     

Surface Pretreatments of Silicon Nitride for CVD Diamond Deposition

The efficiency of different surface pretreatments (four standard chemical etchings and four diamond powder abrasive procedures) on silicon nitride (Si₃N₄) substrates for chemical vapor deposition (CVD) of diamond has been systematically investigated. Blank Si₃N₄ samples were polished with colloidal silica (∼0.25 μm). Diamond nucleation and growth runs were conducted in a microwave plasma chemical vapor deposition apparatus for 10 min and 6 h, respectively. Superior results concerning nucleation density ( N _d∼ 10¹⁰ cm⁻² after 10 min), film uniformity, and grain size (below 2 μm after 6 h) were obtained for the mechanically microflawed samples, revealing that chemical etchings (hot and cold strong acids, molten base or CF₄ plasma) are not crucial for good CVD diamond quality on Si₃N₄.     

Nile blue adsorbed onto silica gel modified with niobium oxide for electrocatalytic oxidation of NADH

A study of modified carbon paste electrode employing Nile blue (NB) adsorbed on silica gel modified with niobium oxide (SN) for electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH) is described. The adsorbed organic dye on SN was used to prepare a modified carbon paste electrode to investigate its electrochemical properties. The formal potential (E°′) of the adsorbed NB (−230 mV vs. saturated calomel electrode, SCE) showed a shift of 70 mV towards a more positive potential value, compared to NB dissolved in aqueous solution. In solutions with pH between 6.0 and 8.0 did stability and E°′ remained almost constant. However, for a solution pH lower than 6.0 the E°′ was affected by the acidity of the contacting solution, shifting the E°′ towards more positive values. For the solution pHs between 6.0 and 8.0 the electrocatalytic activity remained almost constant. A linear response range for NADH between 1.0×10⁻⁵ and 5.2×10⁻⁴ mol l⁻¹, at pH 7.0, was observed for the electrode, with an applied potential of −200 mV versus SCE. The formation of an intermediate charge transfer (CT) complex was proposed to the CT reaction between NADH and adsorbed NB. The heterogeneous electron transfer rate, k_obs, was 1400 M⁻¹ s⁻¹ and the apparent Michaelis-Menten constant, was 0.21 mM at pH 7.0 evaluated from rotating disk electrode (RDE) experiments with an electrode coverage of about 5.2×10⁻⁹ mol cm⁻². The increase in the reaction rate between NADH and the immobilized NB compared to those obtained with dissolved NB was assigned to the shift of the E°′ towards more positive values.     

Superabsorbent hydrogel based on modified polysaccharide for removal of Pb2+ and Cu2+ from water with excellent performance

This contribution describes the absorption percentage of Pb²⁺ and Cu²⁺ from water by a superabsorbent hydrogel matrix (SH) made from an anionic polysaccharide copolymerized with acrylic acid (AAc) and acrylamide (AAm). Metal‐absorption tests, upon sequential pH variation, indicated that the SH has pH‐sensitivity for the absorption of both metals from solution, attributed to the functional ionic groups (? COOH) present in the AAc and arabic gum (AG) segments. At the pH 5.0, the SH exhibited good absorption capacity: 73.10% for Pb²⁺, 81.99% for Cu²⁺ in water and 63.64% for Pb²⁺, and 76.67% for Cu²⁺ in saline water with 0.1 mol kg^?1 ionic strength. A replicated 2² full factorial design with a central point was built to evaluate the maximum absorption capacity of the metals into the SH. It was found that both the interaction and main effects of the pH and the initial concentration of metal solution on absorption percentage of the metals were statistically significant. Surface response plots indicated that the absorption capacity of both metals into the SH may be appreciably improved by using the solutions with lower initial concentration of metal and with higher pH values. Metal‐absorption results demonstrated that the SH is a convenient material for absorption of Pb²⁺ and Cu²⁺ from pure aqueous and saline aqueous environments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ethylene-propylene copolymers by a supported Ziegler-Natta catalyst based on TiCl4/MgCl2

Ethylene-propylene copolymers have been prepared by using Ziegler-Natta catalysts based on TiCl₄, MgCl₂, PCl₃ and (n-Bu)₃PO₄. The catalysts TiCl₄/MgCl₂/PCl₃ and TiCl₄/MgCl₂/(n-Bu)₃PO₄ were prepared by reacting TiCl₄ with pretreated MgCl₂. The support was prepared by ball milling of MgCl₂ with varied amounts of PCl₃ or (n-Bu)₃PO₄. The addition of PCl₃ has remarkably increased the MgCl₂ surface area in comparison with (n-Bu)₃PO₄. The effects of PCl₃ and (n-Bu)₃PO₄ on ethylene homopolymerization, ethylene-propylene copolymerization and on copolymer properties were evaluated. The catalyst system containing PCl₃ permitted to synthesize propylene-ethylene copolymers with up to 75% (w/w) of propylene and provided control of copolymer crystallinity. The reduction of the copolymer molecular weight distribution suggested that PCl₃ acted as an internal donor, poisoning some active catalytic sites. Received: 2 April 1997/Revised: 6 June 1997/Accepted: 18 June 1997     

Gaussian,Lobatto and Radau positive quadrature rules with a prescribed abscissa

For a given $\theta \in (a,b)$ , we investigate the question whether there exists a positive quadrature formula with maximal degree of precision which has the prescribed abscissa $\theta $ plus possibly $a$ and/or $b$ , the endpoints of the interval of integration. This study relies on recent results on the location of roots of quasi-orthogonal polynomials. The above positive quadrature formulae are useful in studying problems in one-sided polynomial $L_1$ approximation.     

(CO2 + 2‐propanol) mixture as a foaming agent for polystyrene: A simple thermodynamic model for the high pressure VLE‐phase diagrams taking into account the foam vitrification

The equation of state model developed by Lacombe and Sanchez (J Phys Chem 1976, 80, 2352) is used in the form proposed later by Sanchez and Stone (Polymer Blends, Vol. 1: Formulation, 2000; Chapter 2) to correlate experimental vapor‐liquid equilibrium (VLE) data for the three binaries and the ternary systems. Experimental data from the binary systems carbon dioxide‐isopropyl alcohol (CO₂‐IPrOH), isopropyl alcohol‐polystyrene (IPrOH‐PS), and carbon dioxide‐polystyrene (CO₂‐PS) are used to calculate VLE properties for the ternary system CO₂‐IPrOH‐PS. Two‐dimensional VLE‐phase diagrams were calculated and used to describe from a thermodynamic point of view the pressure, volume, and temperature values that characterize a thermoplastic foam evolution process, from the extruder to the foaming die. For different initial mixture CO₂ + IPrOH concentrations, pressure reduction produces liquid foaming until the vitrification curve arrests the final foam volume expansion. The dependence of the vitreous transition with the system CO₂ + IPrOH concentration while foaming is represented by the Chow (Macromolecules 1980, 13, 362) equation. The calculation procedure is proposed as a design tool to reduce the amount of experimental data usually needed as a requirement previous to the design stage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2663–2671, 2007     

Blends of polyamide 6 with bisphenol-A polycarbonate. I. Thermal properties and compatibility aspects

Blends of polyamide 6 (PA6) and polycarbonate (PC) have been investigated, over a full range of composition, to check interactions between them. SEM observations show that the mixtures are characterized by domains of clearly segregated homophases and voids between the two polymers. DSC and DMTA data indicate the presence of two T_g' s, corresponding to two separate phases, with the T_g of the PC phase decreasing on increasing the PA6 amount. Moreover, the crystallization kinetics of PA6 is slightly showed down by the PC. Chemical reactions between the two polymers are supposed to give rise to low molar mass compounds, as shown by GPC; these species plasticize the PC and partially dissolve into the molten polyamide, causing decrease of PC T_g and reduction of overall crystallization rate of PA6. Apparent influence of PC on melting temperature and enthalpy of PA6 is also discussed.     

Effects of physical refining on contents of waxes and fatty alcohols of refined olive oil

Changes in the contents of waxes and fatty alcohols during deodorization/physical refining of bleached olive oil were studied. Experiments were carried out with 1.85% acidity oil, which was physically refined in a discontinuous deodorizer of 250-kg maximum capacity using nitrogen as stripping gas instead of steam. The variables studied were load and temperature of oil in the deodorizer as well as N₂ flow. Analyses of waxes and alcohols were carried out at different operation times. The maximum content of wax was always observed when the oil reached the deodorization temperature. The variation in the wax content depended on temperature and N₂ flow. Wax decomposition started and continued during the operating time, and a progressive decrease, which was pronounced between 3 and 4 h, was observed. Small changes in waxes were observed between 4 and 5 h. Total content of fatty alcohols diminished throughout the operating time, and changes did not depend on the variables studied.